Automotive articles prepared from filled tpo compositions, and methods of making the same

This application claims the priority of provisional application No. 60/694150 filed on June 24, 2005, the provisional application of which is incorporated herein by reference in its entirety.

The present invention relates to filler-containing thermoplastic polyolefin (TPO) compositions. In one embodiment, the present invention comprises a TPO composition comprising a highly crystalline isotactic propylene homopolymer, an ethylene / α-olefin (EAO) elastomer impact resistance modifier and a reinforced grade plate filler, such as talc. Regarding. In another aspect, the present invention relates to such filler-containing TPO compositions having low gloss, good low temperature impact resistance and excellent flexural modulus and thermal deformation temperature (HDT) properties. In yet another aspect, the present invention relates to articles made from these TPO compositions.

Talc-filled TPO requires a balance between injection molding applications, as well as stiffness and impact resistance at temperatures down to about -30 ° C, scratch resistance and scratch resistance, and deformation resistance at temperatures around 100 ° C. Can be used for other purposes. The flexural modulus of these grades of TPO is generally between about 100,000 psi and 200,000 psi, and HDT is generally below about 110 ° C.

There has been much interest in replacing conventional resins, such as polycarbonate and polystyrene resins, with polyolefin substitutes. Several polypropylene compositions are described in the following patents or applications. U.S. Pat. No. 6,759,475 states that (a) 3 to 65 weight percent of components are soluble in 23 ° C para-xylene, (b) soluble in 135 ° C para-xylene and insoluble in 23 ° C para-xylene. , 35-97 weight percent components, and (c) 0-30 weight percent components insoluble in para-xylene at 135 ° C, are described as resin compositions based on crystalline polypropylene (eg, summary). See book). The component (a) soluble in para-xylene at 23 ° C is elastic with a content of styrene or its derivatives in the range 0-35 weight percent and an intrinsic viscosity (η) in the range 0-1.5 dL / g. It is substantially composed of the component (a1). The component (b) soluble in 135 ° C para-xylene and insoluble in 23 ° C para-xylene has an isotactic pentad fraction (mmmmm) of 97% or higher and a molecular weight distribution of 6 or higher (Mw). It is substantially composed of crystalline polypropylene constituents (b1) having a molecular weight distribution (Mz / Mw) of / Mn) and 6 or more. The component (c) insoluble in para-xylene at 135 ° C is substantially composed of the filler (c1).

U.S. Patent Application No. 2004/0044107 describes a propylene resin composition having good moldability, good balance of physical properties, good appearance, lower gloss, and scratch resistance. These compositions can be used in vehicle interior parts (see, eg, abstract). This polypropylene resin composition contains the following components: crystalline homopolypropylene with an MFR of 500 to 3,000 g / 10 min; with crystalline homopolypropylene and ethylene-propylene copolymer rubber with an ethylene content of 45-80% by weight. Polypropylene consisting of; polypropylene consisting of crystalline homopolypropylene and ethylene-propylene copolymer rubber having an ethylene content of 25% by weight or more and up to 45% by weight; and ethylene-α-olefin copolymer rubber (see, eg, abstract). ).

U.S. Pat. No. 6,660,797 describes a propylene-based composition for molded polypropylene resin products that excels in scratch resistance and moldability, as well as balanced properties between high rigidity and high impact strength. Also provided are methods for molding this propylene-based composition to provide high performance industrial and automotive parts, especially automotive interior parts (see, eg, abstract). An example of this propylene resin composition contains the following components (A) and (B) as described below (see, for example, column 2, lines 14-49). Component (A) is a propylene resin consisting of the following components (a1), (a2) and (a3); 90-40 weight percent: (a1) 60-83 weight percent crystalline propylene homopolymer. It is composed of a component (a1-1 unit) and a 17-40 weight percent ethylene / propylene random copolymer component (a1-2 unit) containing 30-52 weight percent ethylene, with a weight average molecular weight of 230,000-600,000. Have, as well as 25 cm²15-150 g / 10 min melt flow rate (230 ° C, 2.16 kg) and 100 or less gels for (area) and 0.5 mm (thickness) molded products with sizes of 50 μm or larger. Number of propylene / ethylene block copolymers; 100 parts by weight; (a2) Alkenes with an average particle size of 0.5 to 15 μm; 0 to 200 parts by weight; (a3) 20 to 50% by weight of carbon atoms 3 to 8 Ethylene / α-olefin copolymer rubber containing α-olefin and having a melt flow rate of 0.3 to 100 g / 10 min (230 ° C, 2.16 kg); 0 to 20 parts by weight. Component (B) is a propylene-based resin material consisting of the following components (b1) and (b2); 10 to 60% by weight: (b1) 100 ° when fractionated with orthodichlorobenzene as a solvent. This component, which accounts for 8% by weight or more of the insoluble component below C, has a component insoluble in orthodichlorobenzene below 120 ° C, and is insoluble below 100 ° C, is 200,000 or more. A propylene homopolymer or propylene / ethylene block copolymer with a weight average molecular weight and a melt flow rate of 0.3 to 70 g / 10 min (230 ° C, 2.16 kg); 15 to 80 parts by weight; and (b2) an average of 0.5 to 15 μm. Solvent or homopolymer with particle size; 20 to 85 parts by weight (see, eg, column 2, lines 14-49).

Further polypropylene compositions are described in US Pat. Nos. 5,286,776 and 6,667,359. Other polyolefin compositions and secondary processed products made from them, such as automotive parts, are described in US Pat. Nos. 2005/0029692, 2004/0188885 and 2004/0094986. Additional propylene-based polymers and compositions are described in US Patent Publication No. 2005/0272858 (see also International Publication No. 2004033509) and US Patent Publication No. 2004/0122196. However, the compositions disclosed in these references and those discussed above are complex and expensive due to the number of polymeric components in each composition, and / or the books described herein. It does not meet one or more of the desired fluid, mechanical or thermal properties of the compositions of the invention. In addition, some of the compositions disclosed in these references require polypropylene / (ethylene / polypropylene) heterogeneous rubbers that are not advantageous for low temperature impact resistance.

Low cost polyolefin compositions with simple polymer formulations that can be used to form manufactured parts with excellent mechanical and thermal properties, such as injection molded parts, continue to be needed. Further, a filler-containing TPO composition that can be used to form reinforced lightweight products such as lightweight injection molded parts is needed. There is also a need for such compositions that can be used to form products with improved hot and cold performance properties. These and other needs were met by the present invention:

According to the present invention, structures made from TPO compositions containing crystalline isotactic propylene homopolymers, EAO elastomer impact resistant modifiers and reinforced grade plate fillers are conventional molding resins such as polycarbonates. It is a low-cost alternative to resins and polystyrene-based resins.

The present invention has low gloss, measured by Instrumented Dart Impact Test (ASTM D3763) and Izod Notched Impact (ASTM D256) up to about -30 ° C. For TPO compositions with good low temperature impact resistance, flexural modulus greater than about 1930 MPa (ASTM D790, modulus of 1%), and HDT (ASTM D634) above about 100 ° C.

Such compositions include: (a) a highly crystalline isotactic propylene homo with a bending elasticity (ASTM D790) greater than about 1930 MPa and an HDT (ASTM D634) higher than about 100 ° C. Polymers, (b) Tg below -30 ° C as measured by a differential scanning calorimetry (DSC) and 190 ° C and 0.1 radians measured per second using an Advanced Rheometirc Expansion System (ARES) flowmeter. An ethylene / α-olefin elastomer impact resistance modification with a tan delta of less than about 2 and an HDT measured by ASTM D648 at 0.455 MPa above the peak melting temperature of its impact resistant modifier as measured by DSC. Quality agents (or ethylene / α-olefin copolymers), and (c) plate-like fillers. In such compositions, the ratio of homopolymers to impact modifiers (A: B) is between about 9: 1 and about 6: 4.

Typically, the ARES fluid meter operates with a strain of 15 percent. The DSC procedure for measuring the glass transition temperature (Tg) is: initial equilibration at 200 ° C for 3 minutes, followed by ramp down to -90 ° C at 10 ° C / min, followed by equilibration for 5 minutes. And then finally, including a ramp-up to 200 ° C at 10 ° C / min. The amount of plate-like filler in the TPO composition can vary widely, but typically the compositions of the present invention have a flexural modulus efficiency factor of about 3 or more and about. Heat deflection efficiency of 1.5 or higher Use enough filler to have factor). This coefficient is determined by the benchmarking method described below. The ratio of the filler (C) to the composition (A + B + C), i.e. (C :( A + B + C)), is required to achieve the desired composition flexural modulus and HDT. ,adjust. The TPO composition of the present invention may contain one or more other components such as pigments and / or scratch and scratch inhibitors. This pigment is generally added as a color concentrate, and the articles made from these compositions exhibit good color and may not require painting.

Accordingly, the present invention provides a polyolefin composition having a thermal deformation temperature (HDT) greater than about 100 ° C and a flexural modulus greater than about 1930 MPa, which compositions are: A) Crystalline isotactic propylene homopolymer with flexural modulus greater than about 1930 MPa and HDT higher than about 100 ° C; B) Tg below about -30 ° C, tan delta less than about 2 measured at 190 ° C at 0.1 radian / sec, peak melting temperature of the ethylene / α-olefin copolymer measured by a differential scanning calorimeter. Ethylene / α-olefin copolymer with HDT above; and C) Plate-shaped filler And the weight ratio of this homopolymer: copolymer (A: B) is between about 9: 1 and about 6: 4.

In one embodiment, the weight percent of the filler based on the total weight of the propylene homopolymer and the ethylene / α-olefin copolymer and the filler is ethylene / based on the total weight of the propylene homopolymer and the ethylene / α-olefin copolymer. Greater than the weight percent of the α-olefin copolymer.

In another aspect, the compositions of the invention further comprise at least one additive selected from pigments, flame retardants, scratch and scratch inhibitors, or combinations thereof.

In another aspect of the invention, the propylene homopolymer has a flexural modulus greater than 2070 MPa and an HDT greater than 110 ° C, more preferably an HDT greater than 2210 MPa and an HDT greater than 120 ° C.

In another aspect of the invention, the α-olefin of the ethylene / α-olefin copolymer is a C3 to C20α-olefin, more preferably a C4 to C20α-olefin. In a further embodiment, the α-olefin of the ethylene / α-olefin copolymer is selected from propylene, 1-butene, 1-hexene or 1-octene, more preferably 1-butene, 1-hexene or 1-octene. Is selected from. In another aspect of the invention, the ethylene / α-olefin copolymer has a Tg lower than -30 ° C, preferably lower than -40 ° C, and even more preferably lower than -50 ° C. In another embodiment, the difference between the "HDT" and the "melting point, Tm" of the ethylene / α-olefin copolymer is at least 4, preferably at least 6, and even more preferably at least 8. In another embodiment, the tan delta of the ethylene / α-olefin copolymer as measured at 190 ° C. and 0.10 radians / sec is 2 or less, more preferably 1.8 or less.

In another aspect of the invention, the filler is plate talc. In a further embodiment, the composition comprises a sufficient amount of filler to have a flexural modulus effect factor of 3 or more and an HDT efficiency factor of 1.5 or more. In another embodiment, the composition comprises 25 weight percent, more preferably 30 weight percent talc based on the total weight of the composition. In another embodiment, the composition comprises talc, preferably 30 weight percent or more, more preferably 35 weight percent or more, based on the total weight of the composition. In another embodiment, the weight percent of the filler based on "total weight of propylene homopolymer and ethylene / α-olefin copolymer and filler" is in "total weight of propylene homopolymer and ethylene / α-olefin copolymer". Greater than the weight percent of the ethylene / α-olefin copolymer based on.

In a further embodiment, the composition further comprises one or more different ethylene / α-olefin copolymers. In a further embodiment, the weight percent of the filler based on "the total weight of the propylene homopolymer and the ethylene / α-olefin copolymer and one or more other different ethylene / α-olefin copolymers and the filler" is ". Ethylene / α-olefin copolymer and one or more based on "total weight of propylene homopolymer and ethylene / α-olefin copolymer and one or more different ethylene / α-olefin copolymers" Greater than the weight percent of other different ethylene / α-olefin copolymers.

The present invention also provides articles containing at least one component formed from the compositions of the present invention.

Further, the present invention provides a molded article containing at least one component formed from the composition of the present invention. In a further aspect, the molded product is a computer part, building and construction material, household appliances, container, part of furniture, household appliances, footwear or toys.

The present invention also provides a method for producing the composition of the present invention. In a further embodiment, the polypropylene homopolymer and the ethylene / α-olefin copolymer are polymerized in a separate reactor, and the polypropylene homopolymer and the ethylene / α-olefin copolymer are then mixed with a plate filler. One way to include that. In a further embodiment, the polypropylene homopolymer and the ethylene / α-olefin copolymer are polymerized in a separate reactor, and the polypropylene homopolymer and the ethylene / α-olefin copolymer are then mixed with a plate filler. That method, including that.

The present invention also provides compositions that include a combination of two or more embodiments or embodiments as described herein. The present invention also provides a method for producing the compositions of the present invention, which method comprises a combination of two or more embodiments or embodiments as described herein.

The present invention also provides articles that include a combination of two or more embodiments or embodiments as described herein. The present invention also provides a method of making an article of the invention, which method comprises a combination of two or more embodiments or embodiments as described herein.

Polypropylene is the main polymer component of this formulation, which ultimately determines the maximum flexural modulus and HDT that can be achieved. Conventional propylene homopolymers have a flexural modulus (1% secant) less than about 1520 MPa (220.4 kpsi) and HDT lower than 90 ° C, and are not rigid enough to be useful in these compositions. Rigidity cannot be maintained up to a sufficiently high temperature. Overall goals for low gloss, low temperature impact resistance, improved flexural modulus (eg, flexural modulus greater than about 1520Mpa, 1% polymer), and improved HDT (eg, higher than about 90 ° C). To achieve, preferably, this polypropylene is a high crystalline isotactic homopolymer with a flexural modulus greater than about 1930 MPa (280 kpsi) and an HDT higher than about 100 ° C. A more preferred grade of high crystalline isotactic homopolymer has a flexural modulus greater than about 2070 MPa (300 kpsi) and an HDT higher than about 110 ° C. The most preferred grade of high crystalline isotactic homopolymers have a flexural modulus greater than about 2210 MPa (320 kpsi) and an HDT higher than about 120 ° C. In one embodiment, the propylene homopolymer is higher than about 90 ° C, preferably higher than about 100 ° C, even more preferably higher than about 110 ° C, even more preferably higher than about 120 ° C, and Most preferably it has an HDT higher than about 130 ° C. In another embodiment, the propylene homopolymer is greater than about 1720 MPa (250 kpsi), preferably greater than 1930 MPa (280 kpsi), more preferably greater than about 2210 MPa (320 kpsi), and most preferably greater than about 2210 MPa (320 kpsi). Has a large flexural modulus.

Excellent low temperature impact resistance is provided by modification of high crystalline isotactic homopolymer polypropylene with an EAO elastomer impact modifier (or ethylene / α-olefin). To provide the required impact resistance at -30 ° C, the EAO elastomer impact resistance modifier is lower than -30 ° C, more preferably lower than -40 ° C, and most preferably -50 °. It has a glass transition temperature (Tg) lower than C.

In addition, two other characteristics of the elastomeric impact resistance modifier affect the properties of the composition. First, the EAO elastomer impact resistance modifier chooses a grade with an HDT that is significantly higher than its melting point, as it will be well above its melting point before the highly crystalline isotactic propylene homopolymer begins to melt. Is desirable. Table 1 below shows the deltas obtained by subtracting the DSC peak melting temperature (Tm) from the HDT measured with various EAO elastomers. Preferred grades of EAO elastomer impact resistance modifiers have positive deltas, more preferred grades have 4 or more deltas, and even more preferred grades have 6 or more deltas. , And the most preferred grades have 8 or more deltas.<tables num="1"><img file="JP5118030B2_D0001.tif" /></tables>

The Engage elastomer is an ethylene-octene copolymer and the ENR elastomer is an ethylene-butene copolymer. The Dow Chemical Company manufactures both EAO elastomers.

Second, the elastomeric tan delta, measured at 190 ° C at 0.1 radians per second (rad / sec), correlates with the gloss of the final injection molded part. The lower the tan delta, the lower the luster. The viscosities at Tandelta and Poise measured under these conditions are shown in Table 1 above. The correlation between tandelta and 20 degree gloss (Minolta glossometer, ASTM D523) measured for impact resistant modified benchmarking formulations using a number of different EAOs is shown in Table 2 below. The data in this table are compounds containing 70 parts by weight of J707PT polymer blend (35 MFR Mitsui Chemicals impact resistant copolymer polypropylene with 30 parts by weight of various EAOs available from The Dow Chemical Company). based on. Specialty Minerals without fillers and 10 weight percent ABT-2500 plate talc was added to test this polymer blend. Neither impact-resistant copolymers nor talc meet the criteria of the present invention, but they have EAOs with low tan deltas at 190 ° C and 0.1 radians / sec, but otherwise have a 20 degree luster of glossy systems. It helps to demonstrate how dramatically the reduction can be achieved. This data shows that the choice of elastomer has a significant effect on the loss of polypropylene gloss due to the addition of filler (here talc). This polypropylene can be diverse and includes both homopolymers and copolymers and both nucleated and non-nucleated polymers. High MFR polypropylene is generally very glossy, and the addition of EAO has some effect on reducing its gloss to a matte finish.<tables num="2"><img file="JP5118030B2_D0002.tif" /></tables>

Preferred grades of EAO elastomer impact resistance modifiers have Tg and delta properties as described above, and are about 2 or less, more preferably about 1.8 or less, and most preferably about 1.6 or It also has a tan delta measured at 190 ° C and 0.1 radians / sec below that.

The low gloss obtained by using the EAO elastomer impact resistance modifier with tan delta described above makes it possible to provide parts that are colored during the molding process by the use of color concentrates. This mold-in-color process eliminates the need for a painting step if the compound has an acceptablely low gloss. Color concentrates often reduce surface friction and reduce surface damage caused by scratches and scratches, as it is widely known that paints improve the resistance of parts to scratch and scratch damage. Further modified with reduced material. Common additives known in the art include silicon-based materials such as high molecular weight polydimethylsiloxane, waxy materials such as elcamide that bloom the surface, and combinations of hard tough plastics such as nylon and surfactants. It is some kind of special material.

Propylene homopolymer The propylene homopolymer may be a linear homopolymer, a nucleated homopolymer, or a combination thereof.

The propylene homopolymer preferably has a melt flow rate (MFR) of about 0.1 to 150, preferably 1 to 100 g / 10 min, even more preferably 3 to 75 g / 10 min, and even more preferably 5 to 50 g / 10 min. Has (230 ° C / 2.16 kg weight). All individual values and subranges from 0.1 to 150 g / 10 min are included herein and disclosed herein.

This polypropylene homopolymer also preferably has a melting point higher than 145 ° C. In another embodiment, the propylene component has a melting point of 130 ° C to 180 ° C, preferably 140 ° C to 170 ° C, Tm.

In another embodiment, the polypropylene homopolymer has a crystallization temperature of 110 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and most preferably 140 ° C. or higher, Tc.

As used herein, "nucleated" refers to a polymer modified by the addition of a nucleating agent such as Millad® (dibenzylsorbitol commercially available from Milliken). Other conventional nucleating agents can also be used. A plate-like filler such as talc can act as a nucleating agent, eliminating the need for the addition of another nucleating agent.

As the polymerization process used to produce the refractory polymer, pay close attention to the slurry process performed at about 50 to 90 ° C and 0.5 to 1.5 MPa (5 to 15 atm), and the removal of the amorphous polymer. Both the vapor phase process and the liquid monomer process have to be paid. The polypropylene can be made by using any of a variety of single sites, metallocenes and geometry constraining catalysts with their associated processes. The polymerization can be carried out in a stirring tank reactor, a gas phase reactor, a single continuous stirring tank reactor and a single slurry loop reactor and other suitable reactors.

In a preferred embodiment, the polypropylene homopolymer simply uses a Ziegler-Natta catalyst, which comprises a titanium-catalyzed active metal species supported on a magnesium chloride support and suspended in mineral oil. 1. It is produced by a continuous agglomerated phase (concentrated propylene) stirring reaction device. The suspension catalyst can be pumped directly to the reactor. Hydrogen may be used as the chain transfer agent to control the molecular weight. The polymerization can be carried out in a stirring tank reactor, a gas phase flow bed reactor, a single continuous stirring tank reactor and a single slurry loop reactor. Such polymerization and resulting polypropylene homopolymers are described in US Patent Publication No. 2005/0272858 (see also International Publication No. 2004033509) and US Patent Publication No. 2004/0122196. Each of these three applications is incorporated herein by reference in its entirety.

In one embodiment, the propylene homopolymer has a molecular weight distribution (Mw / Mn) of 2 to 6, more preferably 2 to 5, and most preferably 3 to 5. All individual values and subranges from 2 to 6 are included herein and disclosed herein. In another embodiment, the molecular weight distribution is 6 or less, more preferably 5.5 or less, and even more preferably 5 or less.

In another embodiment, the propylene homopolymer has a density of 0.88 to 0.92 g / cc, preferably 0.89 to 0.91 g / cc. All individual values and subranges from 0.88 to 0.92 g / cc are included herein and disclosed herein.

In another embodiment, the propylene homopolymer is in a number of 10,000 g / mol to 200,000 g / mol, more preferably 15,000 g / mol to 150,000 g / mol, and most preferably 30,000 g / mol to 100,000 g / mol. It has an average molecular weight (Mn). All individual values and subranges from 10,000 g / mol to 200,000 g / mol are included herein and disclosed herein.

In another embodiment, the propylene homopolymer weighs 80,000 g / mol to 400,000 g / mol, more preferably 100,000 g / mol to 300,000 g / mol, and most preferably 120,000 g / mol to 200,000 g / mol. It has an average molecular weight (Mw). All individual values and subranges from 80,000 g / mol to 400,000 g / mol are included herein and disclosed herein.

Ethylene / α-olefin copolymer The compositions of the present invention contain at least one ethylene / α-olefin copolymer, which may optionally contain a diene. As used herein, "copolymer" refers to a polymer in which at least two monomers are polymerized. This includes, for example, copolymers, terpolymers and tetrapolymers. Specifically, ethylene is at least one comonome, typically 3 to 20 (C3 to C20) carbon atoms, preferably 4 to 20 (C4 to C20) carbon atoms, and even more preferably 4 to 12 carbon atoms. Includes polymers made by polymerizing with (C4 to C12) and even more preferably alpha olefins (α-olefins) having 4 to 8 (C4 to C8) carbon atoms. Alpha-olefins include, but are not limited to, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene. Preferred α-olefins include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene. The α-olefin is preferably a C4 to C8 α-olefin.

Copolymers include ethylene / butene (EB) copolymers, ethylene / hexene-1 (EH), ethylene / octene (EO) copolymers, ethylene / alpha-olefin / diene modified (EAODM) copolymers, such as ethylene / Included are propylene / diene modified (EPDM) copolymers and ethylene / propylene / octenter polymers. Preferred copolymers include EB, EH and EO copolymers.

Suitable diene monomers include conjugated and non-conjugated diene. The unconjugated diolefin can be a C6-C15 straight chain, branched chain or cyclic hydrocarbon diene. Examples of non-conjugated diene are linear acyclic diene, eg 1,4-hexadiene and 1,5-heptadiene; branched acyclic diene, eg 5-methyl-1,4-hexadiene, 2 -Methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadene, 3,7-dimethyl-1,6-octadene, 3,7-dimethyl-1,7 -Mixed isomers of octadiene, 5,7-dimethyl-1,7-octadene, 1,9-decadien, and dihydromilsen; monocyclic alicyclic diene, eg, 1,4-cyclohexadiene, 1,5- Cyclooctadiene and 1,5-cyclododecadene; polycyclic alicyclic condensation and crosslinked diene, eg tetrahydroinden, methyltetrahydroinden; alkenyl, alkyridine, cycloalkenyl and cycloalkyridene norbornene, eg 5-methylene-2 -Norbornene (MNB), 5-Etilidene-2-Norbornene (ENB), 5-Vinyl-2-Norbornene, 5-Propenyl-2-Norbornene, 5-Isopropyriden-2-Norbornene, 5- (4-Cyclopentenyl) -2-Norbornene and 5-Cyclohexylidene-2-Norbornene. Preferred non-conjugated dienes include ENB, 1,4-hexadiene, 7-methyl-1,6-octadiene, and more preferably the diene is ENB. Suitable conjugated dienes include 1,3-pentadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 4-methyl-1,3-pentadiene, or 1,3-cyclopentadiene.

Preferred copolymers typically do not contain substantially any diene monomer that induces LCB, but the cost is acceptable and the desired copolymer properties such as processability, tensile strength and elongation are at unacceptable levels. Such monomers may be included as long as they do not decrease to. Such diene monomers include, but are not limited to, dicyclopentadiene, NBD, methylnorbornadiene, vinyl-norbornene, 1,6-octadiene, 1,7-octadiene, and 1,9-decadiene. When added, such monomers can be added in an amount ranging from above 0 to 3 weight percent, more preferably above 0 to 2 weight percent, based on the weight of the copolymer.

The ethylene / α-olefin copolymers of the present invention can be branched and / or unbranched copolymers. The presence or absence of branches in the ethylene / α-olefin copolymer, and the amount of branches in the presence of the branches, can vary widely, which are the desired processing conditions and the desired polymer. It can depend on the characteristics.

The properties of ethylene / α-olefin (EAO) branches are not important to the practice of the present invention and are therefore subject to change for convenience. Preferably, the branch is a long chain branch (LCB). The ability to incorporate LCB into polymer backbones has been known and practiced for many years. US Pat. No. 3,821,143 uses 1,4-hexadiene as a branching monomer to make ethylene / propylene / diene (EPDM) polymers with LCB. Such branching agents are sometimes referred to as H branching agents. U.S. Pat. Nos. 6,300,451 and 6,372,847 also use a variety of H-type branching agents to make polymers with LCB. In U.S. Pat. No. 5,278,272, it was discovered that Geometric Constriction Catalysts (CGCs) have the ability to incorporate vinyl-terminated macromonomers into the polymer backbone to form LCB polymers. Such branches are called T-type branches. Each of these patents (US Pat. Nos. 3,821,143, 6,300,451, 6,372,847 and 5,278,272) is incorporated herein by reference in their entirety.

The '272 patent teaches that such CGCs are specific in their ability to incorporate large unsaturated molecules into the polymer backbone. The amount of LCB that can be incorporated by these CGCs is typically 0.01 LCB / 1000 carbon atoms to 3 LCB / 1000 carbon atoms (both skeletal carbon atoms and branched chain carbon atoms).

Preferably, the type of LCB in the copolymer used in the practice of the present invention is a T-type branch as opposed to an H-type branch. T-type branches are generally described in appropriate reaction conditions in the presence of a geometrically constrained catalyst, eg WO 00/26268 (corresponding US patent, US patent No. 6,680,361; the full text of which is incorporated herein by reference). It is obtained by copolymerization of ethylene or other alpha olefins with chain-terminated unsaturated macromonomers under what is known as. If extremely high levels of LCB are desired, H-type branching is the preferred method. This is because the T-type branch has a substantial upper limit on the degree of LCB. As discussed in WO00 / 26268, as T-type branching levels increase, the efficiency or throughput of the manufacturing process is significantly reduced until production becomes economically infeasible. T-type LCB polymers can be made with geometry-constrained catalysts without measurable gels, but at very high levels of T-type LCB. Since the macromonomer incorporated into the growing polymer chain has only one reactive unsaturated site, the resulting polymer contains side chains of various lengths only at different intervals along its polymer backbone. ..

H-type branches are generally obtained by copolymerizing an ethylene or other alpha olefin with a diene having two double bonds reactive with a non-metallocene type catalyst in the polymerization process. As the name implies, a diene attaches one polymer molecule to another polymer molecule by a diene bridge. The resulting polymer molecule resembles H, which can be described as a crosslink rather than a long chain branch. H-type branches are commonly used when extremely high levels of branching are desired. With too much diene, the polymer molecule forms so many branches or crosslinks that the polymer molecule is no longer soluble in the reaction solvent (in the solution process), resulting in precipitation from the solution. Gel particles of the polymer will be formed. In addition, the use of H-type branching agents may deactivate metallocene catalysts and reduce catalytic efficiency. Therefore, when using H-type branching agents, the catalyst used is generally not a metallocene catalyst. The catalyst used in the preparation of H-type branched polymers in US Pat. No. 6,372,847 (which is incorporated herein by reference in its entirety) is a vanadium-type catalyst.

Suitable ethylene copolymers include ENGAGE , AFFINITY and NORDEL polymers available from The Dow Chemical Company, and VISTALON and EXACT polymers available from Exxon Mobil Chemical Company. Also included are TAFMER polymers available from Mitsui Chemicals. Preferred ethylene copolymers include ENGAGE and AFFINITY polymers available from The Dow Chemical Company, VISTALON and EXACT polymers available from Exxon Mobil Chemical Company, and Mitsui Chemicals, Inc. Examples include available TAFMER polymers.

In another embodiment, the ethylene / α-olefin copolymer has a molecular weight distribution (Mw / Mn) of 1 to 5, more preferably 1.5 to 4, and most preferably 2 to 3. All individual values and subranges from 1 to 5 are included herein and disclosed herein.

In another embodiment, the ethylene / α-olefin copolymer has a density of 0.80 to 0.90 g / cc, preferably 0.82 to 0.88 g / cc, and most preferably 0.83 to 0.87 g / cc. All individual values and subranges from 0.80 to 0.90 g / cc are included herein and disclosed herein. In another embodiment, the ethylene / α-olefin copolymer has a density of 0.875 g / cc or less, preferably 0.86 g / cc or less, and even more preferably 0.85 g / cc or less.

In another embodiment, the ethylene / α-olefin copolymer is 0.05 to 10 g / 10 min, preferably 0.1 to 5 g / 10 min, and even more preferably 0.2 to 2 g / 10 min, or 0.5 to 1 g / 10 min. It has a minute melt index, I2 (190 ° C / 2.16 kg). All individual values and subranges from 0.05 to 10 g / 10 min are included herein and disclosed herein. In another embodiment, the elastomeric component has a melt index, I2, of 1 g / 10 min or less, preferably 0.5 g / 10 min or less, and even more preferably 0.3 g / 10 min or less.

In another embodiment, the ethylene / α-olefin copolymer is 40,000 g / mol to 200,000 g / mol, more preferably 50,000 g / mol to 150,000 g / mol, and most preferably 60,000 g / mol to 100,000. It has a number average molecular weight (Mn) of g / mol. All individual values and subranges from 40,000 g / mol to 200,000 g / mol are included herein and disclosed herein.

In another embodiment, the ethylene / α-olefin copolymer is 80,000 g / mol to 400,000 g / mol, more preferably 100,000 g / mol to 300,000 g / mol, and most preferably 120,000 g / mol to 200,000. It has a weight average molecular weight (Mw) of g / mol. All individual values and subranges from 80,000 g / mol to 400,000 g / mol are included herein and disclosed herein.

In another embodiment, the ethylene / α-olefin copolymer has a Tg lower than -30 ° C, preferably lower than -40 ° C, and even more preferably lower than -50 ° C.

In another embodiment, the ethylene / α-olefin copolymer is a uniformly branched, linear or uniformly branched, substantially linear ethylene / α-olefin copolymer. Is. The process for making homogeneous polymers is disclosed in US Pat. Nos. 5,206,075 and 5,241,031 and PCT International Application WO93 / 03093, each of which is incorporated herein by reference in its entirety. Further details regarding the production of homogeneous ethylene α-olefin copolymers are disclosed in US Pat. Nos. 5,206,075 and 5,241,031 and PCT International Applications WO93 / 03093 and WO93 / 03414, all four of which are in their entirety. Incorporated herein by reference as.

The terms "uniform" and "uniformly branched" mean that the copolymers are randomly distributed within a given polymer molecule, and substantially all of the polymer molecules have the same ethylene to comonomer ratio. / Used for α-olefin polymers (or copolymers). Uniformly branched ethylene copolymers include linear ethylene copolymers and substantially linear ethylene copolymers.

There are no long-chain branches, but there are short-chain branches derived from comonomer polymerized in the copolymer, and they are uniformly distributed within the same polymer chain and between different polymer chains. The polymer is contained in a uniformly branched linear ethylene copolymer. That is, a uniformly branched linear ethylene copolymer is exactly linear produced using, for example, a uniformly branched distribution polymerization process as described by Elston in US Pat. No. 3,645,992. There are no long chain branches, as is the case with low density polyethylene polymers or linear high density polyethylene polymers. Examples of uniformly branched linear ethylene / α-olefin copolymers include TAFMER polymer supplied by Mitsui Chemicals, Inc. and EXACT supplied by Exxon Mobil Chemical Company. ).

The substantially linear ethylene copolymers used in the present invention are described in US Pat. Nos. 5,272,236 and 5,278,272, the entire contents of which are incorporated herein by reference. As discussed above, substantially linear ethylene copolymers have their comonomer randomly distributed within a given copolymer molecule, and substantially all of the copolymer molecules. , Which have the same ethylene / comonomer ratio in the copolymer. The substantially linear ethylene copolymer is made using a geometry constraining catalyst. Geometric constraint catalysts and examples of such fabrications are described in US Pat. Nos. 5,272,236 and 5,278,272.

In addition, the substantially linear ethylene copolymer is a uniformly branched ethylene polymer with long chain branches. Long-chain branches have approximately the same comonomer distribution as the polymer backbone, and may have approximately the same length as the polymer backbone. As discussed above, "substantially linear" generally means, on average, 0.01 long-chain branches to a total of 1000 carbons per 1000 carbons (including both skeletal and branched carbons). With respect to the polymer substituted with 3 long chain branches per hit.

Commercial examples of substantially linear polymers include ENGAGE Polymer (The Dow Chemical Company) and AFFINITY Polymer (The Dow Chemical Company).

The substantially linear ethylene copolymer forms a specific class of uniformly branched ethylene polymers. They are substantially different from the well-known class of conventional uniform branched linear ethylene copolymers described by Elston in US Pat. No. 3,645,992, and in addition, they are conventional homogeneous Cheegler-Natta catalytic polymerization. Linear ethylene polymers (eg, ultra-low density polyethylene (ULDPE), linear low density polyethylene (LLDPE) or high density polyethylene manufactured using the techniques disclosed by Anderson et al. In US Pat. No. 4,076,698. Not in the same class as (HDPE)), but the same as high pressure, free radical initiation, high branch polyethylene, such as low density polyethylene (LDPE), ethylene-acrylic acid (EAA) copolymers and ethylene vinyl acetate (EVA) copolymers. Not a class.

Plate-shaped filler Any inert material, generally having a disk-like shape, can be used as the plate-like filler in the TPO composition of the present invention. Typically and preferably, the plate-like filler is an Inactive Inorganic Powder, such as talc, kaolin clay or mica, more preferably plate-like talc. Common plate talc and kaolin clay are identified in Tables 3 and 4, respectively. Certain grades of plate talc do not exceed the density of the polymeric resin in which to replace the composition and have sufficient strengthening strength to impart or maintain the desired flexural modulus and HDT of the final composition. Is selected for. Typically, the density of commercial grade resins is about 1.13 g / mL. For compositions made of the high crystalline propylene homopolymers and EAO elastomers of the invention, a filler filling of about 30 weight percent is common, but more or less if desired. You may use it.<tables num="3"><img file="JP5118030B2_D0003.tif" /></tables><tables num="4"><img file="JP5118030B2_D0004.tif" /></tables>

It is noted that during the processing of the compositions of the present invention, under flow stress, the plate fillers are generally aligned parallel to the flow direction of the composition. This flow pattern helps reduce shrinkage of the composition in its flow direction, as well as this flow pattern enhances the resulting polymer product, increasing both thermal deformation temperature and flexural modulus. Can be made to. The effectiveness of a particular filler can be determined by applying a straight line to the data taken at various filler addition levels. The slope of the line, in units of "percentage of increase in properties" divided by "percentage of filler addition", is a measure of the efficiency of a particular filler with respect to an increase in either the thermal deformation temperature or the flexural modulus.

The fortification efficiency of the filler on the composition is assessed by measuring the flexural modulus of the polypropylene and EAO blend and the effect of adding 20 weight percent of the filler on HDT. The flexural modulus efficiency coefficient, which has a unit of percent increase in modulus of elasticity relative to the filler filling percent, can then be calculated. This coefficient is relatively straight in the filler filling range of about 10-40 weight percent. Similar associated thermal deformation efficiency factors for each filler grade by blending high crystalline isotactic propylene homopolymer and EAO elastomer impact resistance modifier with or without 20 weight percent reinforcing filler. Can be calculated to. The thermal deformation efficiency factor is less linear than the flexural modulus efficiency factor and is more susceptible to the specific grades of polypropylene and EAO. As a result, the filler benchmarks of interest generally have a fill of 20 weight percent relative to the high crystalline isotactic homopolymers and EAO elastomer impact resistance modifiers of the present invention. The preferred reinforcing filler grades of the present invention, such as plate talc, are approximately 1.5 or greater when blended with the high crystalline isotactic propylene homopolymer and EAO elastomer impact resistance modifier at a filling rate of 20% by weight. More preferably, it has a thermal deformation efficiency coefficient of about 1.7 or more, and most preferably about 1.9 or more. At the same time, the preferred reinforcing filler grades of the present invention have a flexural modulus efficiency coefficient greater than about 3, preferably greater than about 3.5, and most preferably greater than about 4.

In one embodiment, the particle size of the medium is 0.1 micron to 50 micron, preferably 0.5 micron to 25 micron, and even more preferably 1 micron to 10 micron. All individual values and subranges from 0.1 micron to 50 micron are included herein and disclosed herein.

Preparation of composition As discussed above, the TPO compositions of the present invention contain at least one propylene homopolymer, at least one ethylene / α-olefin copolymer and at least one plate-like filler. Such compositions can be made by any one of a number of different processes, but in general these processes are one of two categories: post-reactor blending, in-reactor blending. It is classified into one or a combination of these. An example of the former is a melt extruder (two or more solid polymers are fed and physically mixed into a substantially uniform composition) and a large number of solutions arranged in parallel. A slurry or gas phase reactor (outputs from each are blended together to form a substantially uniform composition, which is finally recovered in solid form). An example of the latter is a large number of reactors connected in series and a single reactor packed with two or more catalysts. Preferably, the composition is made by post-reactor blending.

The filler may first be blended with one or the other polymer and then the other polymer may be added, but the propylene homopolymer and the ethylene / α-olefin copolymer are generally blended with each other prior to the filler addition. The filler may be added neat or as a masterbatch based on either polymer. All components of the composition are blended with each other until a substantially uniform composition is obtained. Standard mixers and extruders can be used for this blending. The compositions of the present invention can contain other components such as pigments, antioxidants and processing aids.

The TPO composition of the present invention is used in the same manner as conventional polycarbonate-based and polystyrene-based compositions. In particular, the compositions of the present invention are well suited for the manufacture of soft touch instrument panels and structures used in the production of similar products.

Composition The compositions of the present invention are preferably 60 to 90% by weight, preferably 65 to 85% by weight, and even more preferably 70 to 75% by weight, based on the total weight of the propylene homopolymer and the ethylene / α-olefin copolymer. Contains% propylene homopolymer. All individual values and subranges of 60 to 90 weight percent (polypropylene homopolymers) are included herein and disclosed herein. The compositions of the present invention are preferably 10-40% by weight, preferably 15-37% by weight, and even more preferably 20-35% by weight, based on the total weight of the propylene homopolymer and the ethylene / α-olefin copolymer. Contains% ethylene / α-olefin copolymer. All individual values and subranges of 10 to 40 weight percent (ethylene / α-olefin copolymer) are included herein and disclosed herein.

In one embodiment, the composition contains 25 to 50 weight percent, preferably 30 to 45 weight percent, and even more preferably 35 to 40 weight percent plate-like filler based on the total weight of the composition. .. All individual values and subranges of 25 to 50 weight percent (plate filler) are included herein and disclosed herein.

In another embodiment, the composition has a crystallization temperature of 110 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and most preferably 140 ° C. or higher, Tc.

In another embodiment, the composition has an HDT of 110 ° C or higher, preferably 120 ° C or higher, more preferably 130 ° C or higher, and most preferably 140 ° C or higher, as measured by ASTM D648. ..

In another embodiment, the composition does not contain another propylene-based polymer other than the propylene homopolymer component.

In another embodiment, the composition comprises 50% by weight or more, 60% by weight or more, and more preferably 70% by weight or more of propylene homopolymers based on the total weight of the composition.

In another embodiment, the composition comprises 40 weight percent or less, preferably 35 weight percent or less, and even more preferably 30 weight percent or less of an ethylene / α-olefin copolymer based on the total weight of the composition. contains.

In another embodiment, the composition does not contain a copolymer containing only ethylene and propylene monomer units.

In another embodiment, the composition does not contain a styrene block copolymer.

In another embodiment, the composition contains only one ethylene / α-olefin copolymer.

In one embodiment, the composition does not contain EPDM polymer.

In another embodiment, the composition does not contain an EPR polymer.

In another embodiment, the composition does not contain block copolymers.

In another embodiment, the composition contains a non-halogen intumescent, as described in US Pat. No. 6,737,131, which is incorporated herein by reference. As described in this patent, "intmescence" is defined as the carbonized layer formation process that occurs due to the reaction of expansion additives in plastics when exposed to flames or high heat. These additives react to create a carbon adiabatic barrier that eliminates combustion. Preferred non-halogen swelling additives are Hoechst Chemical Company products (phosphate compounds), Exolit® MR; Great Lakes Chemical Company products (phosphate compounds), Char guard 32911 or NH-1511; Amgard, a product of Spin Flam; Albright &amp; Wilson (ethylenediamine phosphate), a product of Monsanto Chemical Company (phosphate compound) EDAP; product of Budauheim (melamine--pyrophosphate), Budget 311; product of a company, NCENDX P-30; and product of Unitex Corp (ethylenediamine phosphate), FRX44 can be mentioned.

In another embodiment, the composition contains a flame retardant that is a metal hydrate (eg, aluminum trihydrate, magnesium hydroxide or a combination thereof). In a further embodiment, the flame retardant is a metal hydrate and is present in an amount between 25 weight percent and 75 weight percent based on the total weight of the composition. In another embodiment, the surface of the metal hydroxide may be coated with one or more materials, including silane, titanate, zirconate, carboxylic acid, and maleic anhydride Graft I polymer. In another embodiment, the average particle size of the metal hydrate can range from less than 0.1 micrometer to 50 micrometers. In some cases, the use of metal hydroxides with nanoscale particle sizes may be desirable. The metal hydroxide may be natural or synthetic. The flame-retardant composition may contain other flame-retardant additives. Other suitable non-halogenated flame retardant additives include calcium carbonate, I red phosphorus, silica, alumina, titanium oxide, talc, clay, organically modified clay, zinc borate t (zinc t). borate), antimony trioxide, ash stone, mica, magadiate, organically modified magadiate, silicone polymers, phosphate esters, hindered amine stabilizers, ammonium octamolybdate, expanded compounds, and effervescent graphite. Suitable halogenated flame retardant additives include decabromodiphenyl oxide, decabromodiphenylethane, ethylene-big (tetrabromophthalimide), and 1,4: 7,10 dimethanodibenzo (a, e) cyclooctane, 1,2, 3,4,7,8,9,10,13,13,14,14-dodecachloro 1,4,4a, 5,6,7,10,10a, 11,12,12a-dodecahydro-. A further description of such flame retardants can be found in WO 2005/023924, which is incorporated herein by reference in its entirety.

In another embodiment, the composition of the invention comprises a compatible amount of the flame retardant package, which package comprises an alkaline halogenated flame retardant, an aromatic halogenated flame retardant and optionally a flame retardant synergist. .. In a further embodiment, the alkaline flame retardant is hexahalocyclododecane; tetrabromocyclooctane; pentabromochlorocyclohexane; 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane; 1,1,1,3. -Tetrabromononane; or a combination of these. In another embodiment, the aromatic halogenated flame retardant is one or more hexahalodiphenyl ethers; octahalodiphenyl ethers; decahalodiphenyl ethers; decahalobiphenyls, ethane; 1,2-bis (trihalophenoxy) ethane; 1 , 2-bis (pentahalophenoxy) ethane; tetrahalobisphenol-A; ethylene (N, N')-bis-tetrahalophthalimide; tetrabromobisphenol-A Bis (2,3-dibromopropyl ether; tetrahalophthalic anhydride; hexahalobenzene; halogenated indan; halogenated phosphate; polystyrene halide; polymers of bisphenol-A and epichlorohydrin; or these In yet another embodiment, the flame retardant synergizer comprises one or more metal oxides, halogenated paraffins, triphenylphosphates, dimethyldiphenylbutane, polycumyls, or combinations thereof. ..

In another embodiment, the composition comprises from about 0.5 to about 8 parts by weight of alkaline halogenated flame retardant; from about 0.5 to about 8 parts by weight of aromatic halogenated flame retardant; from 0 to about 6 parts by weight of flame retardant synergistic. Contains agents (all based on the total weight of the composition). A further description of such flame retardants can be found in WO 2002/12377, which is incorporated herein by reference in its entirety.

Advantageously, the composition may further comprise the polymer or at least one of the types of additives conventionally added to the polymer composition. These additives include, for example, process oils; antioxidants; surfactants; UV stabilizers; scratch / scratch inhibitors, such as polydimethylsiloxane (PDMS) or functionalized polydimethylsiloxane or IRGASURF®. SR100 (Ciba Specialty Scratch formulations containing (available from Chemicals) or ercamides; Anti-adhesives; Dispersants; Foaming agents; Linear or substantially linear EAO; LDPE; LLDPE; Lubricants; Oxides; antibacterial agents such as organic metals, isothiazolones, organic sulfur and mercaptans; antioxidants such as phenols, secondary amines, phosphites and thioesters; antioxidants such as tetraammonium compounds, amines , And ethoxylated, propoxydated or glycerol compounds. Examples of the functionalized polydimethylsiloxane include hydroxyfunctionalized polydimethylsiloxane, amine-functionalized polydimethylsiloxane, vinyl-functionalized polydimethylsiloxane, aryl-functionalized polydimethylsiloxane, alkyl-functionalized polydimethylsiloxane, and carboxyl-functionalized polydimethylsiloxane. Examples include, but are not limited to, mercaptan-functionalized polydimethylsiloxane and derivatives thereof.

The compositions of the present invention may also contain additional additives. Additional additives include hydrolysis stabilizers; lubricants such as fatty acids, fatty alcohols, esters, fatty amides, metal stearate salts, paraffin and microcrystalin waxes, silicones and ortholates; mold release agents such as fine particles. Or powdered solids, soaps, waxes, silicones, polyglycols, and composite esters such as trimethylol propane tristearate or pentaerythritol tetrastearate; pigments, dyes and colorants; plasticizers such as dibasic acids (or theirs). Esters of (anhydrous) and monohydric alcohols, such as o-phthalates, adipates and benzoates; heat stabilizers such as organic simmercaptide, octyl esters of thioglycolic acid, and barium or cadmium carboxylates; hindered amines, o -Ultraviolet stabilizers used as hydroxy-phenylbenzotriazole, 2-hydroxy, 4-alkoxybenzophenone, salicylate, cyanoacrylate, nickel chelate and benzylene malonate and oxalanilide; and zeolites, molecular sieves, antistatics and Other known deodorants include, but are not limited to.

A preferred hindered phenolic antioxidant is Irganox® 1076 Antioxidant, available from Ciba Specialty Chemicals. One of ordinary skill in the art can easily select any suitable combination of additives, the amount of the additive and the method of incorporating the additive into the composition without undue experimentation. In general, each of the above additives, when used, does not exceed 45 weight percent based on total composition weight, and is advantageously from about 0.001 to about 20 weight percent, preferably 0.01 to 15 weight percent, and even more preferably. Is 0.1 to 10 weight percent.

In one embodiment of the invention, the composition of the invention comprises at least one polydimethylsiloxane (PDMS) to improve the scratch resistance of the resulting product. This polydimethylsiloxane is generally present in an amount of 0.1 to 10 weight percent based on the weight of the polymer composition. Suitable polydimethylsiloxanes, 100,000 centistokes chromatography click greater, more preferably 1 × 10⁶From 2.5 × 10⁶Centistokes with a viscosity at 25 ° C can be mentioned. In a further embodiment, the composition also comprises an ethylene homopolymer or ethylene copolymer grafted with maleic anhydride or a succinic anhydride group, preferably the grafted ethylene homopolymer or copolymer is the composition. Consists of less than 20% of. In a further embodiment, the composition also comprises at least one additive, such as a plasticizer, pigment or colorant, UV stabilizer, or filler. Examples of the filler include calcined or non-fired fillers. Suitable fillers include, but are not limited to, calcium carbonate and siliceous stone. Ingredients suitable for scratch-resistant formulations are described in more detail in US Pat. No. 5,902,854. The entire contents of the patent are incorporated herein by reference in their entirety.

Further scratch resistant formulations useful in the compositions of the present invention contain IRGASURF® SR 100 with one or more additives as described herein. Particularly suitable formulations are aliphatic amides in polyethylene carriers such as IRGASURF® SR 100 and one or more fillers such as siliceous stones and ethylenes grafted with maleic anhydride or succinic anhydride groups. Contains homopolymers or copolymers. Other scratch-resistant polyolefin formulations are described in US Patent Publication No. 2006009554 (the corresponding patent of WO 2006/003127), which is incorporated herein by reference in its entirety.

In a particularly preferred embodiment, the composition comprises a scratch concentrate, which is also 10 to 30 weight percent at least one colorant and / or UV stabilizer, 5 to 15 weight. At least one polydimethylsiloxane in percent, at least one filler in 30 to 50 percent by weight, and at least one ethylene homopolymer or copolymer grafted with maleic anhydride or succinic anhydride in 10 to 35 percent by weight. Contains. The weight percentage is based on the total weight of the scratch concentrate.

Article of the present invention Articles can be made by injection molding, extrusion, extrusion followed by either male or female thermoforming, low pressure molding, or compression molding.

Far from exhaustive, a partial list of articles that can be made from the compositions of the present invention is polymer films, cloth coating sheets, polymer sheets, foams, tubes, fibers, coatings, computer parts, building materials, For household appliances, power housings, trash cans, storage or packaging containers, lawn furniture strips or cloths, lawnmowers, garden hoses, and other garden equipment parts, refrigerator gaskets, acoustic systems, utility carts. Includes parts, desk edging, toys and ship parts. This composition can also be used for roofing materials such as roofing membranes. In addition, the composition can be used in making footwear components such as shafts for boots, especially industrial work boots. One of ordinary skill in the art can easily grow this list without undue experimentation. Additional articles include extruded variants and wall-based variants.

The parts produced by molding the compositions of the present invention are excellent in formability and mechanical strength, including excellent flexural modulus and breaking point tensile elongation, high rigidity and high temperature and low temperature impact resistance. ing.

The parts made from the compositions of the present invention are lightweight and provide design freedom due to their ease of processing. Such compositions give rise to parts that have improved stiffness, fluidity and impact resistance while reducing molding shrinkage and dimensional changes during heat treatment in the mold. Thus, such compositions allow the manufacture of injection molded parts with reduced wall thickness and improved thermal and mechanical properties as well as improved appearance.

The composition of the present invention is sufficiently fluid at the molding temperature to fill the mold. Overall, the compositions of the present invention have excellent moldability and high rigidity, and parts with excellent mechanical strength, impact resistance, ductility and heat deformation using this composition. Can be formed. Such parts have a good appearance, have reduced molding dimensional changes and a reduced coefficient of linear thermal expansion. The present composition can produce injection-molded parts having a thinner wall thickness than those of parts made from conventional PC / ABS resin. In addition, such parts are lighter than parts made from polycarbonate / ABS blends. In general, parts made from the compositions of the present invention are approximately 7 weight percent lighter than polycarbonate / ABS blends.

Definition All numerical ranges listed herein include all values from their lowest and highest values in 1-unit increments, provided that there is a gap of at least 2 units between any lowest and highest value. The condition is that there is. As an example, if a compositional, physical or other property such as molecular weight, melt index, etc. is stated to be 100 to 1,000, then all individual values, such as 100, 101, 102, etc., and Subranges such as 100 to 144, 155 to 170, 197 to 200, etc. are to be construed as explicitly listed herein. For ranges that contain values less than 1 or fractions greater than 1 (eg 1.1, 1.5, etc.), one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. For ranges containing single digit numbers less than 10, one unit is generally considered to be 0.1. These are merely examples of what can be considered concretely, and it is believed that all possible combinations of the very large number of values between the listed minimum and maximum values are explicitly stated in this application. There must be. Numerical ranges are listed as discussed here in relation to density, weight percent of ingredients, tan deltas, molecular weight and other properties.

As used herein, the term "composition" includes a mixture of materials containing the composition, as well as reaction and degradation products formed from the materials of the composition.

As used herein, the term "polymer" refers to a polymer compound made by polymerizing monomers, whether of the same type or of different types. Thus, this general term includes the term homopolymers commonly used to refer to polymers made from only one type of monomer, and the term copolymers defined later herein.

As discussed above, as used herein, the term "copolymer" refers to a polymer made by the polymerization of at least two different types of monomers. Thus, the term copolymer includes polymers commonly used to refer to polymers made from two different types of monomers, and polymers made from more than two different types of monomers.

As used herein, the terms "ethylene / α-olefin copolymer", "ethylene polymer" or similar terms refer primarily to polymers formed from ethylene monomer units (more than 50 mol percent). The molar percentage is based on the total number of moles of polymerizable monomer.

As used herein, the term "blend" or "polymer blend" means a composition of two or more polymers. Such blends may or may not be miscible. Such blends may or may not be phase separated. Such blends may or may not contain one or more domain structures as determined by transmission electron microscopy.

Measurement The term "MI" is measured using ASTM D-1238 for polyethylene polymers, condition 190 ° C / 2.16 kg, and 230 ° C / 2.16 kg for polypropylene polymers, at g / 10 min. Melt index, I2 or I₂Means.

Density is measured according to ASTM D-792. The measured density is the "quick density", which means that the density was determined one hour after molding.

Gel permeation chromatography The average molecular weight and molecular weight distribution of ethylene-based polymers were determined by a gel permeation chromatograph system consisting of Polymer Laboratories Model 200 series high temperature chromatographs. The column and rotary compartment were operated at 140 ° C for polyethylene-based polymers. The columns used were three Polymer Laboratories 10-micron Mixed-B columns. The solvent was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The solvent used as the mobile phase and to prepare the sample contained 200 ppm butylated hydroxytoluene (BHT). The ethylene polymer was prepared by light stirring at 160 ° C for 2 hours, and the propylene polymer was dissolved for 2.5 hours. The injection volume was 100 microliters and the flow rate was 1.0 ml / min. Calibration of the GPC column set has a molecular weight in the range of 580 to 8,400,000, Polymer This was done using polystyrene standard materials with a narrow molecular weight distribution purchased from Laboratories (UK). The peak molecular weight of the polystyrene standard was converted to polyethylene molecular weight using the following equation (Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M polyethylene = A × (M polystyrene)^B(In the formula, M is the molecular weight, A has a value of 0.4315 and B is equal to 1.0).

Polyethylene equivalent molecular weight calculations were performed using Viscotek TriSEC software Version 3.0. The molecular weight for polypropylene-based polymers is the Mark-Houwink ratio according to ASTM D6474.9714-1 (in this case a = 0.702 and logK = -3.9 for polystyrene, and a = 0.725 and logK = -3.721 for polypropylene). Can be determined using. For polypropylene-based samples, the column and rotary compartment were operated at 160 ° C.

Differential scanning calorimetry Differential scanning calorimetry (DSC) can be used to measure crystallinity in polyethylene (PE) -based and polypropylene (PP) -based samples. The sample is pressed into a thin film at a temperature of 190 ° C. Weigh about 5 to 8 milligrams of thin film sample and place in DSC pan. Bend the edge of the lid onto the pan to ensure a closed atmosphere. The sample pan is placed in a DSC cell and then heated to a temperature of about 180-200 ° C for PE (230 ° C for PP) at a rate of about 10 ° C / min. Hold the sample at this temperature for 3 minutes. The sample is then cooled to -90 ° C for PE (-90 ° C for PP) at a rate of 10 ° C / min and kept at that temperature for 3-5 minutes. The sample is then heated at a rate of 10 ° C / min until completely melted (second heating; about 180 ° C for PE and 230 ° C for PP). Unless otherwise stated, the melting point (Tm) of each polymer sample is determined from the second thermal curve obtained from the DSC, as explained above. The crystallization temperature (Tc) is measured from the first cooling curve.

The following examples illustrate the invention and are not, expressly or implicitly, limiting the invention. Unless otherwise stated, all parts and percentages are by weight.

Experiment Five grades of polypropylene are listed in Table 5 below.

Profax PD 702 is a conventional propylene homopolymer sold by Basell.

JP 707 is a conventional on-site, heterophase impact resistant propylene copolymer of propylene and ethylene sold by Mitsui Chemicals, Inc.

Accpro 9934X, now identified as Innovene H35Z-02, is a nucleated, 35MFR, high crystalline isotactic propylene homopolymer.

D118 is a development grade of nucleated high crystalline propylene homopolymer available from The Dow Chemical Company. This polymer has about 41,000 g / mol of Mn, about 183,000 / mol of Mw, and about 4.5 Mw / Mn.

CDC-1 is a nucleating-free version of the D118 propylene homopolymer that has been viscous-fractured to 35 melt indexes by shear and peroxide.

CDC-2 is another version of the D118 propylene homopolymer, which was prepared with a nucleating agent and then viscously disrupted to 35 MRFs.<tables num="5"><img file="JP5118030B2_D0005.tif" /></tables>

By testing the physical properties of the CDC grade, the effect of nucleation can be clearly seen.

A number of EAO elastomer impact resistant modifiers are available for use in the practice of the present invention, including ethylene / octene, ethylene / butene and ethylene / propene copolymers.

ENR 7380 is for impact resistance modification due to its low Tg, low tan delta measured at 190 ° C and 0.1 radians per second, and the balance of the difference of 10.3 ° C between its melting point and HDT. A preferred EAO elastomer.

In the compositions described below, polypropylene homopolymers and ethylene / α-olefins were mixed in a twin-screw extruder without a plate filler. The polymer was supplied at a total supply of 30 lbs per hour. The screw was rotated at 300 rpm. The temperature for the barrel zone after the first supply zone, as well as for the transfer and die, was set to 200 ° C. Pellets were made with a Gala underwater pelletizer.

Impact resistance modifications result in a reduction in both polypropylene flexural modulus and HDT, as shown in Tables 6 and 7 below. All formulations were prepared using 70 weight percent selected polypropylene and 30 weight percent selected EAO, each weight percentage being based on the total weight of the polypropylene and EAO. The 8000 Series Engage Elastomer is a copolymer of ethylene and 1-octene. The 7000 Series Engage Elastomer is a copolymer of ethylene and 1-butene. Engage 8100 has Mn of about 75,000 g / mol, Mw of about 150,000 g / mol, and Mw / Mn of 2.0. Engage 8150 has about 87,000 g / mol of Mn, about 176,000 g / mol of Mw, and 2.0 of Mw / Mn. ENR 7380 has about 82,000 g / mol of Mn, about 174,000 g / mol of Mw, and 2.1 of Mw / Mn.<tables num="6"><img file="JP5118030B2_D0006.tif" /></tables>

The data in Table 6 show that the percentage reduction in flexural modulus (1% modulus of splitting) does not change significantly within this elastomer group. Similar behavior is seen with respect to the percentage of reduction in HDT (approximately 25% of HDT, regardless of propylene and, regardless of elastomer), as shown in Table 7 below. Again, the properties for a neat polymer blend of 70 weight percent selected polypropylene and 30 weight percent selected elastomer are shown.<tables num="7"><img file="JP5118030B2_D0007.tif" /></tables>

The importance of plate-like fillers is their strengthening properties. Table 8 below shows the effect of adding talc at the 10 weight percent level on the flexural modulus of each conventional polypropylene grade. The second part of this table shows how the 10 and 20 weight percent levels of three different talcs show the flexural modulus of impact resistant modified random copolymer polypropylene at 30 weight percent in various EAO grades on a polymer basis. It indicates whether to increase. In each case, the weight percent of talc is based on the total weight of its polypropylene, EAO and talc.

Those skilled in the art will know how to formulate compositions (percentages of polypropylene, EAO and filler components) to supplement additional additives such as color concentrates and other additive concentrates.

To study the effects of individual grades of talc, the impact resistance of two grades of polypropylene (homomopolymer and impact resistant copolymer) was improved with eight different grades of EAO and three different grades of talc. Polypropylene grades were 35MFR homopolymers, Basell Profax PD702, and 35MFR impact resistant copolymers, J707PT (heterophase EPR or PER impact resistant polypropylene, manufactured and sold by Grand Polymer in a reactor).

Compounds were prepared by feeding selective polypropylene, selective elastomers and selective talc to a twin screw extruder under the conditions used in previous studies. The ratio of polypropylene to elastomer was fixed at 70 weight percent polypropylene to 30 weight percent elastomer. Each weight percentage is based on the total weight of the polypropylene and its EAO. When the compound was prepared from J707PT, in fact, the result of this practice was the two elastomers present in the final compound, the first of which was from a two-phase polypropylene copolymer and the second. The elastomer was from a formulation.

The ratio of polypropylene supplied to the extruder to ethylene elastomer was kept constant at 70 parts by weight to 30 parts by weight. The polymer supplied was adjusted and the talc was increased to reach the target amount of talc content. Thus, formulations containing a total of 10 weight percent talc were prepared with 63 weight percent polypropylene and 27 weight percent elastomer and 10 weight percent talc. Similarly, the 20 weight percent talc formulation contained 56 weight percent selective polypropylene grade, 24 weight percent selective elastomer and 20 weight percent selective talc.<tables num="8"><img file="JP5118030B2_D0008.tif" /></tables>

Another way to express this same information, which normalizes the response to individual talc grades at various levels, is to express the same information as an increase in flexural modulus per percent of talc filling. This description is defined as the unnuclear flexural modulus efficiency coefficient. The coefficient is dimensionless. The coefficients are reported in Table 9 below.<tables num="9"><img file="JP5118030B2_D0009.tif" /></tables>

Similar studies can be conducted on the effects of fortifying fillers on HDT. Since the difference between conventional grade polypropylene and EAO HDT is relatively small, impact resistance modification effects are expected for high crystalline isotactic homopolymer polypropylene grades, as reported in Table 10 below. Lower than the one.<tables num="10"><img file="JP5118030B2_D0010.tif" /></tables>

As can be seen from Tables 9 and 10 above, the reinforcing fillers should be benchmarked for their efficiency in increasing HDT (ASTM D634, 0.445MPa) and 1 percent secant flexural modulus (ASTM D790). Can be done. Based on these efficiency factors, filler selections can be compared to prepare TPO compositions with properties equivalent to those of conventional resins such as PC / ABS. Of the plate talc grades reported in the table above, the Impact 710 gives the best balance of properties.

The polypropylene grades reported above were not nucleated. The combination of TPO composition and talc is known to result in polypropylene nucleation due to the large surface area and irregular shape of talc. Therefore, part of the benefit from the addition of talc is the nucleation effect of talc. Most of the high crystalline isotactic homopolymer polypropylene grades as sold are nucleated and both nucleated and non-nucleated to emphasize their rigidity (flexural modulus) and HDT. Performance was evaluated. The results are reported in Table 11 below.

For this study, we chose to use high crystalline homopolymer polypropylene with an MFR of 35. First, this grade was manufactured without nucleating agents and labeled CDC0501. The material was reprepared and only then a nucleating agent was added prior to viscous fracture of the polymer. This nucleated grade was labeled CDC0505. In both cases, 70 weight percent of each high crystalline polypropylene and 30 weight percent ethylene / 1-butene copolymer, ENR 7380, were used to prepare an impact resistant modified blend, but the extruder was supplied with talc. There wasn't. In subsequent experiments, polypropylene, elastomers and talc were fed to the twin screw extruder in appropriate proportions to make each highly crystalline polypropylene impact resistant modified, talc-filled compound. The 20 weight percent talc-containing composition received a supply of 56 weight percent polypropylene, 24 weight percent ENR 7380 and 20 weight percent talc. The composition containing 30 weight percent talc contains 49 weight percent polypropylene and 21 weight percent ENR. It received a supply of 7380 and 30 weight percent talc. Finally, the 40 weight percent talc-containing composition received a supply of 42 weight percent polypropylene, 18 weight percent ENR 7380 and 40 weight percent talc. These characteristics were measured and reported in Table 11.<tables num="11"><img file="JP5118030B2_D0011.tif" /></tables>

The benefits of nucleation are clearly visible in neat propylene homopolymers, which produce HDTs as high as 25.9 degrees and secant elastic moduli as high as approximately 85,000 psi. These benefits are diminished when impact resistant modifications are made with ENR 7380 at 30 weight percent of all polymer additives (polypropylene and EAO) to produce TPO compositions. The difference in flexural modulus is less than 30,000 psi and the difference in HDT is less than 11 ° C. Filling the TPO composition with talc loses the benefits of nucleation. These data allow a flexural modulus of 142057 psi and an HDT of 85.6 ° C to be a benchmark for assessing the strengthening effect of the reinforcing filler. This is useful because most common commercial grades of high crystalline isotactic propylene homopolymers are all nucleated for flexural modulus and HDT elevation.

The correlations identified above can be used to screen alternative reinforcing plate fillers with standard formulations based on the more widely available nucleated high crystalline isotactic propylene homopolymers. The polymer formulation is 70 weight percent nucleated high crystalline isotactic propylene homopolymer vs. 30 weight percent EAO elastomer impact resistance modifier. Accpro 9934X polypropylene and ENR 7380 EAO were used for the next comparison of filler efficiencies. Some grades of plate fillers tested include delaminated kaolin clay and plate talc from Canadian suppliers, as listed in Table 12.<tables num="12"><img file="JP5118030B2_D0012.tif" /></tables>

Using 142057 psi as the flexural modulus for a nucleus-free, filler-free, impact-resistant modified formulation, and a nuclear-free flexural modulus efficiency coefficient of 3, a 20 lb-fill filler fill has a flexural modulus of 227,291 psi. Should be. Similarly, a reinforcing filler that meets the requirements of the present invention with an HDT efficiency factor of 1.5 also has an HDT of 111.3 ° C. JetFil plate talc grade meets these requirements, but kaolin grade does not.

The present invention has been described in some detail by the particular embodiments described above, but the details are for purposes of illustration only. One of ordinary skill in the art can make many modifications and modifications without departing from the spirit and scope of the invention as described in the subsequent claims.