Golf balls incorporating thermoplastic blend

A golf ball incorporating a durable thermoplastic polyurethane composition and a method for producing the same.

Professional golfers and amateur golfers today use multi-piece solid golf balls. Basically, a two-piece solid golf ball contains a solid inner core protected by an outer cover. The inner core is made of natural or synthetic rubber such as polybutadiene, styrene butadiene, polyisoprene. The cover surrounds the inner core and can be made of a variety of materials including ethylenic acid copolymer ionomers, polyamides, polyesters, polyurethanes, and polyureas.

Three-piece, four-piece, and even five-piece balls have become more common over the years. More golfers are competing with these multi-piece balls for several reasons, including new manufacturing techniques, lower material costs, and desirable ball play characteristics. Many golf balls used today have a multi-layer core that includes an inner core and at least one peripheral outer core layer. For example, the inner core may be made of a relatively soft and elastic material, and the outer core may be made of a harder and more rigid material. The "dual core" subassembly is encapsulated by a single or multi-layered cover to provide the final ball assembly. Different materials are used in these golf ball configurations to impart specific characteristics and play characteristics to the ball.

For example, in recent years there has been a great deal of interest in producing golf ball covers using polyurethane compositions. Basically, the polyurethane composition contains a urethane bond formed by reacting an isocyanate group (-N = C = O) with a hydroxyl group (OH). Polyurethanes are produced by the reaction of polyfunctional isocyanates with polyols in the presence of catalysts and other additives. The chain length of the polyurethane prepolymer is extended by reacting with hydroxyl ends and amine curing agents.

US Pat. No. 5,971,870 of Sullivan et al. Describes that thermoplastic or thermosetting polyurethanes and ionomers are suitable materials for making outer covers and any inner cover layers. The cover layer can be formed on the core by injection molding, compression molding, casting or other conventional molding techniques. Preferably, each cover layer is formed separately. In one embodiment, the inner cover layer is first injection molded onto the core in the cavity mold, then any intermediate cover layer is injection molded onto the inner cover layer in the cavity mold, and finally the outer cover layer is dimples. Injection molded onto the intermediate cover layer in the cavity mold.

US Pat. No. 7,131,915 of Sullivan et al. Describes that the outer cover can be made from a polyurethane composition and that various aliphatic and aromatic diisocyanates are suitable for making polyurethane. Depending on the type of curing agent used, the polyurethane composition may be thermoplastic or thermosetting in nature. Sullivan's '915 patent further discloses that the compositions for the intermediate and inner cover layers may be selected from the same types of materials used for the outer cover layer. In other embodiments, ionomers such as HNP can be used to form the intermediate layer and inner cover layer. The castable reactive liquid used to form the urethane elastomer material can be applied onto the core using a variety of techniques such as spraying, dipping, spin coating or flow coating.

As discussed earlier, both thermoplastic and thermosetting polyurethanes can be used to form golf ball covers. Thermoplastic polyurethanes have minimal crosslinks and any bonds in the polymer network are primarily due to hydrogen bonds or other physical mechanisms. Due to the low level of cross-linking, thermoplastic polyurethane is relatively flexible. The crosslinked bonds in the thermoplastic polyurethane can be reversibly broken by increasing the temperature, such as during molding or extrusion. That is, the thermoplastic material softens when exposed to heat and returns to its original state when cooled. On the other hand, thermosetting polyurethane cures irreversibly when cured. Crosslinks are set irreversibly and are not destroyed when exposed to heat. Therefore, thermosetting polyurethanes that typically have high levels of crosslinks are relatively rigid.

One advantage of using thermoplastic polyurethane, urea, and / or hybrid (TPU) compositions to form golf ball covers is that they have good processability. The resulting thermoplastic material generally has good melt flow properties and various molding methods may be used to form the cover. Therefore, thermoplastic polyurethanes, ureas and / or hybrids have been used for many years, especially in golf ball covers.

Unfortunately, there are drawbacks associated with using the material, such as being less durable and less tough than other polymers. For this reason, the resulting thermoplastic polyurethane golf ball cover may not have high mechanical strength, impact resistance, and cutting and scratch (groove shear) resistance.

Therefore, manufacturers have used various methods of treating thermoplastic polyurethanes to increase the durability and strength of the polymer. For example, isocyanates can be added to the masterbatch and then the masterbatch can be added to the thermoplastic polyurethane composition prior to molding. In another example, the molded thermoplastic polyurethane cover can be immersed in an isocyanate solution. Treating thermoplastic polyurethane materials with isocyanates helps to improve mechanical strength, impact durability, and physical properties such as material cutting and scratch (groove shear) resistance. In some cases, not only is the physical property increased, but it may actually increase beyond the value of the unrefined material.

For example, Kennedy, III, US Pat. No. 8,920,264 and Matroni, US Pat. No. 9,119,990 disclose an isocyanate immersion method in which a golf ball with a thermoplastic polyurethane cover is treated with a solution of isocyanate. The isocyanate solution can contain a solvent such as acetone or methyl ethyl ketone (MEK), at least one isocyanate compound, and a catalyst. The balls are immersed in an isocyanate solution, which allows the isocyanate compound to penetrate the cover. Since the isocyanate compound crosslinks the thermoplastic polyurethane cover material, the physical characteristics of the cover such as durability and scratch resistance are improved.

Manufacturers have also attempted to coat a treated and / or coated layer around the TPU cover layer to improve golf ball properties. In one approach, the difference in the relative proportions of different isocyanate functional groups in each of the TPU cover layer and the coating layer allowed the coating layer to react with the TPU cover layer.

However, such an approach requires additional processing steps that can be time consuming, thus reducing efficiency and increasing manufacturing costs. The relevant and permitted US application serial numbers 15 / 813,463 ("'463 application") and US application serial number 15 / 813,486 ("'486 application") address these issues and at least one layer (i). A novel solution consisting of a thermoplastic polymer (thermoplastic polyurethane, urea and / or polyurethane-urea hybrid) (TPU) and (ii) a polymethylmethacrylate-based copolymer or a mixture having multiple core-shell polymers. Where the core and / or shell comprises a polymethylmethacrylate-based copolymer. The resulting material, as well as the golf ball, is reliable, has excellent physical and play performance characteristics, but is easier and more cost effective without the need for additional treatment or coating layers. Can be manufactured.

Subsequently, the relevant US application serial numbers 16 / 186,806 ("'806 application") and US application serial number 16 / 186,856 ("'856 application") introduced thermoplastic blends. These thermoplastic blends incorporate some of the teachings and advantages of the materials of parent applications "463" and "486", ionomer, TPU, and polymethyl (meth) acrylate-based copolymers, and / or simply these. A novel golf ball and layer having the desired physical and play performance properties of multiple core-shell polymers with a core and / or shell having in one layer was produced. This is done without encountering problems associated with the manufacture and use of traditional TPUs. Such golf balls and layers are reliably durable and can be easily and cost-effectively manufactured within the existing golf ball manufacturing process. Prior to creating TPU / ionomer blends such as U.S. Patent No. 7,700,689 (Egashira et al.) And / or U.S. Patent Application Publication No. 2011/0224023 (Tutmark) and / or U.S. Patent Application Publication No. 2018/0147452 (Song et al.) Attempts have neither addressed nor resolved these issues.

However, he developed different ionomer / TPU blends based on some of the teachings of the materials in the parent applications "46" 3 and "486" and encountered problems previously associated with the manufacture and use of traditional TPUs. There is still a need to combine multiple unique desired chemical, physical, and play performance characteristics in a single layer without doing so.

Such novel golf balls and ionomer / TPU blends are particularly useful if they can be cost-effectively manufactured within the existing manufacturing process. The golf ball of the present invention and the method for manufacturing the golf ball meet and solve such a demand.

<p><patcit num="1"><text>US Pat. No. 5,971,870</text></patcit><patcit num="2"><text>US Pat. No. 7,131,915</text></patcit><patcit num="3"><text>US Pat. No. 8,920,264</text></patcit><patcit num="4"><text>US Pat. No. 9,119,990</text></patcit><patcit num="5"><text>US Pat. No. 7,700,689</text></patcit><patcit num="6"><text>US Application Publication No. 2011/0224023 Specification</text></patcit><patcit num="7"><text>US Application Publication Number 2018/0147452 Specification</text></patcit></p>

Advantageously, in one embodiment, the golf ball of the present invention comprises a core and (i) at least one ionomer; (ii) at least one thermoplastic polyurethane; and (iii) at least one core shell. Having at least one layer with a thermoplastic blend of the polymer, the core and shell of this core-shell polymer has a polymethyl (meth) acrylate-based copolymer; and the ionomer is about 45 weight by weight of the total weight of the blend. It is present in an amount greater than or equal to%, and the core-shell polymer is present in an amount of 2% to 35% by weight of the total weight of the blend. In different such embodiments, the component (iii) of the blend is at least one polymethyl (meth) acrylate-based copolymer. The thermoplastic polyurethane may be present in the blend in an amount of about 8% to about 50% by weight. In other embodiments, the thermoplastic polyurethane may be present in an amount of about 25% by weight to about 45% by weight. In yet another embodiment, the thermoplastic polyurethane may be present in an amount of about 35% to about 50% by weight.

In certain embodiments, ionomers are present in the blend in greater amounts than the amount of thermoplastic polyurethane. In one embodiment, ionomers are present in an amount of about 45% to about 70% by weight.

In certain embodiments, the thermoplastic polyurethane is present in an amount of about 10% to about 40% by weight and the core-shell polymer is present in an amount of about 5% to about 20% by weight.

In some examples, at least one polymethyl (meth) acrylate-based copolymer is present in an amount of about 15% to about 35% by weight.

The golf ball of the present invention can include at least one layer containing a three-component thermoplastic blend consisting of: (i) at least one ionomer; (ii) at least one different thermoplastic polymer consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof; (iii) multiple core-shell polymers It has at least one layer having a three-component thermoplastic blend consisting of, where at least one of the cores and shells of each core-shell polymer has one or more polymethyl (meth) acrylate-based copolymers. The three-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is% by weight of the core-shell polymer, and I is&gt; 45, 2 C &lt;35.

Each core-shell polymer may have a diameter of about 0.05 micron to about 20.0 micron. In certain embodiments, the diameter of each core-shell polymer is from about 0.05 micron to about 0.20 micron.

In one embodiment, at least one of the plurality of core-shell polymers has a urethane-containing core. In another embodiment, at least one of the plurality of core-shell polymers has a non-urethane-containing core.

In different embodiments, the golf balls of the invention are (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. Different Thermoplastic Polymers; (iii) Have at least one layer with a three-component thermoplastic blend consisting of at least one polymethyl (meth) acrylate-based copolymer. The three-component thermoplastic blend comprises (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight% of the polymethyl (meth) acrylate-based copolymer, where I is&gt; 45 and 2 C &lt;35.

In a particular formulation of this different embodiment, 15 C &lt;35. In a specific such embodiment, 8 T 50.

On the other hand, whenever the component (iii) of the three-component thermoplastic blend comprises either a plurality of core-shell polymers or at least one polymethyl (meth) acrylate-based copolymer, the following additional examples are possible.

In one embodiment, T is about 8 to 45. In another embodiment, T is greater than 45, up to about 50.

In one such embodiment, I&gt; T. In another such embodiment, T&gt; I. In yet another such embodiment, T = I.

In a particular embodiment, 45 &lt;I &lt;70. In another embodiment, I is 48-90 and T is 8-50.

In a particular embodiment, T is 10-40 and C is 3-30.

The polymethyl (meth) acrylate-based copolymer is: polymethyl (meth) acrylate-based n-butyl acrylate; polymethyl (meth) acrylate-based ethyl acrylate; polymethyl (meth) acrylate-based n-butyl acrylate styrene; polymethyl (meth). Acrylate-based butadiene styrene; Polymethyl (meth) acrylate-based acrylonitrile butadiene styrene; Polymethyl (meth) acrylate-based ethylene propylene diene (EPDM); Polymethyl (meth) acrylate-based EPDM-styrene; Polymethyl (meth) acrylate-based glycidyl Methacrylate-ethyl acrylate; polymethyl (meth) acrylate-based glycidyl; (meth) acrylate-n-butyl acrylate; polymethyl (meth) acrylate-based styrene-acrylonitrile; polymethyl (meth) acrylate-based butadiene; and combinations thereof. It may be selected from the group.

The polymethyl (meth) acrylate-based copolymer is: (meth) acrylate derived from saturated alcohol; (meth) acrylate derived from unsaturated alcohol; aryl (meth) acrylate; cycloalkyl (meth) acrylate; hydroxyalkyl ( Meta) Acrylate; Glycoldi (methacrylate); Ether alcohol (meth) acrylate; (Meta) acrylic acid amide; (Meta) acrylic acid nitrile; Sulfur-containing (meth) acrylate; and polyfunctional (meth) acrylate; And may have a (meth) acrylate selected from the group consisting of combinations thereof.

The polymethyl (meth) acrylate-based copolymer is methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, isohexyl acrylate, n-heptyl acrylate, isoheptyl acrylate. , Capryl acrylate, (1-methylheptyl acrylate), n-octyl acrylate, ethylhexyl acrylate, isooctyl acrylate, methylheptyl acrylate, n-nonyl acrylate, isononyl acrylate, 3,5,5-trimethylhexyl acrylate, n-decyl An acrylate selected from the group consisting of acrylates, lauryl acrylates, n-amyl acrylates, n-hexyl acrylates, capryl acrylates (1-methylheptyl acrylates), n-octyl acrylates, isooctyl acrylates, such as n-methylheptyl acrylates, 2 -May have ethylhexyl acrylate, capryl acrylate.

Polymethyl (meth) acrylate-based copolymers may contain comonomer selected from the group consisting of 1-alkene; branched alkene; acrylonitrile; styrene; maleic acid derivative; diene; and combinations thereof.

Polymethyl (meth) acrylate-based copolymers include alternating polymethyl (meth) acrylate-based copolymers, block polymethyl (meth) acrylate-based copolymers, random polymethyl (meth) acrylate-based copolymers, and graft polymethyl (meth) acrylate-based copolymers. Copolymers, gradient polymethyl (meth) acrylate-based copolymers, and combinations thereof may be selected from the group.

In one example, the three-component thermoplastic polymer has a material hardness from about 20 shore D to about 65 shore D.

The three-component thermoplastic blend may have a material hardness different from the material hardness of the thermoplastic polymer.

In one example, the three-component thermoplastic blend has a material hardness greater than about 20 shore D and up to about 70 shore D.

In one embodiment, the at least one layer described above is a cover layer surrounding the subassembly, having a hardness H different from the hardness H (ii) of (ii) by at least about 5 shore D hardness points, where (ii) is. It has a hardness of about 20 shore D to about 70 shore D.

In another embodiment, at least one layer surrounds the subassembly and is surrounded by an outer cover layer, with an inner cover layer having a hardness H that differs from hardness H (ii) in (ii) by at least about 5 shore D hardness points. Where (ii) has a hardness of about 20 shore D to about 70 shore D.

In some embodiments, the golf ball of the present invention comprises (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. One different thermoplastic polymer; and (iii) having at least one layer consisting of a three-component thermoplastic blend consisting of multiple core-shell polymers, wherein at least one of the cores and shells of each core-shell polymer is one or more. Has a polymethyl (meth) acrylate-based copolymer. Also, in other embodiments, the golf balls of the invention consist of (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. It has at least one layer consisting of a three-component thermoplastic blend consisting of at least one different thermoplastic polymer; and (iii) at least one polymethyl (meth) acrylate-based copolymer.

Advantageously, the golf balls of the present invention have a core and (i) at least one ionomer; (ii) at least one thermoplastic polyurethane; (iii) maleic acid group modified polymer, glycidyl (meth) acrylate modified polymer, Or at least one reactive crosslinker consisting of a combination thereof (PGM); (iv) may have at least one layer having a thermoplastic blend consisting of at least one catalyst, where the ionomer is about. It is present in an amount of 45% by weight or more, and PGM is present in an amount of about 2% by weight to about 35% by weight. The thermoplastic polyurethane may be present in the blend in an amount of about 8% to about 50% by weight. In another embodiment, the thermoplastic polyurethane may be present in an amount of about 25% by weight to about 45% by weight. In yet another embodiment, the thermoplastic polyurethane may be present in an amount of about 35% to about 50% by weight.

In certain embodiments, ionomers are present in the blend in greater amounts than the amount of thermoplastic polyurethane. In one embodiment, ionomers are present in an amount of about 45% to about 70% by weight.

In one embodiment, the thermoplastic polyurethane may be present in an amount of more than 20% by weight up to about 40% by weight, and the PGM is present in an amount of about 5% to about 30% by weight. In some examples, PGM is present in an amount of about 15% to about 35% by weight.

At least one catalyst is 1,8-diazabicyclo- [5.4.0] undeca-7-ene (DBU), triphenylphosphine imidazole catalyst, chromium III complex, oxo-central trinuclear CrIII complex, 1,4-diazabicyclo [ 2.2.2] You may choose from the group consisting of octane, liquid epoxy catalysts, and combinations thereof.

At least one catalyst may be a tertiary amine.

At least one catalyst may be included in the four-component thermoplastic blend in an amount of 0.1-10 parts based on 100 parts PGM. At least one catalyst may be included in the four-component thermoplastic blend in an amount of 1.0 to 5.0 parts based on 100 parts of PGM.

The golf balls of the present invention are (i) at least one ionomer; (ii) at least one different thermoplastic polymer consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof; (iii) At least one reactive crosslinker consisting of a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM); and (iv) a four-component thermoplastic consisting of at least one catalyst. It may include at least one layer having a blend. The four-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight% of PGM, where I&gt; 45 and 2 C &lt;35.

In one embodiment, T is 25-50. In another embodiment, T is about 25-50. In yet another embodiment, T is greater than 25 and up to 50. In yet another embodiment, T is 30-50. In one embodiment, T is 35-50. In an alternative embodiment, T is 40-50. T is greater than 40 and may be up to about 50.

In different embodiments, T is about 8-45.

In one embodiment, I&gt; T. In another embodiment, T&gt; I. In yet another such embodiment, T = I.

In a particular embodiment, I &lt;90. In another particular embodiment, 45 &lt;I &lt;70.

In different embodiments, I is 48-90.

In one such particular embodiment, T is greater than 20, up to about 40, and C is 3-30.

In one particular embodiment, 15 C &lt;35. In another particular embodiment, 20 C &lt;35.

In one example, at least one catalyst is 1,8-diazabicyclo [5.4.0] undeca-7-ene (DBU), triphenylphosphine imidazole catalyst, chromium III complex, oxo-central trinuclear CrIII complex, 1, It may be selected from the group consisting of 4-diazabicyclo [2.2.2] octane, liquid epoxy catalysts, and combinations thereof.

In certain embodiments, the at least one catalyst is a tertiary amine.

The catalyst may be included in the four-component thermoplastic blend in an amount of 0.1-10 parts based on 100 parts PGM. In a particular embodiment, at least one catalyst is included in the four-component thermoplastic blend in an amount of 1.0 to 5.0 parts based on 100 parts of PGM.

In one example, the four-component thermoplastic blend has a material hardness from about 20 shore D to about 65 shore D.

The four-component thermoplastic blend may have a material hardness different from the material hardness of the thermoplastic polymer.

In one example, the four-component thermoplastic blend is greater than about 20 shore D and has a material hardness of up to about 70 shore D.

In one embodiment, at least one layer is a cover layer that surrounds the subassembly and has a hardness H that differs from the hardness H (ii) of (ii) by at least about 5 shore D hardness points, where (ii). Has a hardness of about 20 shore D to about 70 shore D.

In another embodiment, the at least one layer surrounds the subassembly and is surrounded by an outer cover layer having a hardness H that differs from hardness H (ii) in (ii) by at least about 5 Shore D hardness points. It is a layer and (ii) has a hardness of about 20 shore D to about 70 shore D.

In some embodiments, the golf ball of the present invention comprises (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. One different thermoplastic polymer; (iii) at least one reactive crosslinker consisting of a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM); and (iv) at least one It has at least one layer consisting of a four-component thermoplastic blend consisting of a catalyst.

The present invention also relates to a method of making a golf ball of the present invention, wherein the method is: a step of providing a subassembly; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea,. At least one different thermoplastic polymer consisting of a thermoplastic urea-urethane hybrid, or a combination thereof; (iii) at least a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM). It has one reactive cross-linking agent; and (iv) a step of forming at least one layer of a four-component thermoplastic blend consisting of at least one catalyst around the subassembly. The four-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight% of PGM, where I&gt; 45 and 2 C &lt;35.

In another embodiment, the method of making a golf ball of the present invention is: a step of providing a subassembly; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-. At least one different thermoplastic polymer consisting of a urethane hybrid, or a combination thereof; (iii) at least one reactivity consisting of a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM). It has a cross-linking agent; and (iv) a step of forming at least one layer of a four-component thermoplastic blend consisting of at least one catalyst around the subassembly.

In other embodiments, the method is: (i) at least one ionomer; (ii) at least one different thermal consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. Thermoplastic Polymer; (iii) At least one reactive crosslinker consisting of a maleic acid group modified polymer, glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM); and (iv) at least one catalyst. It has a step of providing a subassembly consisting of a component thermoplastic blend; and a step of forming at least one layer having a thermoplastic or thermoplastic composition around the subassembly.

Alternatively, the method is: (i) at least one ionomer; (ii) at least one different thermoplastic consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. Polymers; (iii) at least one reactive crosslinker consisting of a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM); and (iv) a four component consisting of at least one catalyst. It may have a step of providing a subassembly having a thermoplastic blend; and a step of forming at least one layer having a thermoplastic or thermoplastic composition around the subassembly.

The golf balls of the present invention include a core and (i) at least one ionomer; (ii) at least one thermoplastic polyurethane; and (iii) at least one acrylonitrile styrene acrylate, acrylonitrile butadiene styrene, or a combination thereof (ASA). And / or ABS ") may have at least one layer with a thermoplastic blend, where ionomers are present in an amount of about 45% by weight or more, ASA and / or ABS from about 2% by weight. It is present in an amount of about 35% by weight.

The thermoplastic polyurethane may be present in the blend in an amount of about 8% to about 50% by weight. In another embodiment, the thermoplastic polyurethane may be present in an amount of about 25% by weight to about 45% by weight. In yet another embodiment, the thermoplastic polyurethane may be present in an amount of about 35% to about 50% by weight.

In certain embodiments, ionomers are present in the blend in greater amounts than the amount of thermoplastic polyurethane. In one embodiment, ionomers are present in an amount of about 45% to about 70% by weight.

In one embodiment, the thermoplastic polyurethane may be present in an amount greater than 20% by weight and up to about 40% by weight. And ASA and / or ABS are present in an amount of about 5% to about 30% by weight. In some examples, ASA and / or ABS are present in an amount of about 15% to about 35% by weight.

The golf balls of the present invention are (i) at least one ionomer; (ii) at least one different thermoplastic polymer consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof; And (iii) may have at least one layer having a three-component thermoplastic blend consisting of at least one acrylonitrile styrene acrylate, acrylonitrile butadiene styrene, or a combination thereof (ASA and / or ABS). The three-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight% of ASA and / or ABS, I&gt; 45, and 2 C &lt;35.

In one embodiment, T is 25-50. In another embodiment, T is about 25-50. In yet another embodiment, T is greater than 25 and up to 50. In yet another embodiment, T is 30-50. In one embodiment, T is 35-60. In an alternative embodiment, T is 45-60. T may be greater than 45 and up to about 60.

In different embodiments, T is about 8-45.

In one embodiment, I&gt; T. In another embodiment, T&gt; I. In yet another such embodiment, T = I.

In a particular embodiment, 45 &lt;I &lt;70.

In different embodiments, I is 48-90.

In one such particular embodiment, T is greater than 20, up to about 40, and C is 3-30.

In one particular embodiment, 15 C &lt;35. In another particular embodiment, 20 C &lt;35.

The ASA may be composed of at least 60% acrylate and / or the ABS may be composed of at least 60% butadiene.

In one example, the three-component thermoplastic blend has a material hardness from about 20 shore D to about 65 shore D.

The three-component thermoplastic blend may have a material hardness different from the material hardness of the thermoplastic polymer.

In one example, the three-component thermoplastic blend has a material hardness greater than about 20 shore D and up to about 70 shore D.

In one embodiment, at least one layer is a cover layer that surrounds the subassembly and has a hardness H that differs from the hardness H (ii) of (ii) by at least about 5 Shore D hardness points, where (ii). Has a hardness of about 20 shore D to about 70 shore D.

In another embodiment, the at least one layer surrounds the subassembly and is surrounded by an outer cover layer, with an inner cover having a hardness H different from hardness H (ii) in (ii) by at least about 5 Shore D hardness points. It is a layer, where (ii) has a hardness of about 20 shore D to about 70 shore D.

In some embodiments, the golf ball of the present invention comprises (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. It has at least one layer consisting of a three-component thermoplastic blend consisting of one different thermoplastic polymer; and (iii) ASA and / or ABS.

The present invention also relates to a method of making a golf ball of the present invention, wherein the method is: a step of providing a subassembly; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea,. At least one different thermoplastic polymer consisting of a thermoplastic urea-urethane hybrid, or a combination thereof; and (iii) at least one layer consisting of a three-component thermoplastic blend consisting of ASA and / or ABS around the subassembly. Has a step to form on. The three-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight% of ASA and / or ABS, I&gt; 45, and 2 C &lt;35.

In another embodiment, the method of making a golf ball of the present invention is: a step of providing a subassembly; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-. Urethane hybrids, or at least one different thermoplastic polymer consisting of a combination thereof; and (iii) with the step of forming at least one layer around the subassembly with a three-component thermoplastic blend consisting of ASA and / or ABS. Have.

In other embodiments, the method is: (i) at least one ionomer; (ii) at least one different thermosetting consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. A plastic polymer; and (iii) a step of providing a subassembly consisting of a three-component thermoplastic blend consisting of ASA and / or ABS; at least one layer having a thermosetting or thermoplastic composition around the subassembly. It has a step to form.

Alternatively, the method is: (i) at least one ionomer; (ii) at least one different thermoplastic consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. Polymer; and (iii) a step of providing a subassembly having a three-component thermoplastic blend consisting of ASA and / or ABS; forming at least one layer containing a thermosetting or thermoplastic composition around the subassembly. And have steps to do.

Advantageously, the golf balls of the present invention are: with a core; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane; and (iii) at least one polyester elastomer, polyamide elastomer, or a combination thereof. It may have at least one layer with a thermoplastic blend of (PEPA), where ionomers are present in an amount of about 45% by weight or more, and PEPA is from about 2% to about 35% by weight. Exists in quantity. The thermoplastic polyurethane may be present in the blend in an amount of about 8% to about 50% by weight. In another embodiment, the thermoplastic polyurethane may be present in an amount of about 25% by weight to about 45% by weight. In yet another embodiment, the thermoplastic polyurethane may be present in an amount of about 35% to about 50% by weight.

In certain embodiments, ionomers are present in the blend in greater amounts than the amount of thermoplastic polyurethane. In one embodiment, ionomers are present in an amount of about 45% to about 70% by weight.

In one embodiment, the thermoplastic polyurethane may be present in an amount greater than 20% by weight and up to about 40% by weight. And PEPA is present in an amount of about 5% to about 30% by weight. In some examples, PEPA is present in an amount of about 15% to about 35% by weight.

The golf balls of the present invention are: (i) at least one ionomer; (ii) at least one different thermoplastic polymer consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. It may have at least one layer having a three-component thermoplastic blend consisting of "TPU"); and (iii) at least one polyester elastomer, polyamide elastomer, or a combination thereof ("PEPA"). The three-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight percent of PEPA, I&gt; 45, and 2 C &lt;35.

In one embodiment, T is 25-50. In another embodiment, T is about 25-50. In yet another embodiment, T is greater than 25 and up to 50. In yet another embodiment, T is 30-50. In one embodiment, T is 35-50. In an alternative embodiment, T is 40-50. T is greater than 40 and may be up to about 50.

In different embodiments, T is about 8-45.

In one embodiment, I&gt; T. In another embodiment, T&gt; I. In yet another such embodiment, T = I.

In a specific example, 45 &lt;I &lt;70.

In different embodiments, I is 48-90.

In one such particular embodiment, T is greater than 20, up to about 40, and C is 3-30.

In one specific embodiment, 15 C &lt;35. In another specific embodiment, 20 C &lt;35.

In one embodiment, PEPA is selected from the group consisting of polyether polyesters, polyether polyamides, or combinations thereof.

In one example, the three-component thermoplastic blend has a material hardness from about 20 shore D to about 65 shore D.

The three-component thermoplastic blend may have a material hardness different from the material hardness of the thermoplastic polymer.

In one example, the three-component thermoplastic blend has a material hardness greater than about 20 shore D and up to about 70 shore D.

In one embodiment, the at least one layer is a cover layer that surrounds the subassembly and has a hardness H that differs from the hardness H (ii) of (ii) by at least about 5 shore D hardness points, where (ii). ) Has a hardness of about 20 shore D to about 70 shore D.

In another embodiment, the at least one layer surrounds the subassembly and is surrounded by an outer cover layer, with an inner cover having a hardness H different from hardness H (ii) in (ii) by at least about 5 Shore D hardness points. It is a layer, where (ii) has a hardness of about 20 shore D to about 70 shore D.

In some embodiments, the golf ball of the present invention comprises (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. It has at least one layer consisting of a three-component thermoplastic blend consisting of one different thermoplastic polymer; and (iii).

The invention also relates to a method of making a golf ball of the invention, which method: with the steps of providing subassemblies; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea,. It has a step of forming at least one layer consisting of a thermoplastic urea-urethane hybrid, or a combination thereof; and (iii) a three-component thermoplastic blend consisting of PEPA around the subassembly. The three-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight percent of PEPA, I&gt; 45, and 2 C &lt;35.

In another embodiment, the method of making a golf ball of the present invention is: a step of providing a subassembly; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-. It has at least one different thermoplastic polymer consisting of a urethane hybrid, or a combination thereof; and (iii) a step of forming at least one layer having a three-component thermoplastic blend consisting of PEPA around the subassembly.

In other embodiments, the method is: (i) at least one ionomer; (ii) at least one different thermosetting consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. Plastic polymer; and (iii) a step of providing a subassembly consisting of a three-component thermoplastic blend consisting of PEPA; and a step of forming at least one layer having a thermosetting or thermoplastic composition around the subassembly. Has.

Alternatively, the method is: (i) at least one ionomer; (ii) at least one different thermoplastic consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. A step of providing a subassembly having a three-component thermoplastic blend consisting of a polymer; and (iii) PEPA; and a step of forming at least one layer containing a thermosetting or thermoplastic composition around the subassembly. Have.

Detailed description of the invention

Advantageously, the golf ball of the present invention has a novel ionomer, TPU, PGM reactive cross-linking agent (maleic acid group modified polymer, glycidyl (meth) acrylate modified polymer, or the like thereof, in at least one layer, for example, a cover. Combination), and incorporates a novel thermoplastic blend of at least one catalyst. The thermoplastic blends of the present invention are preferably durable, tough, have high mechanical strength, impact durability, and resistance to cutting and scratching (groove shear), and are four-component thermoplastic in a single layer. It achieves the unique properties of the modified ionomers and TPUs in the blend, while not sacrificing the good processability normally associated with the production of thermoplastic materials.

Advantageously, the golf balls of the present invention combine the advantages of ionomers and TPUs and their respective into a single layer without sacrificing processability (eg, having good meltflow properties) or durability and toughness. Include. This thermoplastic blend can be cost-effectively molded using a wide range of methods, yet provides high mechanical strength, impact durability, and cutting and scratch (groove shear) resistance.

The golf balls of the present invention include a core and (i) at least one ionomer; (ii) at least one thermoplastic polyurethane; (iii) a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof ( It may have at least one reactive crosslinker consisting of "PGM"); (iv) at least one layer having a thermoplastic blend consisting of at least one catalyst, wherein the ionomer is about 45% by weight or more. It is present in quantity and PGM is present in an amount of about 2% to about 35% by weight. The thermoplastic polyurethane may be present in the blend in an amount of about 8% to about 50% by weight. In another embodiment, the thermoplastic polyurethane may be present in an amount of about 25% by weight to about 45% by weight. In yet another embodiment, the thermoplastic polyurethane may be present in an amount of about 35% to about 50% by weight.

In certain embodiments, ionomers are present in the blend in greater amounts than the amount of thermoplastic polyurethane. In one embodiment, ionomers are present in an amount of about 45% to about 70% by weight.

In one embodiment, the thermoplastic polyurethane may be present in an amount of more than 20% by weight up to about 40% by weight, and the PGM is present in an amount of about 5% to about 30% by weight. In some examples, PGM is present in an amount of about 15% to about 35% by weight.

At least one catalyst is 1,8-diazabicyclo- [5.4.0] undeca-7-ene (DBU), triphenylphosphine imidazole catalyst, chromium III complex, oxo-central trinuclear CrIII complex, 1,4-diazabicyclo [ 2.2.2] You may choose from the group consisting of octane, liquid epoxy catalysts, and combinations thereof.

At least one catalyst may be a tertiary amine.

At least one catalyst may be included in the four-component thermoplastic blend in an amount of 0.1-10 parts based on 100 parts PGM. At least one catalyst may be included in the four-component thermoplastic blend in an amount of 1.0 to 5.0 parts based on 100 parts of PGM.

The golf balls of the present invention are (i) at least one ionomer; (ii) at least one different thermoplastic polymer consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof; (iii) At least one reactive crosslinker consisting of a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM); and (iv) a four-component thermoplastic consisting of at least one catalyst. It may include at least one layer having a blend. The four-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight% of PGM, where I&gt; 45 and 2 C &lt;35.

In one embodiment, T is greater than 20 and up to about 50. In another embodiment, T is 25-50. In yet another embodiment, T is about 25-50. In yet another embodiment, T is greater than about 25-50. In alternative embodiments, T is greater than 30 to about 50, or about 30 to about 50, or 30 to 60. In certain embodiments, T is 35-60, or about 35-60, or about 35-50, or greater than 35 and up to about 50, or about 40-50. In one embodiment, T is greater than 40, up to about 50. In other embodiments, T is 40-50.

There are different embodiments where 8 T 50, or T is about 8-40.

In one embodiment, I&gt; T. In another embodiment, T&gt; I. In another embodiment, T = I.

In a particular embodiment, I &lt;90. In another particular embodiment, 45 &lt;I &lt;70. In different embodiments, I is 48-90.

In one such particular embodiment, T is greater than 20, up to about 40, and C is 3-30.

In one particular embodiment, 15 C &lt;35. In another particular embodiment, 20 C &lt;35.

In one example, at least one catalyst is 1,8-diazabicyclo [5.4.0] undeca-7-ene (DBU), triphenylphosphine imidazole catalyst, chromium III complex, oxo-central trinuclear CrIII complex, 1, It may be selected from the group consisting of 4-diazabicyclo [2.2.2] octane, liquid epoxy catalysts, and combinations thereof.

A suitable 1,4-diazabicyclo [2.2.2] octane is Dabco 33-LV. Examples of liquid epoxy catalysts include Hycat 2000S, Hycat 3000S, and / or Hycat OA manufactured by Dimension Technology chemical Systems, Inc.

In certain embodiments, the at least one catalyst is a tertiary amine.

The catalyst may be included in the four-component thermoplastic blend in an amount of 0.1-10 parts based on 100 parts PGM. In certain embodiments, the at least one catalyst is included in the four-component thermoplastic blend in an amount of 1.0 to 5.0 parts based on 100 parts of PGM. In another embodiment, the at least one catalyst may be included in the four-component thermoplastic blend in an amount of 5.0 to 10.0 parts based on 100 parts of PGM.

In one example, the four-component thermoplastic blend has a material hardness from about 20 shore D to about 65 shore D.

The four-component thermoplastic blend may have a material hardness different from the material hardness of the thermoplastic polymer.

In one example, the four-component thermoplastic blend is greater than about 20 shore D and has a material hardness of up to about 70 shore D.

In one embodiment, at least one layer is a cover layer that surrounds the subassembly and has a hardness H that differs from the hardness H (ii) of (ii) by at least about 5 shore D hardness points, where (ii). Has a hardness of about 20 shore D to about 70 shore D.

In another embodiment, the at least one layer surrounds the subassembly and is surrounded by an outer cover layer having a hardness H that differs from hardness H (ii) in (ii) by at least about 5 Shore D hardness points. It is a layer and (ii) has a hardness of about 20 shore D to about 70 shore D.

In some embodiments, the golf ball of the present invention comprises (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. One different thermoplastic polymer; (iii) at least one reactive crosslinker consisting of a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM); and (iv) at least one It has at least one layer consisting of a four-component thermoplastic blend consisting of a catalyst.

In certain embodiments, 20 &lt;T &lt;50, or 20 T 50, or 20 &lt;T 50, or 20 &lt;T &lt;40, or 20 T 40, or 25 T &lt;50, or 25 &lt;. T 50, or 25 T &lt;40, or 30 T 50, or 30 T &lt;40, or 40 T 50, or 40 &lt;T &lt;50, or 15 T 50, or 15 T. &lt;30.

In different embodiments, T is about 8 to 45, or 8 T 50, or 8 T &lt;50, or 8 &lt;T 50, or 8 &lt;T &lt;50, or 8 T 40, or 8 . Is. T &lt;40, or 8 &lt;T 40, or 8 &lt;T &lt;40, or 8 T 30, 8 T &lt;30, or 8 &lt;T 30, or 8 &lt;T &lt;30, or 8 T. 20, or 8T &lt;20, or 8 &lt;T20, or 8 &lt;T &lt;20, or 8T15, or 8T &lt;15, or 8 &lt;T15, or 8 &lt;T &lt; It is 15.

In a particular formulation, 5 C &lt;35, or 10 C &lt;35, or 15 C &lt;35, or 15 C 35, or 15 C &lt;25, or 15 C 25, or 20 C. &lt;35, or 20 C 35, or 20 C &lt;25, or 15 C 20.

In a specific embodiment, 45 &lt;I &lt;70, or 45 &lt;I 70, or 45 &lt;I &lt;60, or 45 &lt;I 60, or 55 I &lt;70, or 55 I 70, or 45. &lt;I &lt;90, or 45 &lt;I 90, or 60 &lt;I &lt;90, or 60 &lt;I 90, or 70 &lt;I &lt;90, or 70 &lt;I 90.

Since I is always greater than 45 and 2 C &lt;35, T is always up to about 50. This means that many possible combinations of I, T and C can be coordinated with the target within the scope disclosed herein. In such particular examples, I&gt; 45, C &lt;35, and T&gt; 20. In another such specific embodiment, I&gt; 45, C &lt;30, and T&gt; 25. In yet another such embodiment, I&gt; 45, C &lt;20, and T&gt; 35. In yet another such embodiment, I&gt; 45, C &lt;15, and T&gt; 40. In another embodiment, I&gt; 45, C 2, and T 53.

In certain non-limiting examples, I is 90, T is 8, and C is 2. In another specific non-limiting example, I is 80, T is 15, and C is 5. Yet another specific rational example is 70 for I, 20 for T, and 10 for C. Yet another specific non-limiting example is 60 for I, 25 for T, and 15 for C. An alternative specific non-limiting example is 50 for I, 30 for T, and 30 for C. In different specific non-limiting examples, I is 50, T is 20, and C is 30. In another specific non-limiting example, I is 46, T is 50, and C is 4. In other specific non-limiting examples, I is 45, T is 45, and C is 10. Yet another specific non-limiting example is 47 for I, 43 for T, and 10 for C.

In some embodiments, the golf ball of the present invention comprises (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. One different thermoplastic polymer; (iii) at least one reactive crosslinker consisting of a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM); and (iv) at least one It has at least one layer consisting of a four-component thermoplastic blend consisting of a catalyst. Again, the four-component thermoplastic blend contains (i), (ii), and (iii) in a weight ratio of I: T: C, where I is the weight% of the ionomer and T is the different thermoplastic. % By weight of polymer, C is% by weight of PGM, I&gt; 45, and 2 C &lt;35.

As used herein, the term "thermoplastic polymer" refers to a thermoplastic composition comprising one or more thermoplastic polymers other than the ionomers defined herein. In one such embodiment, the thermoplastic polymer may include thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. The thermoplastic polyurethane itself may include a thermoplastic urethane / polyurethane blend. The thermoplastic urea itself may contain a blend of thermoplastic urea / polyurea. Further, the urea-urethane hybrid itself may include a plurality of different hybrids.

Thermoplastic polymers in a four-component thermoplastic blend are additional materials / components such as fillers, additives, catalysts, wetting agents, colorants, fluorescent whitening agents, cross-linking agents, whitening agents such as titanium dioxide and zinc oxide. , Ultraviolet (UV) light absorber, hindered amine light stabilizer, defoaming agent, processing aid, surfactant, and antioxidant, stabilizer, softener, plasticizer, impact modifier, foaming agent, density Additional materials / ingredients may be included, such as conditioning fillers, stiffeners, other conventional additives such as compatibilizers.

Due to the interaction of the ionomer, thermoplastic polymer, reactive cross-linking agent (PGM), and catalyst, superior mechanical strength, impact durability, and cutting / cut (groove shearing) when compared to a single thermoplastic polymer. ) A durable thermoplastic material can be obtained, which can stably hold a large force and impact of a club face that hits a golf ball on a golf course. Incorporating a reactive crosslinker and catalyst into a four-component thermoplastic blend has a structure interconnected by covalent bonds (chemical bonds) that bond polymer chains, rather than simply ionic bonds (having opposite ions that attract each other). The material is created.

The resulting four-component thermoplastic blend of the present invention has a higher flexural modulus (ASTM D-790), tensile strength (ASTM D-638), and extreme elongation (ASTM D) than the thermoplastic polymer of the four-component thermoplastic polymer. -638) may also have. Relative amounts of ionomers, thermoplastic polymers, reactive crosslinkers (PGMs), and catalysts are modified to achieve the desired Tg, flexural modulus, tensile strength, and / or extreme elongation of the layer of the four-component plastic blend. , Adjustment, and goal setting.

In one example, the thermoplastic polymer is about 20 shore D to about 66 shore D, or 20 shore D to about 60 shore D, or 20 shore D to about 50 shore D, or 20 shore D to about 40 shore D, Or 20 shore D to about 30 shore D, or 30 shore D to about 66 shore D, or 30 shore D to about 60 shore D, or 30 shore D to about 50 shore D, or 30 shore D to about 40 shore D, Or 40 shore D to about 66 shore D, or 40 shore D to about 60 shore D, or 40 shore D to about 50 shore D, or 50 shore D to about 66 shore D, or 50 shore D to about 60 shore D. It may have material hardness.

In one embodiment, the four-part thermoplastic blend is greater than about 20 shore D and up to about 70 shore D, or greater than about 30 shore D up to about 70 shore D, or greater than about 40 shore D and up to about 70 shore D. , Or about 50 shore D up to about 70 shore D, or about 60 shore D up to about 70 shore D, or about 25 shore D to about 70 shore D, or about 25 shore D to about 60 shore D, or About 25 Shore D to about 50 Shore D, or about 25 Shore D to about 40 Shore D, or about 35 Shore D to about 70 Shore D, or about 45 Shore D to about 60 Shore D, or about 50 Shore D to about 50 Shore D. It has a material hardness of 70 shore D, or about 50 shore D to about 60 shore D.

The four-component thermoplastic blend may have a modulus greater than that of the thermoplastic polymer. Therefore, in such an embodiment, the layer of the four-component thermoplastic blend of the present invention may have any known optimum modulus of elasticity that is greater than the modulus of elasticity of the thermoplastic polymer, which is an ionomer, thermoplastic. It is assumed that the relative amounts of the polymer, reactive crosslinker, and catalyst are preselected by preselecting to cover a wide range of competitive properties.

To produce a four-component thermoplastic blend that produces unique and desirable golf ball properties without the aforementioned problems encountered with traditional TPU-containing materials in terms of durability, toughness, mechanical strength, cutting and scratch resistance, ionomers. Must be included in the blend in an amount greater than 45% by weight of the total weight of the four-component thermoplastic blend. On the other hand, the relative requirements of the components (ii) and (iii) of the four-component thermoplastic blend are mutually while maintaining the preselected ionomer requirements in a range greater than 45% by weight of the total weight of the blend. Can be adjusted to. Therefore, as long as the ionomer requirement exceeds 45% by weight, the components (ii) (TPU) and (iii) of the four-component thermoplastic blend will be 2% by weight based on the total weight of the four-component thermoplastic blend. It may be selected in the range of less than 35% by weight and the range of more than 20 and up to 50% by weight.

The requirement for ionomers in a four-component thermoplastic blend is greater than about 45% by weight of the total weight of the blend, while the requirement for component (iii) is up to about 35% by weight, component (ii). There are specific examples in which the amount of (TPU) is greater than 20% by weight and is included in the range up to about 50% by weight.

Layers such as covers containing a four-component thermoplastic blend are approximately 0.010 inches to approximately 0.050 inches, or approximately 0.010 inches to approximately 0.040 inches, or approximately 0.010 inches to approximately 0.030 inches, or 0.010 inches to approximately 0.020 inches, or approximately 0.015. It may have a thickness of about 0.045 inches, or about 0.025 inches to about 0.045 inches, or about 0.035 inches to about 0.050 inches, or about 0.020 inches to about 0.050 inches. It should also be noted that the coating layer and film of the four-component thermoplastic blend may be formed around the golf ball subassembly of the present invention at any known thickness thereof.

The present invention also relates to a method of making a golf ball of the present invention, wherein the method is: a step of providing a subassembly; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea,. At least one different thermoplastic polymer consisting of a thermoplastic urea-urethane hybrid, or a combination thereof; (iii) at least a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM). It has one reactive cross-linking agent; and (iv) a step of forming at least one layer of a four-component thermoplastic blend consisting of at least one catalyst around the subassembly. The four-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight of the different thermoplastic polymer. %, C is the weight% of PGM, where I&gt; 45 and 2 C &lt;35.

In another embodiment, the method of making a golf ball of the present invention is: a step of providing a subassembly; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-. At least one different thermoplastic polymer consisting of a urethane hybrid, or a combination thereof; (iii) at least one reactivity consisting of a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM). It has a cross-linking agent; and (iv) a step of forming at least one layer of a four-component thermoplastic blend consisting of at least one catalyst around the subassembly.

In other embodiments, the method is: (i) at least one ionomer; (ii) at least one different thermal consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. Thermoplastic Polymer; (iii) At least one reactive crosslinker consisting of a maleic acid group modified polymer, glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM); and (iv) at least one catalyst. It has a step of providing a subassembly consisting of a component thermoplastic blend; and a step of forming at least one layer having a thermoplastic or thermoplastic composition around the subassembly.

Alternatively, the method is: (i) at least one ionomer; (ii) at least one different thermoplastic consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. Polymers; (iii) at least one reactive crosslinker consisting of a maleic acid group modified polymer, a glycidyl (meth) acrylate modified polymer, or a combination thereof (PGM); and (iv) a four component consisting of at least one catalyst. It may have a step of providing a subassembly having a thermoplastic blend; and a step of forming at least one layer having a thermoplastic or thermoplastic composition around the subassembly.

Advantageously, the golf ball of the present invention has a novel heat of ionomer, TPU, and ASA and / or ABS (acrylonitrile styrene acrylate, acrylonitrile butadiene styrene, or a combination thereof) on at least one layer, for example, a cover. Incorporates a plastic blend. The thermoplastic blends of the present invention are preferably durable, tough, have high mechanical strength, impact durability, and cut / cut (groove shear) resistance, and in a single layer, each part of the blend. Unique properties can be achieved, while not sacrificing the good processing properties typically associated with the production of thermoplastic materials.

Advantageously, the golf balls of the present invention combine the advantages of ionomers and TPUs and their respective into a single layer without sacrificing processability (eg, having good meltflow properties) or durability and toughness. include. Thermoplastic resin blends can be cost-effectively molded using a variety of methods, yet provide high mechanical strength, impact durability, and cut / cut (groove shear) resistance.

The golf balls of the present invention include a core and (i) at least one ionomer; (ii) at least one thermoplastic polyurethane; and (iii) at least one acrylonitrile styrene acrylate, acrylonitrile butadiene styrene, or a combination thereof (ASA). And / or ABS ") may have at least one layer with a thermoplastic blend, where ionomers are present in an amount of about 45% by weight or more, ASA and / or ABS from about 2% by weight. It is present in an amount of about 35% by weight.

The thermoplastic polyurethane may be present in the blend in an amount of about 8% to about 50% by weight. In another embodiment, the thermoplastic polyurethane may be present in an amount of about 25% by weight to about 45% by weight. In yet another embodiment, the thermoplastic polyurethane may be present in an amount of about 35% to about 50% by weight.

In certain embodiments, ionomers are present in the blend in greater amounts than the amount of thermoplastic polyurethane. In one embodiment, ionomers are present in an amount of about 45% to about 70% by weight.

In one embodiment, the thermoplastic polyurethane may be present in an amount greater than 20% by weight and up to about 40% by weight. And ASA and / or ABS are present in an amount of about 5% to about 30% by weight. In some examples, ASA and / or ABS are present in an amount of about 15% to about 35% by weight.

The golf balls of the present invention are (i) at least one ionomer; (ii) at least one different thermoplastic polymer consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof; And (iii) may have at least one layer having a three-component thermoplastic blend consisting of at least one acrylonitrile styrene acrylate, acrylonitrile butadiene styrene, or a combination thereof (ASA and / or ABS). The three-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight% of ASA and / or ABS, I&gt; 45, and 2 C &lt;35.

In one embodiment, T is greater than 20 and up to about 50. In another embodiment, T is 25-50. In yet another embodiment, T is about 25-50. In yet another embodiment, T is greater than about 25 and up to 50. In an alternative embodiment, T is from 30 to about 50, or greater than about 30 up to about 50, or greater than 30 up to 60. In certain embodiments, T is 35-60, or about 35-60, or about 35-50, or about 40-50. In one embodiment, T is greater than 40, up to about 50. In other embodiments, T is 40-50.

There are different embodiments where 8 T 50, or T is about 8-40.

In one embodiment, I&gt; T. In another embodiment, T&gt; I. In another embodiment, T = I.

In a particular embodiment, I &lt;90. In a particular embodiment, 45 &lt;I &lt;70. In different embodiments, I is 48-90.

In one such particular embodiment, T is greater than 20, up to about 40, and C is 3-30.

In one particular embodiment, 15 C &lt;35. In another particular embodiment, 20 C &lt;35.

The ASA may be composed of at least 60% acrylate and / or the ABS may be composed of at least 60% butadiene.

In one example, the three-component thermoplastic blend has a material hardness from about 20 shore D to about 65 shore D.

The three-component thermoplastic blend may have a material hardness different from the material hardness of the thermoplastic polymer.

In one example, the three-component thermoplastic blend has a material hardness greater than about 20 shore D and up to about 70 shore D.

In one embodiment, at least one layer is a cover layer that surrounds the subassembly and has a hardness H that differs from the hardness H (ii) of (ii) by at least about 5 Shore D hardness points, where (ii). Has a hardness of about 20 shore D to about 70 shore D.

In another embodiment, the at least one layer surrounds the subassembly and is surrounded by an outer cover layer, with an inner cover having a hardness H different from hardness H (ii) in (ii) by at least about 5 Shore D hardness points. It is a layer, where (ii) has a hardness of about 20 shore D to about 70 shore D.

In some embodiments, the golf ball of the present invention comprises (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. It has at least one layer consisting of a three-component thermoplastic blend consisting of one different thermoplastic polymer; and (iii) ASA and / or ABS.

In certain embodiments, 20 &lt;T &lt;50, or 20 T 50, or 20 &lt;T 50, or 20 &lt;T &lt;40, or 20 T 40, or 25 T &lt;50, or 25 &lt;. T 50, or 25 T &lt;40, or 30 T 50, or 30 T &lt;40, or 40 T 50, or 40 &lt;T &lt;50, or 15 T 50, or 15 T. &lt;30.

In different embodiments, T is 8 T 50, or 8 T &lt;50, or 8 &lt;T 50, or 8 &lt;T &lt;50, or 8 to 45, or about 8 to 45, or 8 T . 40, or 8 T &lt;40, or 8 &lt;T 40, or 8 &lt;T &lt;40, or 8 T 30, 8 T &lt;30, or 8 &lt;T 30, or 8 &lt;T &lt;30. , Or 8 T 20, 8 T &lt;20, or 8 &lt;T 20, or 8 &lt;T &lt;20, or 8 T 15, 8 T &lt;15, or 8 &lt;T 15, Or 8 &lt;T &lt;15.

In a particular formulation, 5 C &lt;35, or 10 C &lt;35, or 15 C &lt;35, or 15 C 35, or 15 C &lt;25, or 15 C 25, or 20 C. &lt;35, or 20 C 35, or 20 C &lt;25, or 15 C 20.

In certain embodiments, 45 &lt;I &lt;70, or 45 &lt;I 70, or 45 &lt;I &lt;60, or 45 &lt;I 60, or 55 I &lt;70, or 55 I 70.

Since I is always greater than 45 and 2 C &lt;35, T is always up to about 50. This means that many possible combinations of I, T and C can be voted and adjusted within the scope disclosed here. In such particular examples, I&gt; 45, C &lt;35, and T&gt; 20. In another such specific embodiment, I&gt; 45, C &lt;30, and T&gt; 25. In yet another such embodiment, I&gt; 45, C &lt;20, and T&gt; 35. In yet another such embodiment, I&gt; 45, C &lt;15, and T&gt; 40. In another embodiment, I&gt; 45, C 2, and T 53.

In certain non-limiting examples, I is 90, T is 8, and C is 2. In another specific non-limiting example, I is 80, T is 15, and C is 5. In yet another specific non-limiting example, I is 70, T is 20, and C is 10. In yet another specific non-limiting example, I is 60, T is 25, and C is 15. In another specific non-limiting example, I is 50 and T is 30. In different specific non-limiting examples, I is 50, T is 20, and C is 30. In another specific non-limiting example, I is 46, T is 50, and C is 4. In other non-limiting examples, I is 45, T is 45, and C is 10. Yet another specific non-limiting example is 47 for I, 43 for T, and 10 for C.

In some embodiments, the golf ball of the present invention comprises (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. One different thermoplastic polymer; (iii) has at least one layer consisting of a three-component thermoplastic blend consisting of ASA and / or ABS. Again, the three-component thermoplastic resin blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the different thermoplastic polymer. By weight%, C is the weight% of ASA and / or ABS, I&gt; 45, and 2 C &lt;35.

As used herein, the term "thermoplastic polymer" refers to a thermoplastic composition comprising one or more thermoplastic polymers other than the ionomers defined herein. In one such embodiment, the thermoplastic polymer may include thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. The thermoplastic polyurethane itself may include a thermoplastic urethane / polyurethane blend. The thermoplastic urea itself may contain a blend of thermoplastic urea / polyurea. Further, the urea-urethane hybrid itself may include a plurality of different hybrids.

Thermoplastic polymers in a three-component thermoplastic blend include fillers, additives, catalysts, wetting agents, colorants, fluorescent whitening agents, cross-linking agents, whitening agents such as titanium dioxide and zinc oxide, and UV (UV) light absorption. Agents, hindered amine light stabilizers, defoaming agents, processing aids, surfactants, and antioxidants, stabilizers, softeners, thermoplastics, impact resistance improvers, foaming agents, density adjusting fillers, reinforcing materials, phases Additional materials / ingredients such as other conventional additives such as solubilizers may be further included.

Due to the interaction between ionomers, thermoplastic polymers, ASA and / or ABS, thermoplastics with superior mechanical strength, impact durability, and cut resistance (groove shear) resistance compared to thermoplastic polymers alone. The material is produced and can better and more reliably direct the great force and impact of the club face hitting the golf ball on the course.

The resulting three-component thermoplastic blend of the present invention also has a higher flexural modulus (ASTM D-790), tensile strength (ASTM D-638), and extreme elongation than the thermoplastic polymer of the three-component thermoplastic blend. May have (ASTM D-638). Relative amounts of ionomers, thermoplastic polymers, ASA and / or ABS are modified, adjusted, and / or adjusted to achieve the desired Tg, flexural modulus, tensile strength, and / or final elongation of the layer of the three-component thermoplastic blend. Be targeted.

In one example, the thermoplastic polymer is about 20 shore D to about 66 shore D, or 20 shore D to about 60 shore D, or 20 shore D to about 50 shore D, or 20 shore D to about 40 shore D, Or 20 shore D to about 30 shore D, or 30 shore D to about 66 shore D, or 30 shore D to about 60 shore D, or 30 shore D to about 50 shore D, or 30 shore D to about 40 shore D, Or 40 shore D to about 66 shore D, or 40 shore D to about 60 shore D, or 40 shore D to about 50 shore D, or 50 shore D to about 66 shore D, or 50 shore D to about 60 shore D. May have material hardness up to.

In one example, the three-component thermoplastic blend is greater than about 20 shore D and up to about 70 shore D, or greater than about 30 shore D, up to about 70 shore D, or greater than about 40 shore D, up to about. Greater than 70 shore D, or about 50 shore D, up to about 70 shore D, or greater than about 60 shore D, up to about 70 shore D, or about 25 shore D to about shore 70D, or about 25 shore D to about 60 shore D, or about 25 shore D to about 50 shore D, or about 25 shore D to about 40 shore D, or about 35 shore D to about 70 shore D, or from about 45 shore D to about 60 shore D It has a material hardness of up to D, or from about 50 shore D to about 70 shore D, or from about 50 shore D to about 60 shore D.

The three-component thermoplastic blend may have a modulus greater than that of the thermoplastic polymer. Therefore, in such an embodiment, the layer of the three-component thermoplastic blend of the present invention is greater than the modulus of elasticity of the thermoplastic polymer, and the relative amounts of the ionomer, the thermoplastic polymer, and the component (iii) are preselected. Note that a wide range of play characteristics may be targeted with any known suitable modulus predetermined by.

To produce a three-component thermoplastic blend that produces unique and desirable golf ball properties without the aforementioned problems encountered with traditional TPU-containing materials in terms of durability, toughness, mechanical strength, cutting and scratch resistance. Ionomer should be included in excess of 45% by weight of the total weight of the blend. On the other hand, the relative requirements of the components (ii) and (iii) of the three-component thermoplastic blend can be adjusted to each other while maintaining the preselected requirements of the ionomer in the range above 45% by weight. Therefore, as long as the ionomer requirement exceeds 45% by weight, the components (ii) (TPU) and (iii) of the three-component thermoplastic blend will be 2% to 35% by weight based on the total weight of the three-component thermoplastic blend. It may be selected within the range of less than% by weight and within the range of 20 to 50% by weight, respectively.

The requirement for ionomers in the three-component thermoplastic blend is greater than about 45% by weight of the total weight of the blend, while the requirement for component (iii) is up to about 35% by weight, component (ii) (TPU). There are certain embodiments where the amount of is greater than 20% by weight and is within a range of up to about 50% by weight.

Layers such as covers containing a three-component thermoplastic blend are approximately 0.010 inches to approximately 0.050 inches, or approximately 0.010 inches to approximately 0.040 inches, or approximately 0.010 inches to approximately 0.030 inches, or approximately 0.010 inches to approximately 0.020 inches, or approximately. It may have a thickness of 0.015 inch to about 0.045 inch, or about 0.025 inch to about 0.045 inch, or about 0.035 inch to about 0.050 inch, or about 0.020 inch to about 0.050 inch. It should also be noted that the coating layer and film of the three-component thermoplastic blend may be formed around the golf ball subassembly of the present invention at any known thickness thereof.

The present invention also relates to a method of making a golf ball of the present invention, wherein the method is: a step of providing a subassembly; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea,. At least one different thermoplastic polymer consisting of a thermoplastic urea-urethane hybrid, or a combination thereof; and (iii) at least one layer consisting of a three-component thermoplastic blend consisting of ASA and / or ABS around the subassembly. Has a step to form on. The three-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight% of ASA and / or ABS, I&gt; 45, and 2 C &lt;35.

In another embodiment, the method of making a golf ball of the present invention is: a step of providing a subassembly; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-. Urethane hybrids, or at least one different thermoplastic polymer consisting of a combination thereof; and (iii) with the step of forming at least one layer around the subassembly with a three-component thermoplastic blend consisting of ASA and / or ABS. Have.

In other embodiments, the method is: (i) at least one ionomer; (ii) at least one different thermosetting consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. A plastic polymer; and (iii) a step of providing a subassembly consisting of a three-component thermoplastic blend consisting of ASA and / or ABS; at least one layer having a thermosetting or thermoplastic composition around the subassembly. It has a step to form.

Alternatively, the method is: (i) at least one ionomer; (ii) at least one different thermoplastic consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. Polymer; and (iii) a step of providing a subassembly having a three-component thermoplastic blend consisting of ASA and / or ABS; forming at least one layer containing a thermosetting or thermoplastic composition around the subassembly. And have steps to do.

Advantageously, the golf ball of the present invention incorporates a novel thermoplastic blend of ionomer, TPU, and PEPA (polyester elastomer, polyamide elastomer) or a combination of these (PEPA) in at least one layer such as a cover. .. The thermoplastic blends of the present invention are preferably durable, tough, have high mechanical strength, impact durability, and cut / scratch (groove shear) resistance, and are single-layer, three-component thermoplastic blends. It incorporates the unique properties of each part, without sacrificing the good processability associated with the production of thermoplastics.

Advantageously, the golf balls of the present invention combine the advantages of ionomers and TPUs and their respective into a single layer without sacrificing processability (eg, having good meltflow properties) or durability and toughness. include. Thermoplastic resin blends have high mechanical strength, impact durability, and cutting / scratch (groove shear) resistance, although they can be cost-effectively molded using a variety of methods.

The golf balls of the present invention are: with a core; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane; and (iii) at least one polyester elastomer, polyamide elastomer, or a combination thereof (PEPA). It may have at least one layer having a thermoplastic blend of, where ionomers are present in an amount of about 45% by weight or more and PEPA is present in an amount of about 2% to about 35% by weight. The thermoplastic polyurethane may be present in the blend in an amount of about 8% to about 50% by weight. In another embodiment, the thermoplastic polyurethane may be present in an amount of about 25% by weight to about 45% by weight. In yet another embodiment, the thermoplastic polyurethane may be present in an amount of about 35% to about 50% by weight.

In certain embodiments, ionomers are present in the blend in greater amounts than the amount of thermoplastic polyurethane. In one embodiment, ionomers are present in an amount of about 45% to about 70% by weight.

In one embodiment, the thermoplastic polyurethane may be present in an amount greater than 20% by weight and up to about 40% by weight. And PEPA is present in an amount of about 5% to about 30% by weight. In some examples, PEPA is present in an amount of about 15% to about 35% by weight.

The golf balls of the present invention are: (i) at least one ionomer; (ii) at least one different thermoplastic polymer consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof; And (iii) may have at least one layer having a three-component thermoplastic blend consisting of PEPA. The three-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight percent of PEPA, I&gt; 45, and 2 C &lt;35.

In one embodiment, T is greater than 20 and up to about 50. In another embodiment, T is 25-50. In yet another embodiment, T is about 25 to 50. In yet another embodiment, T is greater than about 25 and up to 50. In an alternative embodiment, T is from 30 to about 50, or greater than about 30 to about 50, or greater than 30 to 60. In certain embodiments, T is 35-60, or about 35-60, or about 35-50, or more than 35 to about 50, or about 40-50. In one embodiment, T is greater than 40, up to about 50. In other embodiments, T is 40-50.

There are different embodiments where 8 T 50, or T is about 8-40.

In one embodiment, I&gt; T. In an alternative embodiment, T&gt; I. In another embodiment, T = I.

In a particular embodiment, I &lt;90. In a specific example, 45 &lt;I &lt;70. In different embodiments, I is 48-90.

In one such particular embodiment, T is greater than 20, up to about 40, and C is 3-30.

In one specific embodiment, 15 C &lt;35. In another specific embodiment, 20 C &lt;35.

In one embodiment, PEPA is selected from the group consisting of polyether polyesters, polyether polyamides, or combinations thereof.

In one example, the three-component thermoplastic blend has a material hardness from about 20 shore D to about 65 shore D.

The three-component thermoplastic blend may have a material hardness different from the material hardness of the thermoplastic polymer.

In one example, the three-component thermoplastic blend has a material hardness greater than about 20 shore D and up to about 70 shore D.

In one embodiment, the at least one layer is a cover layer that surrounds the subassembly and has a hardness H that differs from the hardness H (ii) of (ii) by at least about 5 shore D hardness points, where (ii). ) Has a hardness of about 20 shore D to about 70 shore D.

In another embodiment, the at least one layer surrounds the subassembly and is surrounded by an outer cover layer, with an inner cover having a hardness H different from hardness H (ii) in (ii) by at least about 5 Shore D hardness points. It is a layer, where (ii) has a hardness of about 20 shore D to about 70 shore D.

In some embodiments, the golf ball of the present invention comprises (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. It has at least one layer consisting of a three-component thermoplastic blend consisting of one different thermoplastic polymer; and (iii) PEPA.

In certain embodiments, 20 &lt;T &lt;50, or 20 T 50, or 20 &lt;T 50, or 20 &lt;T &lt;40, or 20 T 40, or 25 T &lt;50, or 25 &lt;. T 50, or 25 T &lt;40, or 30 T 50, or 30 T &lt;40, or 40 T 50, or 40 &lt;T &lt;50, or 15 T 50, or 15 T. &lt;30.

In different embodiments, T is about 8 to 45, or 8 T 50, or 8 T &lt;50, or 8 &lt;T 50, or 8 &lt;T &lt;50, or 8 T 40, or 8 . T &lt;40, or 8 &lt;T 40, or 8 &lt;T &lt;40, or 8 T 30, 8 T &lt;30, or 8 &lt;T 30, or 8 &lt;T &lt;30, or 8 T. 20, or 8T &lt;20, or 8 &lt;T20, or 8 &lt;T &lt;20, or 8T15, or 8T &lt;15, or 8 &lt;T15, or 8 &lt;T &lt; It is 15.

In a particular formulation, 5 C &lt;35, or 10 C &lt;35, or 15 C &lt;35, or 15 C 35, or 15 C &lt;25, or 15 C 25, or 20 C. &lt;35, or 20 C 35, or 20 C &lt;25, or 15 C 20.

In certain embodiments, 45 &lt;I &lt;70, or 45 &lt;I 70, or 45 &lt;I &lt;60, or 45 &lt;I 60, or 55 I &lt;70, or 55 I 70, or 45 &lt; I &lt;90, or 45 &lt;I 90, or 60 &lt;I &lt;90, or 60 &lt;I 90, or 70 &lt;I &lt;90, or 70 &lt;I 90.

Since I is always greater than 45 and 2 C &lt;35, T is always up to about 50. This means that many possible combinations of I, T and C can be targeted and adjusted within the scope disclosed herein. In such particular examples, I&gt; 45, C &lt;35, and T&gt; 20. In another such specific embodiment, I&gt; 45, C &lt;30, and T&gt; 25. In yet another such embodiment, I&gt; 45, C &lt;20, and T&gt; 35. In yet another such embodiment, I&gt; 45, C &lt;15, and T&gt; 40. In another embodiment, I&gt; 45, C 2, and T 53.

In certain non-limiting examples, I is 90, T is 8, and C is 2. In another specific non-limiting example, I is 80, T is 15, and C is 5. Yet another specific non-limiting example is 70 for I, 20 for T, and 10 for C. Yet another specific non-limiting example is I for 60, T for 25, and C for 15. In certain alternative non-limiting examples, I is 50, T is 30, and C is 20. In different specific non-limiting examples, I is 50, T is 20, and C is 30. In different specific non-limiting examples, I is 46, T is 50, and C is 4. In other specific non-limiting examples, I is 45, T is 45, and C is 10. Yet another specific non-limiting example is 47 for I, 43 for T, and 10 for C.

In some embodiments, the golf ball of the present invention comprises (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. It has at least one layer consisting of a three-component thermoplastic blend consisting of one different thermoplastic polymer; and (iii) PEPA. Again, the three-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio of I: T: C, where I is the weight% of the ionomer and T is the different thermoplastic polymer. By weight%, C is the weight% of PEPA, I&gt; 45, and 2 C &lt;35.

As used herein, the term "thermoplastic polymer" refers to a thermoplastic composition comprising one or more thermoplastic polymers other than the ionomers defined herein. In one such embodiment, the thermoplastic polymer may include thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. The thermoplastic polyurethane itself may include a thermoplastic urethane / polyurethane blend. The thermoplastic urea itself may contain a blend of thermoplastic urea / polyurea. Further, the urea-urethane hybrid itself may include a plurality of different hybrids.

Thermoplastic polymers in a three-component thermoplastic blend include fillers, additives, catalysts, wetting agents, colorants, fluorescent whitening agents, cross-linking agents, whitening agents such as titanium dioxide and zinc oxide, and UV (UV) light absorption. Agents, hindered amine light stabilizers, defoaming agents, processing aids, surfactants, and antioxidants, stabilizers, softeners, thermoplastics, impact resistance improvers, foaming agents, density adjusting fillers, reinforcing materials, phases Additional materials / ingredients such as other conventional additives such as solubilizers may be further included.

Due to the interaction between ionomers, thermoplastic polymers, ASA and / or ABS, thermoplastics with superior mechanical strength, impact durability, and cut resistance (groove shear) resistance compared to thermoplastic polymers alone. The material is produced and can better and more reliably direct the great force and impact of the club face hitting the golf ball on the course.

The resulting three-component thermoplastic blend of the present invention also has a higher flexural modulus (ASTM D-790), tensile strength (ASTM D-638), and extreme elongation than the thermoplastic polymer of the three-component thermoplastic blend. May have (ASTM D-638). Relative amounts of ionomers, thermoplastic polymers, ASA and / or ABS are modified, adjusted, and / or adjusted to achieve the desired Tg, flexural modulus, tensile strength, and / or final elongation of the layer of the three-component thermoplastic blend. Be targeted.

In one example, the thermoplastic polymer is about 20 shore D to about 66 shore D, or 20 shore D to about 60 shore D, or 20 shore D to about 50 shore D, or 20 shore D to about 40 shore D, Or 20 shore D to about 30 shore D, or 30 shore D to about 66 shore D, or 30 shore D to about 60 shore D, or 30 shore D to about 50 shore D, or 30 shore D to about 40 shore D, Or 40 shore D to about 66 shore D, or 40 shore D to about 60 shore D, or 40 shore D to about 50 shore D, or 50 shore D to about 66 shore D, or 50 shore D to about 60 shore D. May have material hardness up to.

In one example, the three-component thermoplastic blend is greater than about 20 shore D and up to about 70 shore D, or greater than about 30 shore D, up to about 70 shore D, or greater than about 40 shore D, up to about. Greater than 70 shore D, or about 50 shore D, up to about 70 shore D, or greater than about 60 shore D, up to about 70 shore D, or about 25 shore D to about shore 70D, or about 25 shore D to about 60 shore D, or about 25 shore D to about 50 shore D, or about 25 shore D to about 40 shore D, or about 35 shore D to about 70 shore D, or from about 45 shore D to about 60 shore D It has a material hardness of up to D, or from about 50 shore D to about 70 shore D, or from about 50 shore D to about 60 shore D.

The three-component thermoplastic blend may have a modulus greater than that of the thermoplastic polymer. Therefore, in such an embodiment, the layer of the three-component thermoplastic blend of the present invention is greater than the modulus of elasticity of the thermoplastic polymer, and the relative amounts of the ionomer, the thermoplastic polymer, and the component (iii) are preselected. Note that a wide range of play characteristics may be targeted with any known suitable modulus predetermined by.

To produce a three-component thermoplastic blend that produces unique and desirable golf ball properties without the aforementioned problems encountered with traditional TPU-containing materials in terms of durability, toughness, mechanical strength, cutting and scratch resistance. Ionomer should be included in excess of 45% by weight of the total weight of the blend. On the other hand, the relative requirements of the components (ii) and (iii) of the three-component thermoplastic blend can be adjusted to each other while maintaining the preselected requirements of the ionomer in the range above 45% by weight. Therefore, as long as the ionomer requirement exceeds 45% by weight, the components (ii) (TPU) and (iii) of the three-component thermoplastic blend will be 2% to 35% by weight based on the total weight of the three-component thermoplastic blend. It may be selected within the range of less than% by weight and within the range of 20 to 50% by weight, respectively.

The requirement for ionomers in the three-component thermoplastic blend is greater than about 45% by weight of the total weight of the blend, while the requirement for component (iii) is up to about 35% by weight, component (ii) (TPU). There are certain embodiments where the amount of is greater than 20% by weight and is within a range of up to about 50% by weight.

Layers such as covers containing a three-component thermoplastic blend are approximately 0.010 inches to approximately 0.050 inches, or approximately 0.010 inches to approximately 0.040 inches, or approximately 0.010 inches to approximately 0.030 inches, or approximately 0.010 inches to approximately 0.020 inches, or approximately. It may have a thickness of 0.015 inch to about 0.045 inch, or about 0.025 inch to about 0.045 inch, or about 0.035 inch to about 0.050 inch, or about 0.020 inch to about 0.050 inch. It should also be noted that the coating layer and film of the three-component thermoplastic blend may be formed around the golf ball subassembly of the present invention at any known thickness thereof.

The invention also relates to a method of making a golf ball of the invention, which method: with the steps of providing subassemblies; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea,. It has a step of forming at least one layer consisting of a thermoplastic urea-urethane hybrid, or a combination thereof; and (iii) a three-component thermoplastic blend consisting of PEPA around the subassembly. The three-component thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight percent of PEPA, I&gt; 45, and 2 C &lt;35.

In another embodiment, the method of making a golf ball of the present invention is: a step of providing a subassembly; (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-. It has at least one different thermoplastic polymer consisting of a urethane hybrid, or a combination thereof; and (iii) a step of forming at least one layer having a three-component thermoplastic blend consisting of PEPA around the subassembly.

In other embodiments, the method is: (i) at least one ionomer; (ii) at least one different thermosetting consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. Plastic polymer; and (iii) a step of providing a subassembly consisting of a three-component thermoplastic blend consisting of PEPA; and a step of forming at least one layer having a thermosetting or thermoplastic composition around the subassembly. Has.

Alternatively, the method is: (i) at least one ionomer; (ii) at least one different thermoplastic consisting of at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. A step of providing a subassembly having a three-component thermoplastic blend consisting of a polymer; and (iii) PEPA; and a step of forming at least one layer containing a thermosetting or thermoplastic composition around the subassembly. Have.

Three-component or three-component thermoplastic blended ionomers may include partially terminated ionomers and highly neutralized ionomers (HNPs), which are blends of two or more partially neutralized ionomers, Includes a blend of two or more highly neutralized ionomers and an ionomer formed from a blend of one or more partially neutralized ionomers and one or more highly neutralized ionomers.

Ionomers are typically ethylene / acrylic acid copolymers or ethylene / acrylic acid / acrylate ternary copolymers in which some or all of the acid groups are neutralized with metal cations. Commercially available ionomers suitable for use in the present invention include, for example, SURLYN from DuPont and Ioteks from Exxon. 8940 (Na), 9650 (Zn), and 9910 (Zn) are examples of low acid ionomer resins with acid groups that are neutralized to some extent by cations. More examples of suitable low acid ionomers, such as Escor 4000/7030 and Escor 900/8000, are disclosed in US Pat. Nos. 4,911,451 and 4,884,814, the contents of which are referenced. Incorporate here. High acid ionomer resins include SURLYN 8140 (Na) and 8546 (Li), which contain approximately 19 percent methacrylic acid. The acid groups of these high acid ionomer resins are neutralized to a predetermined degree by designated cations.

Ionomers are at least partially neutralized after copolymerization of acidic groups or basic monomers such as alkyl (meth) acrylates with at least one other comonomer such as olefin, styrene, or vinyl acetate. May include the polymer obtained by performing the above. Alternatively, an acidic or basic group is incorporated into the polymer and the polystyrene copolymer containing a polymer such as polystyrene or a block copolymer of polystyrene is reacted with a functional reagent such as carboxylic acid or sulfonic acid to form an ionomer. , Then at least partial neutralization may be individualized. Suitable neutralization sources include negatively charged acidic group cations and positively charged basic group anions.

For example, an ionomer is an at least one member selected from the group consisting of unsaturated mono or dicarboxylic acids with 3-12 carbon atoms and esters thereof, obtained by providing cross metal bonds to the polymer of the monoolefin. The polymer may contain from about 1 weight percent to about 50 weight percent unsaturated mono or dicarboxylic acid and / or an ester thereof. In one embodiment, the ionomer is an E / X / Y copolymer, where E is ethylene and X is 0% to about 50% by weight (preferably 0% to about 25% by weight) of the polymer. , Most preferably 0% to about 20% by weight) softening comonomer, eg acrylate or methacrylate, where Y is acrylic acid or methacrylic acid present in only about 5 to about 35% by weight of the weight of the polymer. The acid moiety is neutralized, for example, from about 1% to about 100% by cations, lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, or cations such as aluminum, or a combination thereof ( Preferably at least about 40%, most preferably at least about 60%), forming ionomers.

Any of the acid-containing ethylene copolymers described above may be used to form the ionomers according to the invention. Further, the ionomer may be a low acid or high acid ionomer. As detailed above, the high acid ionomer may be a copolymer of an olefin, such as ethylene, and at least 16% by weight α, β-ethylenically unsaturated carboxylic acid, such as acrylic acid or methacrylic acid. About 10% to about 100% of carboxylic acid groups are neutralized with metal ions. In contrast, low acid ionomers contain about 15 weight percent α, β-ethylenically unsaturated carboxylic acid.

Suitable commercially available ionomer resins include SURLYNs® (DuPont) and Ioteks® (Exxon). Other ionomers suitable for use in the blends of the invention include polyolefins, polyesters, polystyrenes, SBSs, SEBSs, and polyurethanes in the form of homopolymers, copolymers, or block copolymer ionomers.

Ionomers may be blended with highly neutralized polymers (HNPs). As used herein, highly neutralized polymers account for more than about 70 percent of the neutralized acid groups. In one example, about 80 percent or more of the acid groups are neutralized. In another example, about 90 percent or more of the acid groups are neutralized. In yet another embodiment, the HNP is a completely neutralized polymer, i.e., all acid groups (100 percent) in the polymer composition are neutralized.

Suitable HNPs include, but are not limited to, polymers or salts thereof that contain α, β-unsaturated carboxylic acid groups that are highly neutralized with organic fatty acids. Such HNPs are commercially available from DuPont under the trade names HPF, eg HPF1000 and HPF2000. HNP may also be formed using an oxa-containing compound as a reaction treatment aid to avoid treatment problems, as disclosed in US Patent Application Publication No. 2003/0225197. Specifically, HNP is a thermoplastic resin component having an acid or ionic group, ie, an acid polymer or moiety in combination with an oxalic acid, an oxalate, an oxaester, or a combination thereof, and an inorganic metal compound or an organic amine compound. It may contain a neutralizing polymer. As used herein, a partially neutralized polymer should be understood to mean a polymer in which about 10 to about 70 percent of the acidic groups have been neutralized. For example, HNP is about 10 weight percent to about 30 weight percent at least one oxalic acid, about 70 weight percent to about 90 weight percent at least one thermoplastic resin component, and about 2 weight percent to about 6 weight percent. It should be understood to refer to an inorganic metal compound, an organic amine, or a polymer associated with a combination thereof.

In addition, HNP has filed US Patent Application No. 10/875725, entitled "Golf Ball Composition Neutralized with Ammonium-Based and Amine-Based Compounds," filed June 25, 2004 for this applicant's application. As disclosed in, it can be made from an acid copolymer that is neutralized by one or more amine-based or ammonium-based components, or mixtures thereof, the contents of which are incorporated herein by reference.

In addition, one of ordinary skill in the art will appreciate that one or more of the above methods can be used to neutralize HNP. For example, the acid copolymer partially or highly neutralized by the above method is additionally neutralized using a more traditional process, such as neutralization with salts of organic fatty acids and / or appropriate cation sources. Good.

In a specific embodiment, the cores are commercially available from EI du Pont de Nemours and Company, DuPont® HPF ESX 367, HPF 1000, HPF 2000, HPF AD1035, HPF AD1035Soft, HPF AD1040 and AD1172. Includes at least one thermoplastic intermediate core layer formed from ionomers. The coefficient of restitution (COR), compression, and surface hardness of each of these materials are shown in the table when measured on a 1.55 inch injection molded ball aged 2 weeks at 23 ° C / 50% RH.

<tables><img file="JP7074740B2_D0001.tif" /></tables>

In one embodiment, an intermediate layer is placed between the single or multi-layered core and the surrounding cover layer. These intermediate layers may also be referred to as casing layers or inner cover layers. The intermediate layer can be formed from any material known in the art, including thermoplastic and thermosetting materials, but preferably an ethylenic acid copolymer containing at least a partially neutralized acid group. Formed from an ionomer composition comprising. Suitable ethylenic acid copolymers that can be used to form the intermediate layer are generally ethylene copolymers; C.₃~ C₈Includes ethylenically unsaturated mono or dicarboxylic acids; and any softening monomers. These ethylenic acid copolymer ionomers can also be used to form the inner and outer core layers as described above.

Suitable ionomer compositions include partially neutralized ionomers and highly neutralized ionomers (HNPs), blends of two or more partially neutralized ionomers, two or more highly neutralized. Includes a blend of ionomers that have been partially neutralized and one or more highly neutralized ionomers. For the purposes of the present disclosure, "HNP" refers to an acid copolymer after at least 70% of all acid groups present in the composition have been neutralized. Preferred ionomers are O for α-olefins and X for C.₃-C₈It is an α, β-ethylenically unsaturated carboxylic acid, and is a salt of O / X- and O / X / Y-type acid copolymers in which Y is a softening monomer. O is preferably selected from ethylene and propylene. X is preferably selected from methacrylic acid, acrylic acid, ethacryl acid, crotonic acid, and itaconic acid. Methacrylic acid and acrylic acid are particularly preferred. Y is preferably n-butyl (meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylate, ethyl (meth) acrylate and the like. ..

Preferred O / X- and O / X / Y-type copolymers are not limited to this, but ethylene acid copolymers such as ethylene / (meth) acrylic acid, ethylene / (meth) acrylic acid / maleic anhydride, ethylene. / (Meta) acrylic acid, acrylic acid / maleic acid monoester, ethylene / maleic acid, ethylene / maleic acid monoester, ethylene / (meth) acrylic acid / n-butyl (meth) acrylate, ethylene / (meth) acrylic acid / Isobutyl (meth) acrylate, ethylene / (meth) acrylic acid / methyl (meth) acrylate, ethylene / (meth) acrylic acid / ethyl (meth) acrylateter polymer and the like are included. As used herein, the term "copolymer" includes polymers comprising two types of monomers, polymers having three types of monomers, and polymers having three or more types of monomers. Preferred α, β-ethylenic unsaturated monocarboxylic acids or dicarboxylic acids are (meth) acrylic acid, etacrylic acid, maleic acid, crotonic acid, fumaric acid and itaconic acid. (Meta) acrylic acid is most preferred. As used herein, "(meth) acrylic acid" means methacrylic acid and / or acrylic acid. Similarly, "(meth) acrylate" means methacrylate and / or acrylate.

In a particularly preferred version, E is ethylene, X is C3-C8α, β-ethylenically unsaturated carboxylic acid, and Y is a softening monomer, highly neutralized E / X and E / X / Y. Type acid copolymers are used. X is preferably selected from methacrylic acid, acrylic acid, ethacryl acid, crotonic acid, and itaconic acid. Methacrylic acid and acrylic acid are particularly preferred. Y is preferably an acrylate selected from alkyl acrylates and aryl acrylates, preferably selected from (meth) and alkyl (meth) acrylates in which the alkyl group has 1 to 8 carbon atoms, n-. Examples thereof include butyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate. Preferred E / X / Y-type copolymers have X as (meth) acrylic acid and / or Y as (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, Ethyl (meth) acrylate and the like can be mentioned. More preferred E / X / Y-type copolymers are ethylene / (meth) acrylate / n-butyl acrylate, ethylene / (meth) acrylate / methyl acrylate, and ethylene / (meth) acrylate / ethyl acrylate.

The total amount of ethylene in the acid copolymer is typically at least 15% by weight, preferably at least 25% by weight, more preferably at least 40% by weight, even more preferably at least 60% by weight. Represents the weight of the copolymer. The amount of C3 to C8α, β-ethylenically unsaturated monocarboxylic acid or dicarboxylic acid in the acid copolymer is typically 1% to 35% by weight, preferably 5% to 30% by weight, more preferably 5%. Based on the total weight of the weight% copolymer, it is present in an amount of about 0.1% to about 25% by weight, even more preferably from about 10% to about 20% by weight. The amount of any softened comonomer in the acid copolymer is typically 0% to 50% by weight, preferably 5% to 40% by weight, more preferably 10% to 35% by weight, and even more. It is preferably present in an amount of 20% to 30% by weight. "Low acid" and "high acid" ionomer polymers as well as blends of such ionomers can be used. Generally, low acid ionomers are considered to contain an acid moiety of 16% by weight or less, whereas high acid ionomers are considered to contain an acid moiety of more than 16% by weight.

The various O / X, E / X, O / X / Y, and E / X / Y type copolymers are optionally at least partially neutralized with a cationic source in the presence of high molecular weight organic acids. For example, it is disclosed in US Pat. No. 6,756,436, the entire disclosure of which is incorporated herein by reference. The acid copolymer can be reacted with any high molecular weight organic acid and cation source at the same time or prior to the addition of the cation source. Suitable cation sources include metal ion sources such as compounds of alkali metals, alkaline earth metals, transition metals, and rare earth elements; ammonium and monoamine salts; and combinations thereof. Preferred cation sources are compounds of magnesium, sodium, potassium, cesium, calcium, barium, manganese, copper, zinc, lead, tin, aluminum, nickel, chromium, lithium and rare earth metals.

On the other hand, the three-component thermoplastic blend of the present invention may be at least one thermoplastic polyurethane, a thermoplastic urea, a thermoplastic urea-urethane hybrid, or a combination / blend thereof. Generally, polyurethane contains a urethane bond formed by reacting an isocyanate group (-N = C = O) with a hydroxyl group (OH). Polyurethane is produced by the reaction of a polyfunctional isocyanate (NCO-R-NCO) with a long chain polyol having a terminal hydroxyl group (OH --- OH) in the presence of a catalyst and other additives. The chain length of the polyurethane prepolymer is extended by reacting it with a short chain diol (OH-R'-OH). The resulting polyurethane has elastomeric properties due to the "hard" and "soft" segments covalently bonded together. This phase separation occurs primarily because the non-polar low melting point soft segments are incompatible with the highly polar melting point hard segments. The hard segments formed by the reaction of diisocyanates with low molecular weight chain extension diols are relatively rigid and immobile. The soft segments formed by the reaction of diisocyanates with long chain diols are relatively flexible and mobile. Since the hard segment is covalently bonded to the soft segment, it inhibits the plastic flow of the polymer chain and creates elastomer elasticity.

The term "isocyanate compound" as used herein means any aliphatic or aromatic isocyanate containing two or more isocyanate functional groups. The isocyanate compound can be a monomer or a monomer unit as it can be polymerized to produce a polymeric isocyanate containing two or more monomeric isocyanate repeating units. The isocyanate compound may have any suitable backbone structure, including saturated or unsaturated, as well as linear, branched or cyclic. The term "polyamine" as used herein means any aliphatic or aromatic compound containing two or more primary or secondary amine functional groups. Polyamine compounds may have any suitable backbone structure, including saturated or unsaturated, and linear, branched or cyclic. The term "polyamine" can be used interchangeably with amine-terminated components. As used herein, the term "polyol" means any aliphatic or aromatic compound containing two or more hydroxyl functional groups. The term "polyol" can be used interchangeably with hydroxy-terminated components.

Thermoplastic polyurethane has minimal crosslinks. Any bond in the polymer network is primarily due to hydrogen bonds or other physical mechanisms. Due to the low level of cross-linking, thermoplastic polyurethane is relatively flexible. The crosslinked bonds in the thermoplastic polyurethane can be reversibly broken by increasing the temperature during molding or extrusion. That is, the thermoplastic material softens when exposed to heat and returns to its original state when cooled. On the other hand, thermosetting polyurethane cures irreversibly when cured. Crosslinks are set irreversibly and are not destroyed when exposed to heat. Therefore, thermosetting polyurethanes that typically have high levels of crosslinks are relatively rigid.

Aromatic polyurethanes can be prepared according to the present invention and these materials are preferably formed by reacting an aromatic diisocyanate with a polyol. Suitable aromatic diisocyanates that can be used in accordance with the present invention include, for example, toluene 2,4-diisocyanate (TDI), toluene 2,6-diisocyanate (TDI), 4,4'-methylene diphenyl diisocyanate (MDI), and the like. 2,4'-Methylene diphenyl diisocyanate (MDI), high molecular weight methylene diphenyl diisocyanate (PMDI), p-phenylene diisocyanate (PPDI), m-phenylene diisocyanate (PDI), naphthalene 1,5-diisocyanate (NDI), naphthalene 1, Includes 5-diisocyanate (NDI), p-xylene diisocyanate (XDI), and their homopolymers and copolymers and blends. Aromatic isocyanates can react with hydroxyl or amine compounds to form durable tough polymers with a high melting point. The resulting polyurethane generally has good mechanical strength and cutting / shear resistance.

Aliphatic polyurethanes can also be produced according to the present invention, and these materials are preferably formed by reacting an aliphatic diisocyanate with a polyol. Suitable aliphatic diisocyanates that may be used in accordance with the present invention are, for example, isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate ("H".₁₂MDI "), meta-tetramethylxylylene diisocyanate (TMXDI), transcyclohexanediisocyanate (CHDI), and homopolymers and copolymers and blends thereof. The obtained polyurethane is generally excellent in light weight and has thermal stability.

Any polyol available to those of skill in the art is suitable for use according to the present invention. Exemplary polyols include, but are not limited to, polyether polyols, hydroxy-terminated polybutadienes (including partially / fully hydrogenated derivatives), polyester polyols, polycaprolactone polyols, and polycarbonate polyols. In one preferred embodiment, the polyol comprises a polyether polyol. Examples include, but are not limited to, particularly preferred polytetramethylene ether glycol (PTMEG), polyethylene propylene glycol, polyoxypropylene glycol, and mixtures thereof. Hydrocarbon chains can have saturated or unsaturated bonded and substituted or unsubstituted aromatic and cyclic groups.

In another embodiment, the polyester polyol is included in the polyurethane material. Suitable polyester polyols include, but are not limited to, polyethylene adipate glycol; polybutylene adipate glycol; polyethylene adipate glycol; o-phthalate-1,6-hexanediol; poly (hexamethylene adipate) glycol; and mixtures thereof. Hydrocarbon chains can have saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups. In yet another embodiment, the polycaprolactone polyol is included in the material of the invention. Suitable polycaprolactone polyols are, but not limited to, 1,6-hexanediol-initiated polycaprolactone, diethylene glycol-initiated polycaprolactone, trimethylolpropane-initiated polycaprolactone, neopentyl glycol-initiated polycaprolactone, 1,4-butanediol-initiated poly. Includes caprolactone and mixtures thereof. Hydrocarbon chains can have saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups. In yet another embodiment, the polycarbonate polyol is included in the polyurethane material of the present invention. Suitable polycarbonates include, but are not limited to, polyphthalate carbonates and poly (hexamethylene carbonate) glycols. Hydrocarbon chains can have saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups. In one embodiment, the molecular weight of the polyol is from about 200 to about 4000.

There are two basic techniques that can be used to make polyurethane: a) one-shot techniques, and b) prepolymer techniques. In the one-shot method, diisocyanate, polyol and hydroxyl end chain extender (hardener) are reacted at once. Prepolymer techniques, on the other hand, include the initial reaction between the diisocyanate and the polyol compound to produce the polyurethane prepolymer, and the subsequent reaction between the prepolymer and the hydroxyl-terminated chain extender. As a result of the reaction between the isocyanate and the polyol compound, unreacted NCO groups will be present in the polyurethane prepolymer. The prepolymer should have less than 14% unreacted NCO groups. Preferably, the prepolymer has 8.5% or less unreacted NCO groups, more preferably 2.5% to 8%, most preferably 5.0% to 8.0% unreacted NCO groups. As the weight% of unreacted isocyanate groups increases, so does the hardness of the composition.

Either the one-shot method or the prepolymer method may be used to produce the polyurethane composition of the present invention. In one embodiment, a one-shot method is used in which the isocyanate compound is added to the reaction vessel and then the curing agent mixture containing the polyol and the curing agent is added to the reaction vessel. The components are mixed together such that the molar ratio of isocyanate group to hydroxyl group is preferably in the range of about 1.00: 1.00 to about 1.10: 1.00. In the second embodiment, the prepolymer method is used. In general, prepolymer techniques are preferred as they provide better control of chemical reactions. The prepolymer method provides a more homogeneous mixture, resulting in a more consistent polymer composition. The one-shot method is heterogeneous (more random) and results in a mixture that gives the manufacturer less control over the molecular structure of the resulting composition.

Polyurethane compositions can be formed by chain-extending a polyurethane prepolymer with a single chain extender or a mixture of chain extenders, as further described below. As mentioned above, the polyurethane prepolymer can be chain extended by reacting it with a single chain extender or a mixture of chain extenders. In general, prepolymers can be reacted with hydroxyl-terminated hardeners, amine-terminated hardeners, and mixtures thereof. The curing agent extends the chain length of the prepolymer and enhances its molecular weight. In general, thermoplastic polyurethane compositions are typically formed by reacting isocyanate blends with polyols in a 1: 1 stoichiometric ratio. Thermosetting compositions, on the other hand, are crosslinked polymers, typically produced by reaction of isocyanate blends with polyols, usually with a stoichiometric ratio of 1.05: 1.

During the chain extension step, catalysts can be used to produce the prepolymer or to facilitate the reaction between the isocyanate and the polyol compound between the prepolymer and the chain extender. Preferably, the catalyst is added to the reactants before making the prepolymer. Suitable catalysts are, but are not limited to, bismuth catalysts; zinc octanate; stannous octanoate; tin catalysts such as bis-butyltin dilaurate, bis-butyltin diacetate, tin octate; tin chloride (IV), bis. -Butyl tin dimethoxydo, dimethyl-bis [1-oxononyl] oxy] stannan, di-n-octyl tin bis-isooctyl mercaptoacetate; amine-based catalysts such as triethylenediamine, triethylamine, tributylamine; organic such as oleic acid and acetic acid Includes acids; delayed catalysts; and mixtures thereof. The catalyst is preferably added in an amount sufficient to catalyze the reaction of the components in the reaction mixture. In one embodiment, the catalyst is contained in an amount of about 0.001% to about 1% by weight, preferably 0.1% to 0.5% by weight of the composition.

The hydroxyl chain extender (hardener) is preferably ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; 2-methyl-1,3-propanediol; 2-methyl-1,4-butanediol; monoethanolamine; Diethanolamine; Triethanolamine; Monoisopropanolamine; Diisopropylamine; Dipropylene glycol; Polypropylene glycol; 1,2-Butanediol; 1,3-Butanediol; 1,4-Butanediol; 2,3-Butanediol; 2, 3-Dimethyl-2,3-Butanediol; Trimethylol Propane; Cyclohexyldimethylol; Triisopropanolamine; N, N, N', N'-Tetra- (2-Hydroxypropyl) -Ethethylene Diamine; Diethylene Glycolbis- (Aminopropyl) ) Ether; 1,5-pentanediol; 1,6-hexanediol; 1,3-bis- (2-hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol; 1,3-bis- [2- (2) -Hydroxyethoxy) ethoxy] cyclohexane; 1,3-bis-{2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} cyclohexane; trimethylolpropane; preferably polytetramethylene with a molecular weight of about 250 to about 3900. Selected from the group consisting of ether glycol (PTMEG); and mixtures thereof.

-Methylene-bis (2,3-dichloroaniline) (ie, 2,2', 3,3'-tetrachloro-4,4'-diaminodiphenylmethane, or "MDCA"); and mixtures thereof. One particularly suitable amine-terminated chain extender is Ethacure 300 (dimethylthiotoluenediamine or a mixture of 2,6-diamino-3,5-dimethylthiotoluene and 2,4-diamino-3,5-dimethylthiotoluene). ). The amine hardener chain extender used usually has a cyclic structure and a low molecular weight (250 or less).

When the polyurethane prepolymer is reacted with the hydroxyl end curing agent during the chain extension step as described above, the resulting polyurethane composition comprises a urethane bond. On the other hand, when the polyurethane prepolymer is reacted with the amine-terminated hardener during the chain extension step, the excess isocyanate groups in the prepolymer react with the amine groups in the hardener. The resulting polyurethane composition comprises a urethane bond and a urea bond and may be referred to as a polyurethane / urea hybrid. The concentrations of urethane and urea bonds in the hybrid composition may vary. In general, the hybrid composition may contain a mixture of about 10 to 90% urethane and about 90 to 10% urea bonds.

More specifically, when the polyurethane prepolymer is reacted with a hydroxyl end curing agent during the chain extension step, the resulting composition is essentially a pure polyurethane composition comprising a urethane bond having the following general structure: be:<chemistry><img file="JP7074740B2_D0002.tif" /></chemistry>In the equation, x is the chain length, i.e. about 1 or more, R and R₁Is a straight or branched hydrocarbon chain with about 1 to about 20 carbons.

However, when the polyurethane prepolymer is reacted with an amine-terminated hardener during the chain extension step, the excess isocyanate groups in the prepolymer react with the amine groups in the hardener and have the following general structure:<chemistry><img file="JP7074740B2_D0003.tif" /></chemistry>In the equation, x is the chain length, i.e. about 1 or more, R and R₁Is a straight or branched hydrocarbon chain with about 1 to about 20 carbons.

The polyurethane composition used to form the cover layer may comprise other polymeric materials such as aliphatic or aromatic polyurethanes, aliphatic or aromatic polyureas, aliphatics or Aromatic polyurethane / urea hybrids, olefin copolymers Ionomer compositions, polyethylene eg low density polyethylene, linear low density polyethylene, and high density polyethylene; polypropylene; rubber reinforced olefin polymers; acid copolymers that are not part of the ionomer copolymers, eg Poly (meth) acrylic acid; plastomer; flexsomer; styrene / butadiene / styrene block copolymer; styrene / ethylene-butylene / styrene block copolymer; dynamic vulgarized elastomer; ethylene and vinyl acetate copolymer; ethylene and methyl acrylate copolymer; Polyvinyl chloride resin; Arkema Polyamides containing Pebax® thermoplastic polyether blockamides available from Inc, poly (amide-ester) elastomers, and graft copolymers of ionomers and polyamides; crosslinked trans-polyisoprenes and blends thereof; from DuPont. Polyester-based thermoplastic elastomers such as Hytrel® available; Polyester-based thermoplastic elastomers such as Elastollan® available from BASF; Polycarbonates such as Xylex® available from SABIC Innovative Plastics / Polyester Blend; Contains a maleic anhydride graft polymer such as Fusabond® available from DuPont; and a mixture of the aforementioned materials.

In addition, the polyurethane composition may contain fillers, additives, and other ingredients that do not impair the properties of the final composition. These additional materials include catalysts, wetting agents, colorants, optical brighteners, cross-linking agents, whitening agents such as titanium dioxide and zinc oxide, ultraviolet (UV) light absorbers, hindered amine light stabilizers, defoaming agents. Agents Surfactants and other conventional additives can be included. Other suitable additives include antioxidants, stabilizers, softeners, internal and external plasticizers, impact modifiers, foaming agents, density adjusting fillers, reinforcing materials, compatibilizers and other plasticizers. Can be mentioned. Some examples of useful fillers include zinc oxide, zinc sulphate, barium carbonate, barium sulphate, calcium oxide, calcium carbonate, clay, tungsten, tungsten carbide, silica and mixtures thereof. Rubber regrind (recycled core material) and polymers, ceramics, metals, and glass microspheres may also be used. Generally, the additive is present in the composition in an amount of about 1 to about 70% by weight based on the total weight of the composition, depending on the desired properties.

Thermoplastic polyurea compositions are typically formed by reacting isocyanate blends with polyamines in a 1: 1 stoichiometric ratio. Polyurea prepolymers can be chain-extended by reacting with a single hardener or a blend of hardeners. In general, prepolymers can be reacted with hydroxyl-terminated hardeners, amine-terminated hardeners, and mixtures thereof. Usually, the prepolymer and the curing agent are mixed so that the isocyanate group and the hydroxyl group or the amine group are mixed in a chemical ratio of 1.05: 1.

During the chain extension step, a catalyst may be used to facilitate the reaction between the isocyanate and the polyamine compound for producing the prepolymer, or between the prepolymer and the curing agent. Preferably, the catalyst is added to the reactants before making the prepolymer. Suitable catalysts have previously been identified in connection with facilitating the reaction between isocyanates and polyol compounds to produce prepolymers, or the reaction between prepolymers and chain extenders in the chain extension step. Includes, but is not limited to.

The hydroxyl chain extender (curing) agent is preferably selected from the same partial loops previously identified in connection with the polyurethane composition.

Suitable amine chain extenders (curing) agents that can be used to extend the chains of the polyurea prepolymers of the present invention are not limited to those previously identified in relation to the chain extension of polyurethane prepolymers, 4,4 '-Bis (sec-butylamino) -diphenylmethane, N, N'-dialkylamino-diphenylmethane, trimethylene glycol-di (p-aminobenzoate), polyethylene glycol-di (p-aminobenzoate), polytetramethylene glycol- Di (p-aminobenzoate); saturated diamines such as ethylenediamine, 1,3-propylenediamine, 2-methylpentamethylenediamine, hexamethylenediamine, 2,2,4- and 2,4,4-trimethyl-1,6 -Hexanediamine, imino-bis (propylamine), imide-bis (propylamine), methylimimino-bis (propylamine) (ie N- (3-aminopropyl) -N-methyl-1,3-propanediamine), 1,4-bis (3-aminopropoxy) butane (ie, 3,3'-[1,4-butanediylbis (oxy) bis] -1-propaneamine), diethylene glycol-bis (propylamine) (ie, diethylene glycol- Di (aminopropyl) ether), 4,7,10-trioxatridecane 1,3-diamine, 1-methyl-2,6-diamino-cyclohexane, 1,4-diamino-cyclohexane, poly (oxyethylene-oxy) Propylene) Diamine, 1,3- or 1,4-bis (methylamino) -cyclohexane, isophoronediamine, 1,2- or 1,4-bis (sec-butylamino) -cyclohexane, N, N'-diisopropyl- Isophoronediamine, 4,4'-diamino-dicyclohexylmethane, 3,3'-dimethyl-4,5-di4,3'-diaminodicyclohexylmethane, 3,3'-dichloro-4,4'-diaminodicyclohexylmethane, N, N'-Dialkylaminodicyclohexylmethane, polyoxyethylenediamine, 3,3'-diethyl-5,5'-dimethyl-4,4'-diamino-dicyclohexylethane, polyoxypropylenediamine, 3,3'-diethyl-5,5' -Dichloro-4,4'-diaminodicyclohexylmethane, polytetramethylene etherdiamine, 3,3', 5,5'-tetraethyl-4,4'-diamino3,3'-dichloro-4,4'-diaminodicyclohexyl Methane (ie 4,4'-methylenebis (2,6-diethylaminocyclohexane)), 3,3'-dichloro-4,4'-diaminodicyclohexylmethane, 2,2'-dichloro-3,3', 5,5 '-Tetraethyl-4,4'-diaminodicyclohexylmethane, polyoxypropylene ether diamine capped with (ethylene oxide), 2,2', 3,3'-tetrachloro-4,4'-diaminodicyclohexylmethane, 4,, 4'-bis (sec-butylamino) -dicyclohexylmethane; triamines such as diethylenetriamine, dipropylenetriamine, (propylene oxide) based triamine (ie polyoxypropylenetriamine), N- (2-aminoethyl) -1 , 3-Propylene diamine (ie N-Diaminodicyclohexylmethane (ie 4,4'-methylenebis (2,6-diethylaminocyclohexane)), 3,3'-dichloro-4,4'-diaminodicyclohexylmethane, 2,2'-dichloro-3,3', 5,5'-Tetraethyl-4,4'-diaminodicyclohexylmethane, polyoxypropylene etherdiamine capped with (ethylene oxide), 2,2', 3,3'-tetrachloro-4,4'-diaminodicyclohexylmethane , 4,4'-bis (sec-butylamino) -dicyclohexylmethane; triamines such as diethylenetriamine, dipropylenetriamine, (propyleneoxide) based triamine (ie, polyoxypropylenetriamine), N- (2-aminoethyl) ) -1,3-Propylenediamine (ie N-Diaminodicyclohexylmethane (ie 4,4'-methylenebis (2,6-diethylaminocyclohexane)), 3,3'-dichloro-4,4'-diaminodicyclohexylmethane, 2,2'-dichloro-3,3', 5,5'-Tetraethyl-4,4'-diaminodicyclohexylmethane, polyoxypropylene etherdiamine capped with (ethylene oxide), 2,2', 3,3'-tetrachloro-4,4'-diaminodicyclohexylmethane , 4,4'-bis (sec-butylamino) -dicyclohexylmethane; triamines such as diethylenetriamine, dipropylenetriamine, (propyleneoxide) based triamine (ie, polyoxypropylenetriamine), N- (2-aminoethyl) ) -1,3-Propylenediamine (ie N₃-Amine), glycerin-based triamine, all saturated); tetraamine, eg, N, N'-bis (3-aminopropyl) ethylenediamine (ie, N)₄-Amine) (both saturated), triethylenetetramine; also contains other amines such as tetraethylenepentamine (saturated as well).

When the polyurea prepolymer is reacted with an amine terminal curing agent during the chain extension step, the resulting composition is essentially a pure polyurea composition. On the other hand, when the polyurea prepolymer is reacted with the hydroxyl-terminated hardener during the chain extension step, the excess isocyanate groups in the prepolymer react with the hydroxyl groups in the hardener to form urea bonds and form polyurea. Form to form a polyurea urethane hybrid. Here, the terms urea and polyurea are used interchangeably.

This chain extension step, which occurs when the polyurea prepolymer is reacted with a hydroxyl hardener, an amine hardener, or a mixture thereof, increases the molecular weight and extends the chain length of the prepolymer. When the polyurea prepolymer reacts with the amine curing agent, a polyurea composition having a urea bond is produced. Reaction of the polyurea prepolymer with a hydroxyl curing agent yields a polyurea / urethane hybrid composition containing both urea and urethane bonds. The polyurea / urethane hybrid composition is different from the pure polyurea composition. The concentrations of urea and urethane bonds in the hybrid composition vary. In general, the hybrid composition may contain a mixture of about 10-90% urea and about 90-10% urethane bonds. The resulting polyurea or polyurea / urethane hybrid composition has elastomeric properties based on the phase separation of the soft and hard segments. Soft segments formed from polyamine reactants are generally flexible and mobile, while hard segments formed from isocyanates and chain extenders are generally hard and immobile.

[Thermoplastic Polyamide Elastomer]

As used in the present invention, the term "polyamide elastomer" is meant to include a copolymer of a polyamide block and a polyether block, i.e., a polyether block amide polymer, and a mixture of these copolymers and the aforementioned polyamides. I want to be understood. Polymers with polyamide blocks and polyether blocks result from polycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, which are, among other things, a) polyamides with diamine chain ends. Co-condensation of the sequence with a polyoxyalkylene sequence having a dicarboxylic acid chain end; b) Co-condensation of a polyamide sequence with a dicarboxylic acid chain end with a polyoxyalkylene sequence having a diamine end, which is α-ω -Dihydroxylated Aliase polyoxyalkylene sequences obtained by cyanoethylation and hydrogenation, known as polyether diols; c) Copolycondensation of polyamide sequences with dicarboxylic acid chain ends with polyether diols (obtained). The substance is, in certain cases, a polyether ester amide).

Polyamide sequences containing dicarboxylic chain terminals are generated, for example, in the presence of chain-restricted dicarboxylic acids, initiated by the condensation of lactam or the α'ω-aminocarboxylic acid of the dicarboxylic acid with a diamine. Polyamide blocks are advantageously made of polyamide-12. The number average molecular weight of the polyamide sequence is 300 to 15,000, preferably 600 to 5,000. The molecular weight of the polyether sequence is 100 to 6,000, preferably 200 to 3,000.

Polymers containing polyamide blocks and polyether blocks can have randomly distributed units. These polymers can be prepared by simultaneous reaction of the precursor of the polyether and the polyamide block. For example, polyetherdiols, lactams (or α, ω-amino acids) and chain-restricted diacids can be reacted in the presence of small amounts of water. A variety of randomly reacted reactants are also statistically distributed along the polymer chains, although polymers with essentially significantly variable length polyether blocks and polyamide blocks are obtained.

These polymers having a polyamide block and a polyether block, for example, whether they are derived from the copolycondensation of the pre-prepared polyamide and the polyether sequence or from a one-step reaction, eg, 20 ~. It has a shore D hardness of 90, preferably 25-85, more preferably 30-80, even more preferably 35-78, and an intrinsic viscosity of 0.8-2.5 measured in metacresol at 25 ° C.

Regardless of whether the polyester block is derived from polyethylene glycol, polyoxypropylene glycol, or polyoxytetramethylene glycol, they are used as is and are polycondensed or aminated with the polyamide block containing the carboxyl ends. It is converted to a polyether diamine and condensed with a polyamide block containing a carboxyl end. They can also be mixed with polyamide precursors and chain limiting agents to form polymers with polyamide blocks and polyether blocks with statistically distributed units. Polymers with polyamides and polyether blocks are disclosed in US Pat. Nos. 4,331,786, 4,115,475, 4,195,015, 4,839,441, 4,864,014, 4,230,838 and 4,332,920n. , These contents are incorporated here with reference. The polyether may be, for example, polyethylene glycol (PEG), polypropylene glycol (PPG) or polytetramethylene glycol (PTMG). The latter is also known as polytetrahydrofuran (PTHF).

Polyester blocks are introduced into the chains of polymers, including polyamide blocks, and regardless of whether the polyether blocks are in the form of diols or diamines, they are known as PEG blocks or PPG blocks or PTMG blocks for simplicity. ing. The polyether block may also include different units such as units derived from ethylene glycol, propylene glycol or tetramethylene glycol. For polymers with polyamide blocks and polyether blocks, it is advantageous that polyamide is the major component by weight, i.e. in the form of blocks, and optionally the amount of polyamide statistically distributed in the chain. More than 50% by weight of the polymer with blocks and polyether blocks. The amount of polyamide and the amount of polyether are not necessarily such, but are advantageous in the ratio of 50/50 to 80/20 (polyamide / polyether). Polyamide blocks and polyether blocks of the same polymer (B) preferably have molecular weights of Mn of 1000/1000, 1300/650, 2000/1000, 2600/650 and 4000/1000, respectively.

Some examples of commercially available transparent polyamides that can be used in accordance with the present invention are shown in Table IIA-IID below. In the examples provided in Tables IIA-IID, the material properties of the composition (100% polyamide) are provided by themselves. The information contained in Table IIA-IID is reported in technical data sheets made available by various commercial suppliers. These polyamide samples are particularly preferred because of their transparent optical properties. In a particularly preferred embodiment, clear polyamides, Rilsan® G120 Rnew; Rilsan G830 Rnew; Rilsan Clear G850; Rilsan Clear G350; and Rilsan Clear G300 HI are used.

<tables><img file="JP7074740B2_D0004.tif" /></tables><tables><img file="JP7074740B2_D0005.tif" /></tables><tables><img file="JP7074740B2_D0006.tif" /></tables><tables><img file="JP7074740B2_D0007.tif" /></tables><tables><img file="JP7074740B2_D0008.tif" /></tables><tables><img file="JP7074740B2_D0009.tif" /></tables><tables><img file="JP7074740B2_D0010.tif" /></tables><tables><img file="JP7074740B2_D0011.tif" /></tables>

Additional examples of commercially available polyamides that can be used in accordance with this invention are shown in Tables IIIA-D below. In the examples provided in Tables IIIA-D, the material properties of the composition (100% polyamide) are provided by themselves. The information presented in Tables IIIA-D is reported in technical data sheets made available by various commercial suppliers.

<tables><img file="JP7074740B2_D0012.tif" /></tables><tables><img file="JP7074740B2_D0013.tif" /></tables><tables><img file="JP7074740B2_D0014.tif" /></tables><tables><img file="JP7074740B2_D0015.tif" /></tables><tables><img file="JP7074740B2_D0016.tif" /></tables><tables><img file="JP7074740B2_D0017.tif" /></tables><tables><img file="JP7074740B2_D0018.tif" /></tables><tables><img file="JP7074740B2_D0019.tif" /></tables>

[Polyamide blend]

Polyamide blends may also be used according to the present invention. For example, a blend of transparent polyamides or a blend of transparent polyamides and opaque polyamides may be used according to the present invention. Specifically, a blend of transparent polyamide and thermoplastic polyamide elastomer (usually a copolymer of polyamide and polyester / polyether) may be used. The polyamide elastomer may be transparent or opaque. Many polyamide elastomers are composed of hard polyamide segments (eg, nylon 6, nylon 6, 6, nylon 11, nylon 12, etc.) and polyether or polyester as soft segments. Suitable polyamide elastomers that can be used to form the compositions of the present invention include, but are not limited to, for example, polyetheramide block copolymers available as Pebax resins from Arkema, Inc (Columbs, France). In general, these block copolymers have thermoplastic (softening when exposed to heat and returning to their original state when cooled) and elastomeric (releasing when stretched) properties. I have. The ratio of hard segments to soft segments, as well as the length and sequence of the segments, are important factors that determine the properties of the resulting block copolymer.

Generally, the polyether amide block copolymer may be prepared by polycondensation of a polyamide having a carboxyl end group and a polyether glycol. These block copolymers may be prepared using polyethylene glycols, polypropylene glycols, polytetramethylene glycols, copolyethers derived from them, and copolymers of THF and 3-alkyl THF, which are US Pat. No. 4,230,838, It is shown in No. 4,252,920, No. 4,349,661, No. 4,331,786, and No. 6,300,463. These contents are incorporated here with reference. The general structure of the polyether amide block copolymer may be expressed by the following formula (I).

<chemistry><img file="JP7074740B2_D0020.tif" /></chemistry>Represents a polyamide segment containing a terminal carboxyl group or an acid equivalent thereof (eg, acid anhydride, acid chloride or diester).<chemistry><img file="JP7074740B2_D0021.tif" /></chemistry>Is a polyether segment.

Different grades of Pebax polyether amide block copolymers that can be used in accordance with the present invention and their respective properties are listed in Tables IVA and IVB below. The information contained in Tables IVA and IVB is reported in technical data sheets available to commercial suppliers (Arkema, Inc.).

<tables><img file="JP7074740B2_D0022.tif" /></tables><tables><img file="JP7074740B2_D0023.tif" /></tables>

In a particularly preferred version, a blend of polyamide polymers described in US Pat. No. 8,399,557 (Montanari '557), such as Montonari, described above, is used to form the compositions of the invention. These transparent blends (or alloys) have the following (A), (B) and (C), totaling 100% by weight. Below is the important%.

(A) At least one constituent copolymer from 1 to 99%: Highly transparent with a transmittance of more than 65% at 560 nm through a sheet with a thickness of 2 mm. It shows a glass transition temperature of at least 90 ° C. Shows the crystallinity to amorphous or semi-crystalline. It has an amide unit (A1) containing an amide unit produced from at least one alicyclic diamine unit; and (A2) a flexible ether unit.

(B) At least one constituent polymer of 99-1% selected from the following: (Ba) a semi-crystalline copolyamide having an amide unit (Ba1) and an ether unit (Ba2), wherein the semi-crystalline copolyamide The glass transition temperature (Tg) is 65 ° C; and such copolyamide (Ba) based alloys.

(C) 0-50% by weight of at least one polyamide, copolyamide, or copolyamide having ether units other than those used in (A) and (B) above; and / or usually of thermoplastic polymers and copolymers. At least one additive of; the unit or monomer in the composition of (A), (B) and (C) is selected and the properties of the above-mentioned unit or above-mentioned monomer are also selected, and the resulting blend or alloy is Achieves great transparency so that the transmittance of a 2 mm thick sheet at 560 nm exceeds 50%.

The reaction products of the above components (A), (B), and (C) may be used to form a polyamide composition suitable for use in the present invention. Methods for making components (A), (B), and (C) are also described in the Montanari '557 patent. For example, the copolymer (A) can be prepared by charging an alicyclic diamine, and the diacid is charged in an 80 liter autoclave. Purge the reactor with nitrogen, close it, and heat to 260 ° C under pressure with stirring at 40 rpm. After maintaining for 1 hour, reduce the pressure to atmospheric pressure and add the polyether and catalyst. Place the reactor under vacuum for at least 30 minutes to reach 50 mbar (20 mbar if necessary). The couple's rise lasts about two hours. When the viscosity is reached, the reactor is returned to atmospheric pressure, the product is granulated and dried under vacuum at 75 ° C. Also described is how to make the blend. For example, the granular components (A), (B) and (C) can be blended, which is injection molded in an injection molding machine at a temperature of 230 ° C to 330 ° C. Examples of suitable polyamide copolymers described in the Montanari '557 patent, and their related properties, are listed in Table IV below.

<tables><img file="JP7074740B2_D0024.tif" /></tables><u style="Single">Polyamide A</u>-Diamine (3,3''-dimethyl-4,4'-diaminodicyclohexylmethane (BMACM) and diacid (C12 (0.5) -C14 (0.5)) and 25% polyether (polytetramethylene glycol [PTMG]) Polyamide copolymer made from.

<u style="Single">Polyamide B</u>-Polyamide copolymer made from diamine (BMACM) and diacid (C14 (0.5) -C18 (0.5)) and 23% polyether (PTMG).

<u style="Single">Polyamide C</u>-Polyamide copolymer made from diamine (BMACM) and diacid (C12 (0.5) -C14 (0.5)) and 20% polyether (PTMG).

<u style="Single">Polyamide D</u>-Polyamide copolymer made from diamine (BMACM) and diacid (C10 (0.5) -C12 (0.5)) and 12% polyether (PTMG).

Delta Hm (2)-This refers to the melting enthalpy of the DSC during the second heating according to the ISO standard, which is a differential scanning calorimetry.

Transparency: Characterized by the measurement of light transmittance at a wavelength of 560 nm through a 2 mm thick abrasive sheet. The amount of transmitted light expressed as a percentage is measured.

Flex modulus: The flex modulus of the sample is measured either at 80x10x4mm bars according to ISO 178 (MPa) or according to the E'modulus obtained at 23 ° C during the DMA measurement.

Ross-Flex Test ASTM 1052: Drill a 2.5 mm diameter hole in a 2 mm thick flat specimen and bend at 90 ° or -10 ° C at the level of this hole. Withstand as many cycles as possible without breaking.

Break elongation (%): Tension for ISO R527.

Viscosity: Intrinsic viscosity (dl / g) from 0.5 g dissolved in metacresol at 25 oC.

Yellowing: With measurement of the yellow index (YI) of the granules.

[Thermoplastic Polyester Elastomer]

These may be arbitrarily disclosed.

As described above, polyester-based thermoplastic elastomers may be used to form the compositions of the present invention. In general, a "thermoplastic elastomer" is a thermoplastic-like property (which softens when exposed to heat and returns to its original state when cooled) and an elastomer-like property (which returns to its original state when stretched). Refers to the class of polymer that has. Thermoplastic Elastomer Block Copolymers have several blocks with thermoplastic-like properties, and these blocks are sometimes referred to as "hard" segments. There are also some blocks that have elastomer-like properties, and these blocks are sometimes referred to as "soft" segments. The ratio of hard segments to soft segments and the composition of the segments are important factors in determining the properties of the resulting thermoplastic elastomer.

An example of a suitable polyester thermoplastic elastomer that can be used to form the compositions of the present invention is a polyester-polyester block copolymer. In general, these block copolymers contain hard and soft segments with varying lengths and sequences. Hard crystalline polyester segments are usually obtained by reacting an aromatic-containing dicarboxylic acid or diester, such as terephthalic acid, dimethyl terephthalate, with a diol containing about 2 to about 10 carbon atoms. For example, the hard segment may constitute a butylene terephthalate, tetramethylene terephthalate, or ethylene terephthalate unit. Soft elastomer segments typically contain a total of about 3 to about 12 carbon atoms, including up to 3 or 4 oxygen atoms, with the remaining atoms being hydrocarbon atoms, long or short chain poly (alkylene oxide) glycols. Is derived from. Useful poly (alkylene oxide) glycols include, for example, poly (oxyethylene) diols, poly (oxypropylene) diols, and poly (oxytetramethylene) diols. More specifically, the polyether polyols are based on polymers derived from cyclic ethers such as ethylene oxide, 1,2-propylene oxide and tetrahydrofuran. When these cyclic ethers are subjected to ring-opening polymerization, the corresponding polyether glycols such as polyethylene ether glycol (PEG), poly (1,2-propylene) glycol (PPG), and polytetramethylene ether glycol (PO4G, as well) Also called PTMEG).

One preferred polyester thermoplastic elastomer is Ticona-Celanese. Riteflex® material available from Corp. Riteflex TPC-ET products include various grades of polyester-polyester block copolymers, examples of such materials and their respective properties are shown in the table below. Another preferred polyester-polyester block copolymer is commercially available from DoPont under the trademark Hytrel . Hytrel polyester block copolymers come in a variety of grades, including hard (crystalline) segments of polybutylene terephthalate and soft (amorphous) segments based on long chain polyether glycols. These and other examples of polyester-polyether block copolymers that can be used in accordance with the present invention are disclosed in US Pat. Nos. 2,623,031; 3,651,014; 3,763,109; and 3,896,078; The contents of are incorporated here by reference. Various grade books of Hytrel that may be used in accordance with the present invention are set forth in Tables 2 and 3 of US Pat. No. 9,415,268, the contents of which are incorporated herein by reference.

<tables><img file="JP7074740B2_D0025.tif" /></tables><tables><img file="JP7074740B2_D0026.tif" /></tables><tables><img file="JP7074740B2_D0027.tif" /></tables>

As shown in Tables VII and VIII above, the flexural modulus of some Hytrel polyester-polyether block copolymers may be in the range of about 1,000 to about 150,000 psi (or higher). Such block copolymers can be used to form low modulus (or high modulus) core layers according to the present invention.

[Polyester blend]

Blends of polyesters and blends of polyesters with other polymers may be used in accordance with the present invention. For example, the polyester thermoplastic elastomer may be blended with other thermoplastics such as polyamide. Various plasticizers may be used in the polyester-based thermoplastic composition, and these plasticizers will be further discussed below. Suitable polyamide elastomers that can be used to form the compositions of the present invention include, for example, the polyether amide block copolymers available as Pebax resins from Arkema, Inc (Columbs, France). Other suitable polyamides are Nylon 4, Nylon 6, Nylon 7, Nylon 11, Nylon 12, Nylon 13, Nylon 4, 6, Nylon 6, 6; Nylon 6, 9, Nylon 6, 10, Nylon 6, 12, Includes Nylon 12,12, Nylon 13,13, and mixtures thereof. More preferred polyamides are Nylon 6, Nylon 11, Nylon 12, Nylon 4, 6, Nylon 6,6, Nylon 6,9, Nylon 6,10, Nylon 6,12, Nylon 6/66, and Nylon 6/69 and Contains a mixture of them.

Ionomers, thermoplastic polymers, PEPA may be mixed or otherwise combined and molded using any method known to those of skill in the art. In this regard, these components can be added to the masterbatch simultaneously or sequentially prior to molding. Alternatively, one or more of these components may be combined first and then added to the remaining components. Compression and injection molding, retractable pin injection molding (RPIM) methods, reaction injection molding (RIM), liquid injection molding, casting and the like may be used. Note that in some examples a layer of three-component thermoplastic blend is formed around the subassembly by spraying, powder coating, vacuum forming, flow coating, dipping, and / or spin coating.

Many desirable golf ball structures are possible that incorporate at least one layer of a three-component thermoplastic blend with a characteristic gradient within at least one layer and between that layer and adjacent and non-adjacent layers.

You can create a gradient of properties in at least one layer. For example, if at least one layer is a layer surrounding a spherical subassembly, the at least one layer can have an inner surface hardness that differs from the outer surface hardness by up to about 30 Shore A hardness points. In one such embodiment, the inner surface hardness and the outer surface hardness may differ by up to about 5 shore A hardness points. In another embodiment, the inner surface hardness and the outer surface hardness may differ by up to about 10 Shore A hardness points. In yet another embodiment, the inner surface hardness and the outer surface hardness may differ by up to about 15 Shore A hardness points. In yet another embodiment, the inner and outer hardness may differ by up to about 20 Shore A hardness points. In other embodiments, the inner and outer surface hardness is between 2 and 10 shore A hardness points, or between 2 and 10 shore A hardness points, or between 2 and 10 shore A hardness points, or between 5 and 15 shores. It may vary between A hardness points, or between 10 and 20 shore A hardness points, or between 15 and 25 shore A hardness points, or between 20 and about 30 shore A hardness points.

In such an embodiment, the subassembly has a geometric center hardness and subassembly outer surface hardness that differ by up to 5 shore C hardness points, or up to 15 shore C hardness points, or 10 to about 30 shore C hardness points. Good.

On the other hand, the outer surface hardness and subassembly outer surface hardness are up to the shore D hardness point, up to the 10 shore D hardness point, or from about 5 to about 10 shore D hardness points, or from 5 shore D to about 15 shore D hardness points, or about. Different from 10 Shore D to about 25 Shore D hardness points, or 20 Shore D hardness points to about 35 Shore D hardness points, or about 30 Shore D to about 50 Shore D hardness points, or 40 to about 55 Shore D hardness points. good.

In some embodiments, the outer surface may have a shore D hardness of 20 to 70 and the geometric center may have a shore A hardness of 65 to 100. In other embodiments, the outer surface may have a shore A hardness of 65 to 100 and the geometric center may have a shore D hardness of 20 to 70. In one alternative embodiment, the outer surface may have a shore A hardness of 75 to 100 and a shore D hardness of 20 to 40 at the geometric center. In another alternative embodiment, the outer surface may have a shore A hardness of 75-100 and the geometric center may have a shore D hardness of 20-40. In yet another alternative embodiment, the outer surface may have a shore A hardness of 85-100 and the geometric center may have a shore D hardness of 40-60. In yet another alternative embodiment, the outer surface may have a shore A hardness of 90 to 100 and the geometric center may have a shore D hardness of 40 to 70.

In an embodiment where the three-component thermoplastic blend is the spherical core component of a golf ball, the core is from about 20 shore D to about 70 shore D, or from about 40 shore D to about 60 shore D, or from about 20 shore D. It may have a material hardness of about 55 shore D, or about 20 shore D to about 45 shore D, or about 35 shore D to about 65 shore D, or about 55 shore D to about 70 shore D.

In other embodiments where the three-component thermoplastic blend is a spherical core component of a golf ball, the core is about 60 to 100, or about 65 to about 95, or about 70 to about 90, or about 65 to about 86, or It may have a shore A hardness of 75 to 100, or 80 to 100, or 90 to 100.

In one example, the hardness of the three-component thermoplastic blend differs from the hardness of the outer surface of at least one other layer to form a negative or positive hardness gradient up to the Shore D hardness point. In another embodiment, the hardness of the three-component thermoplastic blend differs from the hardness of the outer surface of at least one other layer to form a negative or positive hardness gradient of 1-5 Shore D hardness points. In yet another embodiment, the hardness of the three-component thermoplastic blend is different from the hardness of the outer surface of at least one other layer, forming a negative or positive hardness gradient of Shore D hardness points greater than 5 and up to about 20. do. In yet another embodiment, the hardness of the three-component thermoplastic blend forms a negative or positive hardness gradient of Shore D hardness points above 20 and up to about 45, unlike the hardness of the outer surface of at least one other layer. do. In an alternative embodiment, the hardness of the three-component thermoplastic blend is different from the hardness of the outer surface of at least one other layer, forming a negative or positive hardness gradient of Shore D hardness points greater than 25 and up to about 50. ..

In an alternative embodiment, the layer of the three-component thermoplastic blend is included in the golf ball of the invention as a single solid core with a "positive" or "negative" hardness gradient, or as a "dual core". May be good. At least one of the inner and outer core layers incorporates a three-component thermoplastic material and has a positive or negative hardness gradient.

An example of an example of a "positive" hardness gradient in which a single solid core comprises a three-component thermoplastic blend is as follows: The surface hardness of the core ranges from 25 shore D to 90 shore D, or 45 shore D to 70. In certain embodiments, the surface hardness is 68 shore D, 60 shore D, or 49 shore D. The corresponding hardness at the center of the solid core may range from 30 shore D to 80 shore D, or 40 shore D to 65 shore D, or in a specific embodiment 61 shore D, 52 shore D, respectively. , Or 43 Shore D.

Examples of examples of "negative" hardness gradients in which a single solid core comprises a three-component thermoplastic blend are: The surface hardness of the core ranges from 20 shore D to 80 shore D, or 35 shore D to 60 shore D, and in specific embodiments, the surface hardness is 56 shore D, 45 shore D, or 40 shore D. Good. The corresponding center hardness may range from 30 shore D to 75 shore D, or 40 shore D to 65 shore D, and in a specific embodiment, 61 shore D, 52 shore D, or 43 shore D, respectively. ..

In the dual-core "low spin" embodiment, the inner surface of the outer core layer is harder than the outer surface of the inner core. In the dual-core "high spin" embodiment, the inner surface of the outer core layer is softer than the outer surface of the inner core.

An example of an example of a "positive" hardness gradient in which at least one layer of the dual core comprises a three-component thermoplastic blend is: The outer core surface hardness is 25 shore D to 90 shore D, or 45 shore D to 70 shore D, and in a specific embodiment, 68 shore D, 61 shore D, or 49 shore D. The inner surface of the outer core has a corresponding hardness of 61 shore D, 61 shore D, or 43 shore D, respectively. The surface of the inner core may have 43 shore D, 60 shore D, or 49 shore D, respectively, in the range from 40 shore D to 65 shore D, or in specific embodiments. The center hardness of the inner core may range from 30 shore D to 80 shore D, or 40 shore D to 55 shore D, with 43 shore D, 50 shore D or 43 shore D, respectively, in specific embodiments. be.

Examples of examples of "negative" hardness gradients in which at least one layer of the dual core comprises a three-component thermoplastic blend are: The outer core surface hardness may range from 20 shore D to 80 shore D, or 35 shore D 55 shore D, and in specific embodiments is 45 shore D, 40 shore D, or 52 shore D. The inner surface of the outer core may have a corresponding hardness of 52 shore D, 43 shore D, or 52 shore D, respectively. The surface of the inner core may range from 30 shore D to 75 shore D, or 50 shore D to 65 shore D, and in specific embodiments, 61 shore D, 52 shore D, or, respectively. 56 Shore D is acceptable. The central hardness of the inner core may range from 50 shore D to 65 shore D and, in a specific embodiment, is 61 shore D, 52 shore D, or 61 shore D, respectively. The "negative" gradient is steep.

In the "low spin" embodiment of the present invention, the hardness of the inner core containing the three-component thermoplastic blend (at any point-surface, center, or other) ranges from 30 shore C to 80 shore C, or 40 shore C. It may range from 75 shore C or 45 shore C to 70 shore C. At the same time, the hardness of the outer core layer (surface, inner surface, etc.) may range from 60 shore C to 95 shore C, or 60 shore C to 90 shore C, or 65 shore C to 80 shore C.

In different "low spin" examples of the invention, the hardness (surface, center, or other point) of the inner core containing the three-component thermoplastic blend is from 30 shore C to 80 shore C, or 40 shore C to 75. It may range from shore C or from 45 shore C to 70 shore C. At the same time, the hardness of the outer core layer containing the three-component thermoplastic blend (any point, surface, inner surface, etc.) is 60 shore C to 95 shore C, or 60 shore C to 90 shore C, or 65 shore C to 80 shore. It may be in the range of C.

In an alternative "low spin" embodiment of the invention, the hardness of the inner core (any point, surface, center, etc.) containing the three-component thermoplastic blend is from 30 shore C to 80 shore C, or 40. It may range from Shore C to 75 Shore C, or 45 Shore C to 70 Shore C. At the same time, the hardness of the outer core layer containing the three-component thermoplastic blend (any point, surface, inner surface, etc.) is 60 shore C to 95 shore C, or 60 shore C to 90 shore C, or 65 shore C to 80 shore. It may be in the range up to C.

In the "high spin" example, the hardness of the inner core containing the three-component thermoplastic blend ranges from 60 shore C to 95 shore C, or 60 shore C to 90 shore C, or 65 shore C to 80 shore C. It's okay to have it. At the same time, the hardness of the outer core layer containing the three-component thermoplastic blend may range from 30 shore C to 80 shore C, or 40 shore C to 75 shore C, or 45 shore C to 70 shore C.

In another "high spin" example, the hardness of the inner core containing the three-component thermoplastic blend ranges from 60 shore C to 95 shore C, or 60 shore C to 90 shore C, or 65 shore C to 80 shore C. It may be. At the same time, the hardness of the outer core layer containing the three-component thermoplastic blend may range from 30 shore C to 80 shore C, or 40 shore C to 75 shore C, or 45 shore C to 70 shore C.

In an alternative "high spin" example, the hardness of the inner core containing the three-component thermoplastic blend is 60 shore C to 95 shore C, or 60 shore C to 90 shore C, or 65 shore C to 80 shore C. It may be a range. At the same time, the hardness of the outer core layer containing the three-component thermoplastic blend may range from 30 shore C to 80 shore C, or 40 shore C to 75 shore C, or 45 shore C to 70 shore C.

The property gradient can be a percent neutralization gradient created between the inner and outer surfaces of at least one layer of the three-component thermoplastic resin blend, and alternatives can be at least one of the three-component thermoplastic blends. Gradually develop from the outer surface to the inner surface of the two layers.

In different embodiments, the at least one layer of the golf ball consists of (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. It may have a three-component thermoplastic blend consisting of one different thermoplastic polymer; and (iii) multiple core-shell polymers, where at least one of the cores and shells of each core-shell polymer is one or more polymethyls (meth). ) Has an acrylate-based polymer. The thermoplastic blend contains (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer, T is the weight% of the different thermoplastic polymer, and C is the core-shell polymer. By weight%, I&gt; 45, and 2 C &lt;35.

Each core-shell polymer may have a diameter of about 0.5 micron to about 20.0 micron. In a specific example, each core-shell polymer has a diameter of about 0.05 micron to about 0.20 micron.

In one embodiment, at least one of the plurality of core-shell polymers has a urethane-containing core. In another embodiment, at least one of the plurality of core-shell polymers has a non-urethane-containing core.

In another embodiment, the at least one layer consists of (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. Different thermoplastic polymers; and (iii) at least one polymethyl (meth) acrylate-based copolymer may have a three-component thermoplastic blend consisting of the following: The three-component thermoplastic blend comprises (i), (ii), and (iii) in a weight% ratio I: T: C, where I is the weight% of the ionomer and T is the weight% of the different thermoplastic polymer. , C is the weight% of the polymethyl (meth) acrylate-based copolymer, I&gt; 45 and 2 C &lt;35.

In some embodiments, the at least one layer consists of (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. Two different thermoplastic polymers; and (iii) a three-component thermoplastic blend consisting of multiple core-shell polymers, where at least one of the cores and shells of each core-shell polymer is one or more polymethyl (meth) acrylate-based. Has a copolymer. And in other embodiments, at least one layer consists of (i) at least one ionomer; (ii) at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane hybrid, or a combination thereof. It may consist of a three-component thermoplastic blend consisting of one different thermoplastic polymer; and (iii) at least one polymethyl (meth) acrylate-based copolymer.

In such an embodiment, the polymethyl (meth) acrylate-based copolymer is a polymethyl (meth) acrylate-based n-butyl acrylate polymethyl (meth) acrylate-based ethyl acrylate. Polymethyl (meth) acrylate-based n-butyl acrylate styrene Polymethyl (meth) acrylate-based butadiene styrene; Polymethyl (meth) acrylate-based acrylonitrile butadiene styrene Polymethyl (meth) acrylate-based ethylene propylene diene (EPDM); Polymethyl ( Meta) acrylate-based EPDM-styrene; polymethyl (meth) acrylate-based glycidyl methacrylate-ethyl acrylate; polymethyl (meth) acrylate-based glycidyl; (meth) acrylate-n-butyl acrylate; polymethyl (meth) acrylate-based styrene-acrylonitrile It may be selected from the group consisting of polymethyl (meth) acrylate-based butadiene; and combinations thereof.

Polymethyl (meth) acrylate-based copolymers are (meth) acrylates derived from saturated alcohols; (meth) acrylates derived from unsaturated alcohols; aryl (meth) acrylates; cycloalkyl (meth) acrylates; hydroxyalkyls (meth). ) Acrylate; glycol di (methacrylate); (meth) acrylate of ether alcohol; amide of (meth) acrylic acid; nitrile of (meth) acrylic acid; sulfur-containing (meth) acrylate; polyfunctional (meth) acrylate; and its It may have a (meth) acrylate selected from the group consisting of combinations .

Polymethyl (meth) acrylate-based copolymers include methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, isohexyl acrylate n-heptyl acrylate, isoheptyl acrylate, capryl. Acrylate, (l-methylheptyl acrylate), n-octyl acrylate, ethylhexyl acrylate, isooctyl acrylate, methylheptyl acrylate, n-nonyl acrylate, isononyl acrylate, 3,5,5-trimethylhexyl acrylate, n-decyl acrylate, From the group consisting of isooctyl acrylates such as lauryl acrylate, n-amyl acrylate, n-hexyl acrylate, capryl acrylate (l-methylheptyl acrylate), n-octyl acrylate, n-methylheptyl acrylate, 2-ethylhexyl acrylate, and capryl acrylate. It may contain the acrylate of choice.

Polymethyl (meth) acrylate-based copolymers may have a comonomer selected from the group consisting of 1-alkene; branched alkene; acrylonitrile; styrene; maleic acid derivative; diene; and combinations thereof.

Polymethyl (meth) acrylate-based copolymers include alternating polymethyl (meth) acrylate-based copolymers, block polymethyl (meth) acrylate-based copolymers, random polymethyl (meth) acrylate-based copolymers, and graft polymethyl (meth) acrylate-based copolymers. You may choose from the group consisting of copolymers of, gradient polymethyl (meth) acrylate-based copolymers, and combinations thereof.

The thermoplastic polymers herein have acrylonitrile-butadiene-styrene terpolymer, acrylonitrile-styrene-acrylate, acrylonitrile-ethylene-styrene terpolymer, styrene acrylonitrile copolymer, styrene anhydride maleic acid copolymer, or a combination thereof. good.

The thermoplastic polymers herein may further comprise polycarbonate, maleic anhydride, grafted maleic anhydride, glycidyl methacrylate, modified polyolefins, modified styrene copolymers, or combinations thereof.

The thermoplastic polymers herein are a group consisting of poly (styrene-butadiene-styrene), poly (styrene-isoprene-styrene), poly (styrene-ethylene / butylene-styrene), and poly (styrene ethylene / propylene styrene). May include modified styrene copolymers selected from.

In some embodiments, the three-component thermoplastic blend may have a glass transition temperature Tg-b higher than the glass transition temperature Tg-tp of the thermoplastic polymer.

As used herein, the term polymethylmethacrylate-based copolymer or MMA copolymer includes poly (meth) acrylates, methacrylates, and acrylates. Polymethacrylates can be obtained using known methods such as free radical polymerization of (meth) acrylates. As used herein, the terms (meth) acrylate and methacrylate are used interchangeably.

The term "alternate" means that the MMA copolymer is composed of alternating sequences of different monomers in a ratio of approximately 1: 1. The term "block" means that an MMA copolymer is composed of a relatively long sequence of one monomer followed by a relatively long sequence of different monomers. The term "random" means that the MMA copolymer is composed of two or more different repeating units of randomly distributed (two or more) monomers. The term "graft" means that an MMA copolymer comprises a backbone of one type of monomer and a branch of another type of monomer. The term "gradient" means that the MMA copolymer exhibits a gradual change in composition along the chain, from almost one type of monomer at the beginning of the chain to almost one type at the end of the chain. More specific variations in some of these groups include, for example, star-shaped, comb-shaped, and / or centipede-shaped configurations.

Thermoplastic polymers and MMA copolymers may be mixed and molded using any method known to those of skill in the art. In this regard, the MMA copolymer is incorporated into the masterbatch and then added to the thermoplastic polymer prior to molding. Alternatively, the thermoplastic polymer and the MMA copolymer can be combined by at least one of high shear mixing followed by molding. Compression and injection molding, retractable pin injection molding (RPIM) methods, reaction injection molding (RIM), liquid injection molding, casting, etc. can be used. Note that there are examples in which a layer of the three-component thermoplastic blend of the present invention is formed around the subassembly by spraying, powder coating, vacuum formation, flow coating, immersion, and / or spin coating.

As used herein, the phrase "multiple core-shell polymers" refers to a group or loading of core-shell polymers that are combined with ionomers and thermoplastic polymers to form a three-component thermoplastic blend. In one example, all core-shell polymers of a particular group or loading may be substantially similar in both structure (shape / size) and composition. In other embodiments, the group or at least two core-shell polymers in loading may differ, such as having different core sizes / shapes and / or compositions, and / or having different shell sizes / shapes and / or compositions.

The loading of multiple core shells can be adjusted to change layer properties such as material hardness, flexural modulus, tensile strength and target mechanical strength, impact durability, shear resistance, etc. Depends at least in part on the specific properties of the thermoplastic polymer.

Each core shell may have a diameter of about 0.05 micron to about 20 microns. In one embodiment, each core-shell polymer may have a diameter of about 0.5 micron to about 20.0 micron. In another embodiment, each core-shell polymer has a diameter of about 0.05 micron to about 0.20 micron.

In one embodiment, at least one of the plurality of core-shell polymers has a urethane-containing core. In another embodiment, at least one of the plurality of core-shell polymers has a non-urethane-containing core.

The present invention also relates to a method of making a golf ball of the present invention, wherein the method is: a step of providing a subassembly; (i) an ionomer; (ii) a thermoplastic polymer; and (iii) (a) a plurality of core shells. It has a step of forming at least one layer consisting of a three-component thermoplastic blend of polymers around the subassembly, where each core-shell polymer has at least one core and one or more polymethyl (meth). It has an acrylate-based polymer and / or (b) at least one polymethyl (meth) acrylate-based polymer, where the thermoplastic polymer is at least one thermoplastic polyurethane, thermoplastic urea, thermoplastic urea-urethane. Have a hybrid, or a combination thereof.

In another embodiment, the method is (i) an ionomer (ii) a thermoplastic polymer; (iii) (a) a step of providing a subassembly consisting of a plurality of core-shell polymers, the core and shell of each core-shell polymer. At least one of the above has one or more polymethyl (meth) acrylate-based copolymers and / or (b) at least one polymethyl (meth) acrylate-based copolymer, and the thermoplastic polymer is at least one thermoplastic polyurethane, With the above steps having a thermoplastic urea, a thermoplastic urea-urethane hybrid, or a combination thereof; with the step of forming at least one layer having a thermoplastic or thermoplastic composition around the subassembly.

Core-shell polymers can be prepared by methods such as dispersion, precipitation, emulsion polymerization and the like. See, for example, "Core-shell polymer: a review", Ramli, Ros Azlinawati; Laftah, Waham Ashaier; Hashim, Shahrir, RSC Advances, 2013, 3, 15543-15565 ("Core-shell polymer review article"). I want to be done. The contents are referred to and incorporated here.

Non-limiting examples of suitable core-shell polymers include RayAce 5525, RayCore 9534A, RayCore 9507A, RayCore 9506A, and RayCore 9021A, all Specialty. It is commercially available from Polymers and Inc. RayAce 5525 Core Shell is an alkyd acrylic core shell hybrid with an average particle size of 0.16 microns, and RayCore 9534A, RayCore 9507A, RayCore 9506A, and RayCore 9021A have an average particle size of 9021A. 0.10 micron urethane-acrylic core shell hybrid. Additional examples of core-shell structures are US Pat. No. 4,419,471 (Nelsen et al.); US Pat. No. 4,666,777 (Ash et al.); US Pat. No. 4,876,313 (Lorah); US Pat. No. 5,006,592 (Oshima et al.); 5,183,858 (Sasaki et al.); US Pat. No. 5,206,299 (Oshima et al.); US Pat. No. 5,237,015 (Urban); US Pat. No. 5,242,982 (Oshima et al.); US Pat. No. 5,280,075 (Oshima et al.); US Pat. No. 5,280,076 No. (Sasaki et al.); US Pat. No. 5,290,858 (Sasaki et al.); US Pat. No. 5,304,707 (Blankenship et al.); US Pat. No. 5,324,780 (Oshima et al.); US Pat. No. 5,362,804 (Oshima et al.); Tsai et al. Patent No. 5,403,894 (Tsai et al.); US Pat. No. 5,453,458 (Takeuchi et al.); US Pat. No. 6,777,500 (Lean et al.); And US Pat. No. 6,858,301 (Ganapathiappan). These contents are incorporated here with reference.

Advantageously, the three-component thermoplastics of the present invention may have a glass transition temperature Tg-m higher than the glass transition temperature Tg-tp of the thermoplastic polymer. In this regard, the term glass transition temperature (Tg) refers to the temperature range in which a polymer transitions from a hard vitreous material to a soft rubbery material. If there is a melting temperature in the crystalline state of the material, the glass transition point is always lower than this melting temperature. Tg can be measured by MDSC, which is an extension of conventional DSC (DSC measures temperature and heat flow associated with transitions in a material as a function of temperature or time in a controlled environment. Differential scanning calorimetry (DSC) measurements are made using the DSC calorimeter NETZSCH, type 204).

MDSC divides the total heat flow into an inverted (heat capacity) component and a non-inverted (kinetic) component. The inverting signal includes heat capacity events such as glass transition and melting. Non-inverted signals include kinetic events such as crystallization, crystal integrity and reconstruction, curing and decomposition. Measuring instruments are also commercially available from TA Instruments.

In the three-component thermoplastics of the present invention, the interaction between a thermoplastic polymer with a relatively low Tg and multiple core-shell polymers with a relatively high Tg is improved compared to a layer of the thermoplastic polymer alone. It provides the mechanical strength, impact resistance and cutting fray resistance (groove shearing) resistance, and can better and reliably sustain the large force and impact of the club face when hitting a golf ball on the course.

In this regard, the Tg of the TPU is generally 0 ° C (32 ° F) or less, or -10 ° C or less, or -30 ° C or less, or -40 ° C or less. On the other hand, the Tg of poly (methylmethacrylate) is well above room temperature, around 100 ° C (212 ° F). Each core-shell polymer contains poly (methylmethacrylate) in one of its cores or shells and comprises a shell or core made of different materials, from the Tg of each core-shell polymer, the Tg of the thermoplastic polymer. Is also large, generally less than about 100 ° C (212 ° F).

In one specific example, the RayAce® 5525 alkyd-acrylic core-shell hybrid has a Tg of approximately 29 ° C (84.2 ° F). In another specific example, the Tg of the urethane-acrylic core-shell hybrid RayCore® 9534A, RayCore® 9507A, RayCore® 9506A and RayCore® 9021A is 30 ° C. (86 ° F), 42 ° C ° C (102.2 ° F), and 17 ° C (60.8 ° F). Thus, by mixing thermoplastic polyurethane with these core-shell polymers, it is possible to produce a layer that is superior in mechanical strength, impact resistance, and cutting fraying (groove shearing) resistance as compared with thermoplastic polyurethane. can.

In one example, at least some of the core-shell polymers have a glass transition temperature Tg-cs greater than Tg-tp. In another embodiment, all of the plurality of core-shell polymers have a glass transition temperature Tg-cs greater than Tg-tp. In certain embodiments, Tg-cs and Tg-tp differ by at least 25 ° C.

Non-limiting examples of suitable MMA-containing polymers for incorporation into core-shell structures are also available from Galen Chemicals, LLC, Blendex® 338, Blendex® 362, Blendex®. ) 3160, including Royaltuf® 960A.

In one example, the resulting layer contains the dissimilar three-component thermoplastics of the plurality of core-shell polymers disposed throughout the thermoplastic polyurethane polymer. In another embodiment, the resulting layer contains a heterogeneous three-component thermoplastic of the invention of multiple core-shell polymers disposed throughout the thermoplastic polyurea polymer. In yet another embodiment, the resulting layer contains the heterogeneous three-component thermoplastics of the invention of multiple core-shell polymers disposed throughout the thermoplastic polyurethane-polyurea polymer.

In any of these embodiments, the plurality of core-shells may be substantially similar or include a plurality of core-shells comprising two or more different core-shell types. For example, the plurality may include both a urethane-acrylic core-shell hybrid and an alkyd-acrylic core-shell hybrid. Alternatively, some may all include urethane-acrylic core-shell hybrids, but have different shell thicknesses.

At least one core-shell polymer of the plurality of core-shell polymers has a urethane-containing core, in some embodiments the core is a three-component thermoplastic thermoplastic polymer in one embodiment. It may be formed from the same polyurethane as it is formed. In other such embodiments, the core may be formed from a polyurethane that is different from the one on which the three-component thermoplastic thermoplastic polymer is formed.

In some embodiments, it is envisioned that at least one of the plurality of core-shell polymers has a non-urethane-containing core, and a large number of non-urethane compositions known in the art may form the core. On the other hand, in each of the plurality of core-shell polymers, at least one of the core and / or shell has one or more polymethylmethacrylate (MMA) copolymers. Each core-shell polymer uniquely and collectively contributes to the resulting three-component thermoplastic properties that the core or shell does not have individually, and when further combined with a three-component thermoplastic thermoplastic polymer. , Forming a more durable and robust layer than the three-component thermoplastic thermoplastic resin alone.

The interaction between each of the multiple core-shell polymers and the thermoplastic polymer is thermal with superior mechanical strength, impact durability, and cutting and fraying (groove shear) resistance compared to the thermoplastic polymer alone. It produces a plastic material that better and more reliably sustains the great force and impact of the club face hitting the golf ball on the course.

The resulting creative three-component thermoplastics of the present invention also have greater flexural modulus (ASTM D-790), tensile strength (ASTM D-638) and extremes than ternary thermoplastic thermoplastics. May have elongation (ASTM D-638). Relative amounts of thermoplastic polymers and multiple core-shell polymers are modified and adjusted to achieve the desired Tg, flexural modulus, tensile strength and / or extreme elongation of the three-component thermoplastic layer of the invention. , And the target can be controlled.

In this regard, the resulting three-component thermoplastic of the invention has a low or high flexural modulus as long as the flexural modulus of the three-component thermoplastic of the invention is greater than the flexural modulus of the thermoplastic polymer. It's okay. Thus, the three-component thermoplastic layer of the invention is, for example, within a range having a lower limit of about 300 psi or 1000 psi or 5000 psi or 10000 psi and an upper limit of 15000 or 20000 or 25000 or 30000 or 30000 or 35000 or 45000 or 50000 or 55000 psi. It may have a flexural modulus. In these examples, the flexural modulus of the three-component thermoplastic thermoplastic polymer is at least less than 5%, less than 10%, or at least less than 20%, or at least less than 25%, or at least less than 30%, or at least 35. Less than% less than the flexural modulus of the present invention.

Alternatively, the three-component thermoplastics obtained in the present invention have a lower limit of about 25000 or 30000 or 35000 or 40000 or 45000 or 50000 or 55000 or 60000psi and an upper limit in the range of 70000 or 75000 or 100000 or 150,000psi. It may have a high flexural modulus. In such examples, the modulus of elasticity of the three-component thermoplastic thermoplastic polymer is at least less than 5%, less than 10%, or at least less than 20%, or at least less than 25%, or at least less than 30%, or at least 35. Only less than% may be less than the modulus of elasticity of the three-component thermoplastics of the present invention.

Further, the three-component thermoplastic obtained by the present invention has a low tensile strength or a high tensile strength as long as the tensile strength of the three-component thermoplastic of the present invention is larger than the tensile strength of the three-component thermoplastic thermoplastic polymer. Good. In one non-limiting example, the tensile strength of the resulting layer may be greater than 4500 psi or greater than 5500 psi, or at least 6500 psi, or at least 7500 psi, or at least 8500 psi, or at least 9500 psi.

Further, the three-component thermoplastic obtained by the present invention has a low limit elongation or a high limit elongation as long as the limit elongation of the three-component thermoplastic of the present invention is larger than the limit elongation of the three-component thermoplastic thermoplastic polymer. You can do it. For example, the ultimate elongation may be at least 25%, or at least 50%, or at least 100%, or at least 125%, or at least 150%, or at least 175%, or 200%, or more.

In some embodiments, the shell thickness of each core-shell polymer produces a well-dispersed core-shell polymer that remains structurally intact within the thermoplastic polymer during and / or after melting. You may control the target to do so. In such an embodiment, a shell that is too thin will have its core partially exposed and interconnected to form a cellular structure, thereby resulting in inadequate reinforcement efficiency. The core may not be adequately protected.

On the other hand, if the shell of the core-shell polymer is too thick, it will cause insufficient elasticity, in which case the core-shell will not be used as an efficient impact modifier, but as a hard filler in the three-component thermoplastics of the present invention. It will be useful. Thus, the shell thickness of these core-shell polymers may be targeted and controlled in order to exhibit high efficiency in strengthening the resulting layer composition, regardless of particle size.

In one embodiment, the three-piece golf ball of the present invention has a core, an intermediate layer, and a cover layer, the core is formed of a rubber composition, the intermediate layer is formed of an ionomer composition, and the cover is the third of the present invention. Formed from a component thermoplastic blend. In one such embodiment, there is an ionomer, the thermoplastic polymer of the three-component thermoplastic blend is a thermoplastic polyurethane composition, and each of the plurality of core-shell polymers is an alkyd-acrylic core of RayAce® 5525. -Shell hybrid. In an alternative embodiment, each core-shell polymer is a urethane-acrylic core of RayCore® 9534A, RayCore® 9507A, RayCore® 9506A, and RayCore® 9021A. -One of the shell hybrids. In yet another embodiment, the plurality of core-shell polymers comprises both an alkyd-acrylic core-shell hybrid and a urethane-acrylic core-shell hybrid. In one embodiment, at least one core of the core-shell polymer comprises MMA and the shell is urethane. In another embodiment, at least one core of the core-shell polymer comprises urethane and the shell comprises MMA. In yet another embodiment, at least one of the plurality of core-shell polymers is non-urethane. The hardness of the layers obtained in each of these examples is from about 20 Shore D to about 70, as long as the resulting three-component thermoplastic blend has a hardness different from the hardness of the thermoplastic polymer of the three-component thermoplastic blend. It may be Shore D, and the elasticity of the obtained three-component thermoplastic blend is larger than the elasticity of the thermoplastic polymer of the three-component thermoplastic blend.

In various examples, the thermoplastic polymer of the three-component thermoplastic blend of the present invention may consist of a thermoplastic polyurea composition. In an alternative embodiment, the thermoplastic polymer of the three-component thermoplastic blend of the present invention may consist of a thermoplastic polyurethane-polyurea hybrid composition. In each of such various or alternative embodiments, the three-component thermoplastic blend of the present invention comprises a core-shell polymer as suggested in the embodiment where the thermoplastic polymer composition is polyurethane. good.

Although the golf ball of the present invention contains the three-component thermoplastic blend of the present invention in the outer cover layer, another golf ball layer (inner core, outer core, intermediate layer, etc.) may be used alternativeally or additionally. It should be appreciated that a three-component thermoplastic blend of the invention of the thermoplastic polymer and multiple core-shell polymers may be included.

In contrast, if a mixture free of ionomer components is created, thermoplastic polymers (thermoplastic polyurethanes, thermoplastic ureas, thermoplastic urea-urethane hybrids, or combinations thereof) and multiple core shells and / or polymethylmethacrylates are produced. --The base copolymer (MMA copolymer) may be included in the mixture in a weight ratio of about 98: 2 to about 50:50. In other embodiments, the thermoplastic polymer and the MMA copolymer may be included in the mixture in a weight ratio of 95: 5 to 55:45. In yet another embodiment, the thermoplastic polymer and the MMA copolymer may be included in the mixture in a weight ratio of 93: 7 to 65:35.

Golf balls having various structures may be manufactured according to the present invention. For example, a golf ball having a two-piece, three-piece, four-piece, and five-piece structure and with a single or multi-layered cover material may be manufactured. A representative description of such a golf ball structure is given below and further discussed. The term "layer" as used herein generally means any spherical shape of a golf ball. More specifically, one version produces a two-piece golf ball that includes a covered core. A 3-piece golf ball with a 2-layer core and a 1-layer cover can also be manufactured. The dual core includes an inner core (center) and an outer core layer around it. Other versions produce 4-piece golf balls that include dual cores and dual covers (inner and outer cover layers). In yet another structure, a 4-piece or 5-piece golf ball may be manufactured that includes a dual core, casing layer, cover layer. The term "casing layer" as used herein means a layer of balls placed between the multi-layer core subassembly and the cover. The casing layer may also be referred to as a mantle layer or an intermediate layer. The diameter and thickness of the various layers associated with properties such as hardness and compression may vary depending on the structure of the golf ball and the desired playing characteristics, as further described below.

Accordingly, the golf ball of the present invention may have any number of layers, including, for example, the case of a 4-piece golf ball, in which case the core is a double core surrounded by an ionomer inner cover layer. The outer cover layer of the three-component thermoplastic blend of the present invention is arranged around the inner cover layer. In such an embodiment, the inner core may have a thermosetting composition or a thermoplastic composition, and the outer core layer may be formed from either a thermosetting composition or a thermoplastic composition. I want to be understood. Also, the outer cover layer of the three-component thermoplastic blend of the present invention is a large number of thermoplastic polymers selected from ionomers with PEPA and thermoplastic polyurethanes, thermoplastic polyureas, and polyurea-polyurethane hybrids. May consist of feasible variants and combinations of. Again, the hardness of the outer cover may range from 20 shore D to 70 shore D, but the hardness of the layers of the three-component thermoplastic blend of this invention adjusts the composition of the ionomer and the thermoplastic polymer. By selecting a specific PEPA, varying the relative amount of ionomer, thermoplastic polymer and PEPA in the three-component thermoplastic blend, and modifying the treatment time and temperature, the three-component thermoplastic of the present invention. It should be appreciated that the hardness of the layers of the blend can be targeted and controlled within any known range.

In another embodiment, in a 4-piece golf ball, a rubber-based double core is surrounded by an inner cover layer formed from a three-component thermoplastic blend of the invention consisting of ionomers, thermoplastic polyurea and PEPA. Well, on the other hand, the outer cover layer arranged around it contains a conventional polyurea composition.

In one embodiment, at least one of the core layers is formed from a rubber composition comprising a polybutadiene rubber material. More specifically, in one version, the ball comprises a single inner core formed of a polybutadiene rubber composition. In the second version, the ball contains a dual core that includes an inner core (center) and an outer core layer around it.

In one version, the core has a rubber composition having a rubber material such as, for example, polybutadiene, ethylene-propylene rubber, ethylene-propylene-diene rubber, polyisoprene, styrene-butadiene rubber, polyalkennamer, butyl rubber, halobutyl rubber, or polystyrene elastomer. Formed from things. For example, a polybutadiene rubber composition may be used to form the inner core (center) and the surrounding outer core layer in a two-layer structure. In other versions, the core may be formed from an ionomer composition containing an ethylenic acid copolymer containing an acid group such that more than 70% of the acid groups are neutralized. These highly neutralized polymers (HNPs) may also be used to form at least one core layer in a multi-layer core structure. For example, a polybutadiene rubber composition may be used to form a center and an HNP composition may be used to form an outer core. Such rubber and HNP compositions may be considered here.

In general, polybutadiene is a 1,3-butadiene homopolymer. The double bonds in the 1,3-butadiene monomer are attacked by the catalyst to grow the polymer chain and form a polybutadiene polymer with the desired molecular weight. Polybutadiene rubber may be synthesized using any suitable catalyst depending on the desired properties. Usually, as the catalyst, an alkyl metal such as a transition metal complex (eg, neodymium, nickel, cobalt) or an alkyllithium is used. Other catalysts include, but are not limited to, aluminum, boron, lithium, titanium, and combinations thereof. This catalyst produces polybutadiene rubber with different chemical structures. In the cis bond arrangement, the main internal polymer chain of polybutadiene appears on the same side of the carbon-carbon double bond contained in polybutadiene. In the trans-bonded form, the main internal polymer chain is on the opposite side of the internal carbon-carbon double bond in polybutadiene. Polybutadiene rubber can have various combinations of cis and trans-bonded structures. Preferred polybutadiene rubbers have a 1,4 cis bond content of at least 40%, preferably greater than 80%, more preferably greater than 90%. In general, polybutadiene rubber having a high 1,4 cis bond content has high tensile strength. The polybutadiene rubber may have Mooney clay with relatively high or low Mooney viscosity.

Examples of commercially available polybutadiene rubbers available in accordance with this invention are, but are not limited to, BR01 and BR1220 available from BST Elastomers, Bangkok, Thailand; from DOW Chemicals, Midland, Michigan. Available from SE BR1220LA and SE BR1203; BUDENE 1207, 1207s, 1208, and 1280 available from Goodyear of Akron, Ohio; BR 01, 51 available from Japan Synthetic Rubber Company (JSR) in Tokyo, Japan. , And 730; Buna CB21, CB22, CB23, CB24, CB25, CB29 MES, CB60, CBNd60, CB55NF, CB70B, CBKA8967, and CB1221; from LG Chemical, Korea, Seoul, available from Lanxess, Pittsburgh, Pennsylvania. Available BR1208, UBEPOL BR130B, BR150, BR150B, BR150L, BR230, BR360L, BR710, and BCR617, Italy, Rome Polymeri available from UBE Industry, Japan, Tokyo Obtained from EUROPRENE NEOCIS BR60, INTENE 60AF, and P30AF available from Europa, AFDENE 50 and NEODENE BR40, BR45, BR50, and BR60 available from Karbochem (PTY) in Bruma, South Africa, and Kumho Petrochemical in Seoul, South Korea. Includes possible KBR 01, NdBr40, NdBr-45, NdBr60, KBR710S, KBR710H, and KBR750, as well as DIENE 55NF, 70AC, and 320AC available from Firestone Polymers, Akron, Ohio.

To form the core, polybutadiene rubber is used in an amount of at least about 5% by weight based on the total weight of the composition and is generally from about 5% to about 100% by weight, or 5% or 10% of the composition. A range with a lower limit of% or 20% or 30% or 40% or 50% and an upper limit of 55% or 60% or 70% or 80% or 90% or 95% or 100%. Generally, the concentration of polybutadiene rubber is from about 45 to about 95% by weight. Preferably, the rubber material used to form the core layer comprises at least 50% by weight, more preferably at least 70% by weight of polybutadiene rubber.

The rubber composition of the present invention may be cured by pre-blending or post-blending using a conventional curing process. Suitable curing processes include, for example, peroxide curing agents, sulfur curing agents, high energy irradiation, and combinations thereof. Preferably, the rubber composition comprises an organic peroxide, a high energy irradiation source capable of producing free radicals, and a free radical initiator selected from a combination thereof. In one preferred version, the rubber composition is peroxide cured. Suitable organic peroxides are, but are not limited to, dicumyl peroxide; n-butyl-4,4-bis (t-butylperoxy) valerate; 1,1-di (t-butylperoxy) -3,3. , 5-trimethylcyclohexane; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; di-t-butyl peroxide; di-t-amyl peroxide; t-butyl peroxide; t-butyl cumyl peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3; di (2-t-butyl-peroxyisopropyl) benzene; dilauryl peroxide; dibenzoyl peroxide; t-butylhydroperoxide; and Includes combinations of them. In a preferred embodiment, the free radical initiator is dicumyl peroxide, which is, but not limited to, Perkadox BC commercially available from Akzo Nobel. The peroxide-free radical initiator is generally present in the rubber composition in an amount of at least 0.05 parts by weight based on 100 parts by weight of the total rubber, or the lower limit is 0.05 parts by weight based on 100 parts by weight of the total rubber. 2 parts or 0.1 parts by weight or 1 part by weight or 1.25 parts by weight or 1.5 parts by weight or 2.5 parts by weight or 5 parts by weight, and the upper limit is 100 parts by weight of rubber. There are only quantities within the range of 5 parts by weight or 3 parts by weight or 5 parts by weight or 6 parts by weight or 10 parts by weight or 15 parts by weight. Unless otherwise specified, concentrations are indicated by the number of copies (phr) per 100 copies. The term "number of copies per 100 parts (parts per hand red)" used herein is also known as "phr" or "pph" and is present in the mixture for 100 parts by weight of the polymer. Defined as the number of parts by weight of a particular component. Mathematically, this can be expressed as the weight of the component divided by the total weight of the polymer multiplied by 100 times.

The rubber composition preferably contains a reactive cross-linking aid. Suitable coagents include, but are not limited to, metal salts of unsaturated carboxylic acids with 3 to 8 carbon atoms; unsaturated vinyl compounds and polyfunctional monomers (eg, trimethylolpropanetrimethacrylate); phenylene. Bismaleimide; and combinations thereof. Specific examples of suitable metal salts include, but are not limited to, one or more metal salts of acrylate, diacrylate, methacrylate and dimethacrylate, in which case the metal is magnesium, calcium, zinc, aluminum, lithium. And selected from nickel. In a specific example, the coagent is selected from acrylate, diacrylate, methacrylate and zinc salts of dimethacrylate. In another specific embodiment, the agent is zinc diacrylate (ZDA). When the coagent is zinc diacrylate and / or zinc dimethacrylate, the coagent is typically in a rubber composition with a lower limit of 1 or 5 or 10 or 10 per 100 parts by weight of the total rubber. 15 or 19 or 20 parts by weight, with an upper limit of 24 or 25 or 30 or 35 or 40 or 45 or 50 or 60 parts by weight per 100 parts by weight of the base rubber.

Free radical scavengers such as halogenated organic sulfur, organic disulfides, or inorganic disulfide compounds may be added to the rubber composition. These compounds may function as "softening and accelerating agents". As used herein, a "softening and accelerating agent" can (1) make the core more flexible at a constant "coefficient of restitution" (COR) and / or (2) permeate without a softening and accelerating agent. Means any agent or a blend of them that can be faster (get a larger COR with equal compression) when compared to the core prepared in. Preferred sulfur halide compounds are, but are not limited to, pentachlorothiophenol (PCTP) and salts of PCTP, such as ZnPCTP. By adopting PCTP and ZNPCTP for the inner core of the golf ball, a soft and fast inner core is realized. PCTP and ZnPCTP compounds help increase the elasticity and coefficient of restitution of the core. In specific examples, the softening and accelerating agents are ZnPCTP, PCTP, ditrildisulfide, diphenyldisulfide, dixyldisulfide, 2-nitrorisolcinol and combinations thereof.

The rubber composition of the present invention may contain a filler, which is added to adjust the density and / or specific gravity of the material. Suitable fillers include, but are not limited to, polymer or mineral fillers, metal fillers, metal alloy fillers, metal oxide fillers, and carbonaceous fillers. Fillers may be in any suitable form and include, but are not limited to, flakes, fibers, whiskers, fibrils, plates, particles, and powders. Rubber riglind is a crushed and recycled material (eg, crushed to about 30 mesh particle size) obtained from waste rubber golf balls, which can also be used as a filler. The amount and type of filler used is determined by the amount and weight of other components in the golf ball. This is because the maximum golf ball weight of 45.93g (1.62 ounces) is set by the United States Golf Association (USGA).

Suitable polymer or mineral fillers that may be added to the rubber composition include, for example, precipitated hydrated silica, clay, talc, asbestos, glass fiber, aramid fiber, mica, calcium metasilicate, zinc sulfate, barium sulfate, sulfurized. Includes carbonates such as zinc, lithopons, silicates, silicon carbide, diatomaceous soil, polyvinyl chloride, calcium carbonate and magnesium carbonate. Suitable mineral fillers include titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, lead, copper, boron, cobalt, beryllium, zinc and tin. Suitable metal alloys include steel, brass, bronze, boron carbide whiskers, and tungsten carbide whiskers. Suitable metal oxide fillers include zinc oxide, iron oxide, aluminum oxide, titanium dioxide, magnesium oxide, and zirconium oxide. Suitable particulate carbonaceous material fillers include graphite, carbon black, cotton flocs, natural bitumen, cellulosic flocs, and leather fibers. Microballoon fillers such as glass and ceramic, and fly ash fillers may also be used. In a specific aspect of this embodiment, the rubber composition is carbon black, nanoclay (eg, commercially available from Southern Clay Product, Cloisite and Nanofil Nanoclay, Nanocor). Available Nanomax and Nanomer Nanoclay), talc (eg, Luzenac HAR high aspect ratio talc commercially available from Luzenac America), glass (eg, glass flakes, ground glass, and micro). Includes glass), mica and mica-based pigments (eg, Iriodin fluorescent color pigments commercially available from The Merck Group) and fillers selected from combinations thereof. In a specific example, the rubber composition is modified with organic fiber micropulp.

Further, the rubber composition may contain an antioxidant for preventing deterioration of the elastomer. In addition, processing aids such as high molecular weight organic acids and salts thereof may be added to the composition. In a specific example, the total amount of additives and fillers present in the rubber composition is 15% by weight or less, or 12% by weight or less, or 10% by weight or less, based on the total weight of the rubber composition. Or 9% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less.

The polybutadiene rubber material (base rubber) may be blended with other elastomers according to the present invention. Other elastomers are, but are not limited to, polybutadiene, polyisoprene, ethylene propylene rubber (EPR), ethylene-propylene-diene (EPDM) rubber, styrene-butadiene rubber, styrene block copolymer rubber (eg, . SI , SIS , SB , SBS , SIBS , etc., where S is styrene, I is isobutylene, and B is butadiene), polyalkenamas such as polyoctenyls and butyl rubbers. , Halobutyl rubber, polystyrene elastomer, polyethylene elastomer, polyurethane elastomer, polyurea elastomer, metalrose catalyst elastomer and plastomer, isobutylene and p-alkylstyrene copolymer, isobutylene and p-alkylstyrene halogenated copolymer, butadiene copolymer with acrylonitrile, Includes polychloroprenes, alkyl acrylate rubbers, isoprene chloride rubbers, acrylonitrile isoprene chloride rubbers, and combinations of two or more of these.

In accordance with the present invention, in combination with polymers, free radical initiators, fillers, crosslinkers, and any other material used to form any portion of the center or core of a golf ball, also to those skilled in the art. The mixture may be formed using any known mixing technique. Suitable types of mixing include single-pass and multi-pass mixing and the like. The cross-linking agent and any other additive used to modify the properties of the center or additional layer of the golf ball may be similarly combined by any type of mixing technique. A single-pass mixing process in which the ingredients are added in sequence is preferred, as this type of mixing tends to increase process efficiency and reduce costs. The preferred mixing cycle is a single step in which the polymer, cis-trans catalyst, filler, zinc diacrylate and peroxide are added in sequence.

In one preferred embodiment, the entire core of the multilayer structure or at least one core layer is formed from a rubber composition, wherein the rubber composition is, but is not limited to, a polybutadiene, a polyisoprene, an elastomer propylene rubber (". EPR ), ethylene-propylene-diene (EPDM) rubber, styrene-butadiene rubber, styrene-based block copolymer rubber (SI, SIS, SB, SBS, SIBS, etc. Where "S" is styrene, "I" is isobutylene and "B" is butadiene), polyalkhenamas such as polyoctenamers, butyl rubbers, halobutyl rubbers, polystyrene elastomers, polyethylene elastomers, polyurethane elastomers, polyurea. Elastomers, metallocene-catalyzed elastomers and plastomers, isobutylene and p-alkylstyrene copolymers, isobutylene and p-alkylstyrene halogenated copolymers, butadiene copolymers with acrylonitrile, polychloroprene, alkylacrylate rubber, chlorinated isoprene rubber, acrylonitrile chlorinated It has isoprene rubber and materials selected from the natural and synthetic obligatory groups, including combinations of two or more of these.

As previously discussed, according to the present invention, single-layer and multi-layer cores can be manufactured. For two-layer cores, thermosetting materials such as thermosetting rubber can be used to make outer core layers and also include thermoplastic materials such as acid groups that are at least partially or completely neutralized. The outer core layer can be made using an ethylenic acid copolymer. Suitable ionomer compositions include multiple partially neutralized ionomers and multiple fully neutralized ionomers, which is a blend of two or more partially neutralized ionomers, 2 Ionomers formed from a blend of one or more highly neutralized ionomers (HNPs) and a blend of one or more partially neutralized ionomers with one or more highly neutralized ionomers. include. Suitable ethylenic acid copolymer ionomers and other thermoplastics that can be used to form the core layer are the same materials that can be used to make the inner cover layer, as discussed further below. ..

In another example, a multilayer core comprising an inner core, an intermediate core layer, and an outer core layer may be prepared in accordance with the present invention, where the intermediate core layer is disposed between the intermediate core layer and the outer core layer. To. More specifically, as discussed earlier, the inner core may be constructed from a thermoplastic or thermosetting composition such as a thermosetting rubber. On the other hand, the middle and outer core layers may also be formed from thermosetting or thermoplastic materials. Suitable thermosetting and thermoplastic compositions that can be used to form the intermediate / outer core layer are described above. For example, each of the intermediate core layer and the outer core layer may be formed from a thermosetting rubber composition. Therefore, the intermediate core layer may be formed from the first thermosetting rubber composition, and the outer core layer may be formed from the second thermosetting rubber composition. In another embodiment, the intermediate core layer is formed from a thermosetting composition and the outer core layer is formed from a thermoplastic composition. In the third embodiment, the intermediate core layer is formed from the thermoplastic composition and the outer core layer is formed from the thermosetting composition. Finally, in the fourth embodiment, the intermediate core layer is formed from the first thermoplastic composition and the outer core layer is formed from the second thermoplastic composition.

Other suitable thermoplastic polymers that can be used to form the intermediate layer include, but are not limited to, the following polymers, including homopolymers, copolymers and derivatives thereof. That is, (a) polyesters, especially polyesters modified with adapting groups such as sulfonates or phosphates. These include modified poly (ethylene terephthalate), modified poly (butylene terephthalate), modified poly (propylene terephthalate), modified poly (trimethylene terephthalate), modified poly (ethylene naphthenate), and US Pat. No. 6,353,050. Includes those disclosed in No. 6,274,298, and No. 6,001,930, and blends of two or more of these. The contents of these documents are incorporated herein by reference; (b) polyamides, polyamide-ethers, and polyamide-esters, and those disclosed in US Pat. Nos. 6,187,864, 6,001,930, and 5,981,654, And a blend of two or more of these. The contents of these documents are incorporated herein by reference; (c) polyurethanes, polyureas, polyurethane-polyurea hybrids, and blends of two or more of these; (d) fluoropolymers such as US Pat. No. 5,691,066, No. Disclosed in 6,747,110, and 7,009,002, and a blend of two or more of these. The contents of these documents are incorporated herein by reference; (e) Polyesters such as poly (styrene-maleic anhydride), acrylonitrile-butadiene-styrene, poly (styrene sulfonate), polyethylene styrene and blends of two or more thereof; (f) Polyvinyl chloride and grafted polyvinyl chloride, and blends of two or more of them; (g) Polycarbonate, Polycarbonate / Acrylonitrile-butadiene-Styrene blends, Polycarbonate / Polyester blends, Polycarbonate / Polyester blends, and A blend of two or more of them;

Thermoplastic materials can be "converted" to thermosetting materials by cross-linking polymer chains to form a network structure, and such cross-linked thermoplastic materials are used to form cores and intermediate layers. It is also recognized that it can be done. According to this invention. For example, thermoplastic polyolefins such as linear low density polyethylene (LLDPE), low density polyethylene (LDPE), and high density polyethylene (HDPE) may be crosslinked to form bonds between the polymer chains. Crosslinked thermoplastics typically have improved physical properties and strength over non-crosslinked thermoplastics, especially at temperatures above the melting point of the crystal. Preferably, as described above, the partially or completely neutralized ionomer is covalently crosslinked (ie, covalently bonded at least at some level and irreversible) to make it a thermosetting composition. Including cross-linking). Thermoplastic polyurethanes and polyureas can also be converted to thermosetting materials according to the present invention.

The crosslinked thermoplastic material is a thermoplastic material, such as 1) high energy radiation treatment, eg electron beam or gamma ray irradiation, as disclosed in US Pat. No. 5,891,973, which is incorporated herein by reference. ) Low energy radiation such as UV (UV) or infrared (IR) radiation; 3) Solution treatment, eg isocyanate or silane; 4) Incorporating additional free radical initiator groups into the thermoplastic before molding, and / Alternatively, it may be manufactured by 5) exposure to chemical modifications such as esterification or saponification.

Modifications of the thermoplastic polymer structure can be induced by a number of methods, including exposure of the thermoplastic material to high energy radiation or by chemical processes using peroxides. Radioactive sources include, but are not limited to, gamma rays, electrons, neutrons, protons, X-rays, helium nuclei, and the like. It is usually a gamma ray that uses radioactive cobalt atoms and can be processed to a considerable depth if necessary. For core layers that require a deeper penetration depth, electron beam accelerators or UV and IR sources can be used. Useful UV and IR irradiation methods are disclosed in US Pat. Nos. 6,855,070 and 7,198,576. The thermoplastic core layer can be irradiated with doses greater than 0.05Mrd, preferably in the range of 1Mrd to 20Mrd, more preferably in the range of 2Mrd to 15Mrd, most preferably in the range of 4Mrd to 10Mrd. In one preferred embodiment, the core is irradiated with a dose of 5Mrd to 8Mrd, and in another preferred embodiment, the core is irradiated with a dose of 0.05Mrd to 3Mrd, more preferably 0.05Mrd to 1.5Mrd.

The solid core for a golf ball of the present invention can be manufactured using any suitable prior art such as compression or injection molding. Typically, the core is a spherical structure of uncured or lightly cured rubber slag material. Prior to forming the cover layer, the core structure may be surface treated to increase the adhesion between its outer surface and the adjacent layer. Such surface treatment may include mechanically or chemically polishing the outer surface of the core. For example, the core may be subjected to corona discharge, plasma treatment, silane immersion, or other treatment methods known to those of skill in the art. The cover layer is formed on the core or ball subassembly (the core structure and any intermediate layer placed around the core) using any suitable method as further described below. Prior to forming the cover layer, the ball subassembly may be surface treated to increase the adhesion between its outer surface and the underlying cover material using the techniques described above.

A cover layer can be formed on the core or ball subassembly using conventional compression and injection molding and other methods. In general, compression molding typically involves making a hemispherical shell by injection molding the composition in an injection mold. This produces a semi-cured semi-hard half-shell (or cup). The half shell is then placed in a compression mold around the core or ball subassembly. Heat and pressure are applied and the half shells fuse to form a cover layer on the core or subassembly. Compression molding can also be used to cure the cover composition after injection molding. For example, the thermosetting composition can be injection molded around the core in an unheated mold. After the composition is partially cured, the balls are removed and placed in a compression mold. Heat and pressure are applied to the balls, which causes thermosetting of the outer cover layer.

Retractable pin injection molding (RPIM) methods generally involve the use of upper and lower mold cavities that engage together. The upper and lower cavities form a spherical internal cavity when joined together. The mold cavity used to form the outer cover layer has the details of the inner dimple cavity. The cover material adapts to the internal shape of the mold cavity to form a dimple pattern on the surface of the ball. The injection mold includes retractable support pins located throughout the mold cavity. Retractable support pins move in and out of the cavity. Support pins help maintain the position of the core or ball subassembly while the molten composition flows through the mold gate. The melted composition flows into the cavity between the core and the mold cavity, surrounds the core and forms a cover layer. Covers can be made using other methods, including, for example, reaction injection molding (RIM), liquid injection molding, casting, spraying, powder coating, vacuum forming, flow coating, dipping, spin coating and the like.

As previously discussed, an inner cover layer or intermediate layer, preferably formed from an ethylenic acid copolymer ionomer composition, can be formed between the core or ball subassembly and the cover layer. The intermediate layer containing the ionomer composition may be formed using conventional techniques such as compression or injection molding. For example, the ionomer composition may be injection molded or placed in a compression molding mold to produce a half shell. These shells are placed around the core in a compression mold and the shells fuse to form an intermediate layer. Alternatively, the ionomer composition is injection molded directly onto the core using retractable pin injection molding.

After removing the golf ball from the mold, the golf ball can be subjected to finishing processes such as flash trimming, surface treatment, marking, etc., with one or more coating layers such as spraying, dipping, brushing, or rolling. It may be worn as needed.

For example, in a conventional white golf ball, the outer cover layer containing a white pigment may be surface treated using an appropriate method such as corona, plasma, or ultraviolet (UV) light treatment. In another finishing process, the golf ball is painted with one or more paint coatings. For example, a white or clear primer paint may be applied first to the surface of the ball, then marked on the primer and then a clear polyurethane topcoat. Indications such as trademarks, symbols, logos, letters, etc. may be printed on the outer cover or prime coat layer or top coat layer using pad printing, inkjet printing, dye sublimation, or other suitable printing method. Any of the surface coatings may contain a fluorescent fluorescent whitening agent.

The golf ball of the present invention imparts various advantageous mechanical and competitive performance characteristics to the ball, as further described below. In general, the hardness, diameter, and thickness of the various ball layers may vary depending on the desired ball structure. Accordingly, golf balls of the present invention may have any known total diameter and any known number of different layers and layer thicknesses, and the three-component thermoplastics of the present invention provide the desired competitive characteristics. Incorporated into one or more of these layers to be targeted.

For example, the core may have a diameter in the range of about 0.09 inches to about 1.65 inches. In one embodiment, the diameter of the core of the present invention is from about 1.2 inches to about 1.630 inches. When part of a two-piece ball according to the invention, the core may have a diameter ranging from about 1.5 inches to about 1.62 inches. In other embodiments, the core diameter is from about 1.3 inches to about 1.6 inches, preferably from about 1.39 inches to about 1.6 inches, more preferably from about 1.5 inches to about 1.6 inches. In yet another embodiment, the core has a diameter of about 1.55 inches to about 1.65 inches, preferably about 1.55 inches to about 1.60 inches.

In some embodiments, the core has a lower limit of 0.500 or 0.700 or 0.750 or 0.800 or 0.850 or 0.900 or 0.950 or 1.000 or 1.100 or 1.150 or 1.200 or 1.250 or 1.300 or 1.350 or 1.400 or 1.450 or 1.500 or 1.600 or 1.610 inches. , The upper limit may have an overall diameter within the range of 1.620 or 1.630 or 1.640 inches. In certain embodiments, the core has a lower limit of 0.500 or 0.700 or 0.750 or 0.800 or 0.850 or 0.900 or 0.950 or 1.000 or 1.100 or 1.150 or 1.200 inches and an upper limit of 1.250 or 1.300 or 1.350 or 1.400 or 1.450 or 1.500 or 1.600. Or a multi-layer core with an overall diameter in the range of 1.610 or 1.620 or 1.630 or 1.640 inches. In other specific embodiments, the multilayer core has an overall diameter in the range of 0.500 or 0.700 or 0.750 inch lower limit and 0.800 or 0.850 or 0.900 or 0.950 or 1.000 or 1.100 or 1.150 or 1.200 or 1.250 upper limit or 1.300. Or have an overall diameter in the range 1.350 or 1.400 or 1.450 or 1.500 or 1.600 or 1.610 or 1.620 or 1.630 or 1.640 inches. In another specific embodiment, the multilayer core has a full diameter of 1.500 inches or 1.510 inches or 1.530 inches or 1.550 inches or 1.570 inches or 1.580 inches or 1.590 inches or 1.600 inches or 1.610 inches or 1.620 inches.

In some embodiments, the inner core has an overall diameter of 0.500 inches or more, or 0.700 inches or more, or 1.00 inches or more, or 1.250 inches or more, or 1.350 inches or more, or 1.390 inches or more, or 1.450 inches or more. May have a lower limit of 0.250 or 0.500 or 0.750 or 1.000 or 1.250 or 1.350 or 1.390 or 1.400 or 1.440 inches and an upper limit of 1.460 or 1.490 or 1.500 or 1.550 or 1.580 or 1.600. , The lower limit is 0.250 or 0.300 or 0.350 or 0.400 or 0.500 or 0.550 or 0.600 or 0.650 or 0.700 inch, and the upper limit is 0.750 or 0.800 or 0.900 or 0.950 or 1.000 or 1.100 or 1.150 or 1.200 or 1.250 or 1.300 or 1.350 or 1.400 inch. It may have an overall diameter within the range.

In some embodiments, the outer core layer has an overall thickness with a lower limit of 0.010 or 0.020 or 0.025 or 0.030 or 0.035 inches and an upper limit of 0.040 or 0.070 or 0.075 or 0.080 or 0.100 or 0.150 inches. Also, the lower limit is 0.025 or 0.050 or 0.100 or 0.150 or 0.160 or 0.170 or 0.200 inch, and the upper limit is within the range of 0.225 or 0.250 or 0.275 or 0.300 or 0.325 or 0.350 or 0.400 or 0.450 or 0.450 inch. It may have an overall thickness. Alternatively, the outer core layer is greater than 0.10 inch, or greater than 0.20 inch, or greater than 0.20 inch, or greater than 0.30 inch, or greater than 0.30 inch, or greater than 0.35 inch, or greater than 0.35 inch, or 0.40. It may have a thickness in the range of inches or more, or greater than 0.45 inches, or greater than 0.45 inches, or has a lower limit of 0.005 or 0.010 or 0.015 or 0.020 or 0.025 or 0.030 or 0.035, or. Thickness within the range 0.040 or 0.045 or 0.055 or 0.055 or 0.060 or 0.065 or 0.070 or 0.075 or 0.080 or 0.090 or 0.100 or 0.200 or 0.250 inch, with an upper limit of 0.300 or 0.350 or 0.400 or 0.450 or 0.500 or 0.750 inch. May have.

The intermediate core layer may have any known overall thickness, eg, a lower limit of 0.005 or 0.010 or 0.015 or 0.020 or 0.025 or 0.030 or 0.035 or 0.040 or 0.045 inches and an upper limit of 0.050 or 0.055 or 0.060 or It may be in the range of 0.065 or 0.070 or 0.075 or 0.080 or 0.090 or 0.100 inch.

The core and core layer of the golf ball of the present invention may have various hardnesses depending on the specific golf ball structure and the targeted competition characteristics. The hardness of the core center and / or layer is, for example, 35 shore C to about 98 shore C, or 50 shore C to about 90 shore C, or 60 shore C to about 85 shore C, or 45 shore C to about 75. Or it can be about 85 from 40 Shore C. In other embodiments, the hardness of the core and / or core layer ranges from about 20 shore D to about 78 shore D, or about 30 shore D to about 60 shore D, or about 40 shore D to about 50 shore D. , Or 50 shore D or less, or greater than 50 shore D.

The core compression is generally an overall compression in the range of about 40 to about 110, but examples in which the core compression is as low as 5 are also envisioned. In other embodiments, the overall CoR of the core of the invention is at least 0.750, or at least 0.775, or at least 0.780, or at least 0.785, or at least 0.790, or at least 0.795, or at least 0.800 at 125 ft / s feet. .. The core is also known to contain rubber and may typically be formed from a variety of other materials that are also used in the intermediate and cover layers. The intermediate layer may also have, for example, materials commonly used for cores and covers as described herein.

The middle layer may be considered to include any layer placed between the inner core (or center) of the golf ball and the outer cover, and therefore, in some embodiments, the middle layer is the outer core. It may include a layer, a casing layer, or an inner cover layer. In this regard, the golf ball of the present invention may include one or more intermediate layers. The intermediate layer may be used with a multi-layer cover or a multi-layer core, or both a multi-layer cover and a multi-layer core, as required.

In one non-limiting example, an intermediate layer with a thickness of about 0.010 inches to about 0.06 inches is placed around a core with a diameter in the range of about 1.5 inches to about 1.59 inches.

The intermediate layer is at least partially homopolymer or copolymer, eg, ionomers, predominantly or completely non-ionic thermoplastics, vinyl resins, polyolefins, polyurethanes, polyureas, polyamides, acrylic resins, and They may be formed from these blends, olefin-based thermoplastic rubbers, block copolymers of styrene and butadiene, isoprene or ethylene-butylene rubber, copoly (ether-amide), polyphenylene oxide resins or blends thereof, and thermoplastic polyesters. However, it should also be appreciated that there are examples in which at least one intermediate layer is formed from a material different from that commonly used for core and / or cover layers.

The range of thickness of the intermediate layer of a golf ball is large because the intermediate layer can be widely used as an outer core layer, an inner cover layer, a pincushion layer, and a moisture / vapor barrier layer. When used in the golf balls of the present invention, the intermediate layer or inner cover layer may have a thickness of about 0.3 inches or less. In one embodiment, the thickness of the intermediate layer is from about 0.002 inches to about 0.1 inches, preferably about 0.01 inches or more. For example, for some of the three-piece balls or multi-layer balls according to the invention, the intermediate layer and / or the inner cover layer may have a thickness in the range of about 0.010 inches to about 0.06 inches. In other embodiments, the thickness of the intermediate layer is, for example, about 0.05 inches or less, or about 0.01 inches to about 0.045 inches.

If the ball comprises an intermediate layer or an inner cover layer, the hardness (material) can be, for example, about 50 shore D or higher, more preferably about 55 shore D or higher, and most preferably about 60 shore D or higher. In one embodiment, the shore D hardness of the inner cover is from about 62 to about 90 shore D. In one example, the hardness of the inner cover is about 68 Shore D or higher. In addition, the thickness of the inner cover layer is preferably from about 0.015 inches to about 0.100 inches, more preferably from about 0.020 inches to about 0.080 inches, most preferably from about 0.030 inches to about 0.050 inches, but the target competition characteristics. Please note again that it may be changed accordingly.

The cover typically has sufficient strength, good performance characteristics, and a thickness to achieve durability. In one embodiment, the cover thickness may be, for example, from about 0.02 inches to about 019 inches, or about 0.1 inches or less. For example, the cover may be part of a two-piece golf ball and may have a thickness ranging from about 0.03 inches to about 0.09 inches. In other embodiments, the cover thickness may be about 0.05 inches or less, or about 0.02 inches to about 0.05 inches, or about 0.02 inches to about 0.045 inches.

The cover may be a single-layer, double or multi-layer cover, eg, the lower limit is 0.010 or 0.020 or 0.025 or 0.030 or 0.040 or 0.045 inch and the upper limit is 0.050 or 0.060 or 0.070 or 0.075 or 0.080 or 0.090 or 0.100 or. It may have an overall thickness in the range of 0.150 or 0.200 or 0.300 or 0.500 inches. In certain embodiments, the cover may be a single layer with a thickness of 0.010 or 0.020 or 0.025 inches or 0.035 or 0.040 or 0.050 inches. In other specific embodiments, the cover has an inner cover layer with a thickness of 0.010 or 0.020 or 0.025 inches or 0.035 inches or 0.050 inches and an outer cover with a thickness of 0.010 or 0.020 or 0.025 inches to 0.035 or 0.040 inches. It may consist of a cover layer.

The outer cover preferably has a lower limit of about 0.004 or 0.010 or 0.020 or 0.030 or 0.040 inches and an upper limit of about 0.050 or 0.055 or 0.065 or 0.070 or 0.080 inches of thickness. Preferably, the outer cover has a thickness of about 0.020 inches or less. The outer cover has a surface hardness of 75 shore D or less, 65 shore D or less, or 55 shore D or less, or 50 shore D or less, or 50 shore D or less, or 45 shore D or less. Preferably, the outer cover has a hardness in the range of about 20 to about 70 Shore D. In one example, the outer cover has a hardness in the range of about 25 to about 65 Shore D.

In one embodiment, the cover may be a single layer having a surface hardness of, for example, 60 shore D or higher, or 65 shore D or higher. In certain aspects of this example, the cover is formed from a composition having a material hardness of 60 shore D or higher, or 65 shore D or higher.

In other specific embodiments, the cover has a thickness of 0.010 inch or 0.020 inch to 0.035 inch or 0.050 inch and a composition having a material hardness of 60 or 62 or 65 Shore D to 65 or 70 or 72 Shore D. It may be a single layer formed from an object.

In yet other specific embodiments, the cover has a thickness of 0.010 or 0.025 inches to 0.035 or 0.040 inches and is 62 shore D or less, or less than 62 shore D, or 60 shore D or less, or less than 60 shore D. , Or a single layer formed from a composition having a material hardness of 55 Shore D or less, or less than 55 Shore D.

In yet other specific embodiments, the cover has a thickness of 0.010 or 0.025 inches to 0.035 or 0.040 inches and is 62 shore D or less, or less than 62 shore D, or 60 shore D or less, or less than 60 shore D. , Or a single layer formed from a composition having a material hardness of 55 Shore D or less, or less than 55 Shore D.

In an alternative embodiment, the cover may include an inner cover layer and an outer cover layer. The inner cover layer composition may have a material hardness of 60 or 62 or 65 Shore D to 65 or 70 or 72 Shore D. The thickness of the inner cover layer may have a lower limit of 0.010 or 0.020 or 0.030 inches and an upper limit of 0.035 or 0.040 or 0.050 inches. The outer cover layer composition may have a material hardness of 62 shore D or less, or less than 62 shore D, or 60 shore D or less, or less than 60 shore D, or 55 shore D or less, or less than 55 shore. The outer cover layer may have a lower limit of 0.010 or 0.020 or 0.025 inches and an upper limit of 0.035 or 0.040 or 0.050 inches in thickness.

In yet another embodiment, the cover is a double or multi-layer cover that includes an inner or intermediate cover layer and an outer cover layer. The inner cover layer may have a surface hardness of 70 shore D or less, or 65 shore D or less, or less than 65 shore D, or shore D hardness 50 to 65, or shore D hardness 57-60, shore D hardness 58. Also, the lower bound may be 0.010 or 0.020 or 0.030 inch and the upper bound may have a thickness in the range 0.045 or 0.080 or 0190 inch. The outer cover layer has a material hardness of 65 shore D or less, or 55 shore D or less, or 45 shore D or less, or 40 shore D or less, or 25 shore D to 40 shore D, or 30 shore D to 40 shore D. You can do it. The surface hardness of the outer cover layer may have a lower limit of 20 or 30 or 35 or 40 Shore D and an upper limit of 52 or 58 or 60 or 65 or 70 or 72 Shore D. The outer cover layer may have a thickness in the range 0.010 or 0.015 or 0.025 inch lower limit and 0.035 or 0.040 or 0.045 or 0.050 or 0.055 or 0.075 or 0.080 or 0.115 inch upper limit.

Note that, as already mentioned, in some examples one or more cover layers are formed from a material typically incorporated into a core layer or an intermediate layer.

It should be noted that the golf ball of the present invention may incorporate a conventional coating layer for the purposes normally incorporated. For example, one or more coating layers may have a total thickness of about 0.1 μm to about 100 μm, or about 2 μm to about 50 μm, or about 2 μm to about 30 μm. On the other hand, each coating layer may have a thickness of, for example, about 0.1 μm to about 50 μm, or about 0.1 μm to about 25 μm, or about 0.1 μm to about 14 μm, or about 2 μm to about 9 μm.

Note that the layer of golf balls of the present invention may be incorporated by either casting, compression molding, injection molding, or thermoforming.

The ball obtained by the present invention The ball obtained by the present invention has good impact durability and cutting / shear resistance. The United States Golf Association (USGA) has set a total weight limit for golf balls, in particular the USGA has established a maximum weight of 45.93 g (1.62 ounces) for golf balls. There is no lower limit on weight. In addition, the USGA requires golf balls used in competition to have a diameter of at least 1.68 inches. Since there is no upper limit, many golf balls have a total diameter in the range of about 1.68 to about 1.80 inches. The diameter of the golf ball is preferably about 1.68 to 1.74 inches, more preferably about 1.68 to 1.70 inches. According to the invention, the weight, diameter and thickness of the core and cover layer may be adjusted as needed to ensure that the ball meets the USGA specification with a maximum weight of 1.62 ounces and a minimum diameter of at least 1.68 inches.

Preferably, the golf ball has a coefficient of restitution (COR) of at least 0.750, more preferably at least 0.800 (measured according to the test method below). Golf ball cores generally have a compression in the range of about 30 to about 130, more preferably about 70 to about 110 (as measured by the test method below). These properties allow the player to generate greater ball velocities from the tee and achieve greater distance from their drive. At the same time, the relatively thin outer cover layer means that the player has a more comfortable and natural feel when hitting the ball in the club. The ball is easier to play and its flight path can be controlled more easily. This control allows the player to make better approach shots near the green. Moreover, the outer cover of the present invention has good impact durability and mechanical strength.

The following test methods may be employed to obtain predetermined properties associated with the creative three-component thermoplastic blends of the invention and other materials that may be incorporated into the golf balls of the invention.

<u style="Single">hardness</u>The center hardness of the core is obtained according to the following procedure. The core is gently pushed into a hemisphere holder with an internal diameter slightly smaller than the diameter of the core, so that the core is placed in the hemisphere holder and at the same time exposes the geometric center plane of the core. The core is fixed in the holder by friction and does not move during the cutting and scraping steps, yet the friction is not excessive so as not to disturb the natural shape of the core. The core is mounted so that the core separator is approximately parallel to the top of the holder. The diameter of the core is measured at this orientation and an angle of 80 degrees prior to mounting. In addition, measurements are made from the bottom of the holder to the top of the core, which provides a reference point for future calculations. It also measures the distance from the bottom of the holder to the top of the core to obtain a reference point for future calibration. Roughly cut using a band saw or other suitable cutting tool, slightly above the exposed geometric center of the core, while preventing the core from moving within the holder during this step. The rest of the core, still held in the holder, is secured to the base plate of the surface grinding machine. The exposed "coarse" core surface is polished to a smooth, flat surface to reveal the geometric center of the core, which can be verified by measuring the height from the bottom of the holder to the exposed surface of the core. .. This makes exactly half the original height of the core 0. Ensure that it has been removed within the range of 004 inches. Hold the core in the holder, find the center of the core with a centering ruler, mark it carefully, and measure the hardness with this center mark according to ASTM-D2240. Hardness measurements at any distance from the center of the core are performed by drawing a line extending radially outward from the center mark and measuring the hardness at a distance typically in increments of 2 mm from the center. Hardness at a specific distance from the center should be known and measured on line segments with at least two, preferably four radii, 180 ° or 90 ° apart, respectively, and then averaged. Even if all hardness measurements are performed on a surface passing through the center of geometry, the core is still inside the holder so that its coordination is not disturbed and the measurement surface is always parallel to the bottom of the holder. Also, therefore, make sure it matches the leg of the durometer exactly.

The hardness of the outer surface of a golf ball layer is measured on the actual outer surface of the layer and is taken from the average of a number of measurements taken from the facing hemispheres of the core's separation lines or surface defects, such as holes or protrusions. Be careful not to make the above measurements. Hardness measurements are made according to ASTM D-2240 "Durometer rubber and plastic recess hardness". Due to the curved surface, care must be taken to center the golf ball or golf ball assembly directly below the durometer indenter before the surface hardness is read. One calibrated digital durometer capable of reading up to 0.1 units is used for hardness measurement. The digital durometer must have its legs parallel and attached to the base of the automatic stand. The weight and attack speed on the durometer must be compatible with ASTM D-2240.

In one embodiment, one or more points measured along a "positive" or "negative" gradient may be above or below a line that fits the gradient, with its outermost and innermost values. May be. In another preferred embodiment, the hardest point along a specific steep "positive" or "negative" gradient is the value of the innermost part of the inner core (ie, the geometric center) or the outer core layer (inner surface). May be larger, but the outermost point (ie, the outer surface of the inner core) is larger (when "positive") than the innermost point (ie, the geometric center of the inner core or the inner surface of the outer core layer), or It must be small (when "negative") and able to be maintained without compromising the "positive" and "negative" gradients.

As discussed earlier, the direction of the hardness gradient of a golf ball layer is defined by differences in hardness measurements taken on the outer and inner surfaces of the specific layer. The hardness of the center of the inner core and the hardness of the outer surface of the inner core or outer core layer of the single core ball are easily determined according to the test procedure described above. The outer surface of the inner core layer (or other optional intermediate core layer) of the double core ball is also measured to measure the outer surface of the golf ball layer if the measurement is made before the layer surrounds the additional layer. It is easily measured according to the procedure described here. Once the layer of interest is surrounded by an additional core layer, it will be difficult to determine the hardness of the inner or outer surface of any inner or intermediate layer. Therefore, within the scope of the present invention, the hardness of the inner or outer surface of the core layer is first measured at a position 1 mm from the interface, when necessary, after the inner layer is surrounded by another core layer. The test procedure described is adopted.

Also note that there is a fundamental difference between "material hardness" and "hardness measured directly on a golf ball". Within the scope of the description of the invention, material hardness is measured according to ASTM D2240 and is generally related to measuring the hardness of flat "slabs" or "buttons" made from materials. It should be understood that "material hardness" and "hardness measured directly on the surface of a golf ball" are basically different. Hardness as measured directly on the surface of a golf ball (or other spherical surface) typically results in a hardness value different from the material hardness. This difference in hardness values is, but is not limited to, such as ball structure (ie, core type, number of cores and / or cover layers, etc.), ball (or sphere) diameter, and material composition of adjacent layers. It comes from several factors. It should also be understood that the two measurement methods do not correlate linearly and therefore one hardness value cannot easily correlate with the other hardness value. Shore C hardness (eg Shore C or Shore D hardness) was measured by test method D-2240.

<u style="Single">Elastic modulus</u>As used herein, "modulus" or "modulus flexural modulus" refers to the flexural modulus measured using a standard flex bar according to ASTM D790-B.

<u style="Single">Tensile strength</u>As used herein, tensile strength refers to the tensile strength measured using ASTM D-638.

<u style="Single">Extreme growth</u>As used herein, maximal elongation refers to the ultimate elongation measured using ASTM D-638.

<u style="Single">compression</u>Several different techniques are available, as disclosed in Jeff Dalton's Compression by Any Other Name, Science and Golf IV, Proceeding of World Science Congress of Golf (Eric Thain ed., Routledge, 2002) ("J. Dalton"). Used to measure compression, in which Atti compression, Riehle compression, load / deflection measurements at various fixed loads and offsets, load / deflection measurements at various fixed loads and offsets, and effective elastic coefficients. Is included. For the purposes of the present invention, "compression" refers to the Soft Center Deflection Index ("SCDI"). SCDI is a Dynamic Compression machine that allows you to determine the pounds needed to deflect 10% of the core diameter. Machine, "DCM") is a program change. A DCM is a device that applies a load to a core or ball and measures the number of inches changed by the core or ball under the measured load. An unprocessed load / change curve is generated that matches the Atti compression scale, which yields a number that displays the Atti compression. The DCM does this with a load cell, which is attached to the bottom of a hydraulic cylinder that is pneumatically triggered at a fixed velocity (typically 1.0 ft / s) towards a quiescent core. The cylinder is fitted with an LVDT, which measures the distance traveled by the cylinder during the test time frame. A software-based logarithmic algorithm ensures that measurements are not taken early in the test until at least a continuous 5 increment in load is detected. SCDI is a small variation of this setting. The hardware is the same, but the software and output have changed. In SCDI, size is the number of pounds x inches of force required to bend the core. The amount of deflection of the core is 10% of the core diameter. The DCM is triggered, the cylinder deforms the core by 10% of the diameter, and the DCM returns the required pounds of force (measured from the attached load cell) and deflects the core by that amount. The value displayed is a single number in pounds.

<u style="Single">Coefficient of restitution ("COR")</u>The COR is determined by a known procedure, where a golf ball or golf ball subassembly (eg, a golf ball core) is launched from an air cannon at two predetermined speeds and the COR is calculated at a speed of 125 ft / s. It is decided by. Multiple ballistic light screens are placed between the air cannon and the steel plate at a fixed distance to measure ball velocity. As the ball moves to the steel plate, each light screen is activated and the time on each light screen is measured. As a result, an incident transition time that is inversely proportional to the incident velocity of the ball can be obtained. The ball collides with a steel plate and rebounds through multiple optical screens, measuring the time interval it takes to move between the optical screens. As a result, a pop-out transition time that is inversely proportional to the pop-out speed of the ball can be obtained. COR is the ratio of the pop-out transition time interval to the incident transition time interval, COR = V_{out out}/ V_in= T_in/ T_{out out}Is calculated as.

Here, the thermosetting and thermoplastic layers may be treated to create a positive or negative hardness gradient within and between the golf ball layers. In the golf ball layer of the present invention in which a thermosetting rubber is used, a gradient forming process and / or a gradient forming rubber formulation may be used. The gradient generation process and formulations are, for example, US Patent Application No. 12 / 048,665 filed March 14, 2008, US Patent Application No. 11 / 829,461 filed July 27, 2007, 2007. US Patent Application No. 11 / 772,903 filed on July 3, 2007, US Patent Application No. 11 / 832,163 filed on August 1, 2007, US Patent Application No. 11 filed on August 1, 2007. Fully disclosed in Nos. 11 / 832,197, these disclosures are incorporated herein by reference.

The golf ball of the invention, which incorporates at least one layer of the three-component thermoplastics of the invention as described herein, merely illustrates some of the many embodiments of the invention. Please note. It should be noted that one of ordinary skill in the art can make various changes and additions to such golf balls without departing from the spirit and scope of the invention. All such examples are intended to be included in the appended claims.

The golf ball of the present invention may further incorporate markings, which, as used herein, is believed to mean any symbol, letter, character group, design, etc. that may be added to the dimple surface of the golf ball. Be done.

The golf ball of the present invention typically has a dimple coverage of about 60% or more, preferably about 65% or more, more preferably about 75% or more. Any known dimple pattern may be employed with any number of dimples of any shape or dimension. For example, the number of dimples may be 252 to 456, or 330 to 392, and may have any width and edge angle. The pattern separation line structure may be a straight line or a staggered wave parting line (SWPL).

In any of these embodiments, the single layer core may be replaced with a core consisting of two or more layers. However, at least one core layer has a hardness gradient.

Other matters in the working example, or, even if not explicitly stated, all numerical ranges, quantities, values, percentages, eg, these with respect to the quantity of material, and others in the specification, even if the value, quantity or Even if the term "about" is not displayed in relation to the range, it can be read as if "about" is placed before it. Therefore, unless indicated otherwise, the parameters of the numbers expressed in the specification and claims are approximate, depending on the desired properties intended to be obtained by the present invention. Change. At a minimum, of course, it does not constrain the application of the doctrine of equivalents, but the parameters of each number should be interpreted in the light of the number of significant digits recorded and the usual rounding process.

Although the numerical ranges and parameters indicating the broad range of the present invention are approximate values, the numerical values shown in the particular embodiment are reported as accurately as possible. However, the numbers essentially contain certain errors that inevitably result from the standard deviation found in each test measurement. Further, it should be noted that when numerical ranges of various ranges are described herein, any combination of these values, including the listed values, may be used.

Although the golf ball of the present invention is described herein with reference to specific means and materials, the invention is not limited to the disclosed matters and all within the scope of the claims. Please understand that it extends to the equality.

It should be appreciated that the manufacturing methods, compositions, structures and products described and exemplified herein represent only some embodiments of the present invention. It will be appreciated by those skilled in the art that various modifications and additions can be made to the composition, structure and product without departing from the spirit and scope of the invention. It should be noted that all such examples are included in the appended claims.