Polyamide blend

[Detailed Description of the Invention]

The present invention relates to the polyamide molding composition made tough by the polymer-like strengthening agent, and more particularly a polyamide blend thing. Improvement of the shock strength of polyamide resin is interesting for many years from the resistance over crush of polyamide fabrication products, i.e., a brittle fracture, being a substance desired to any forming products. Big restriction and intermediary To have. [ as opposed to the usefulness of such a product in the tendency destroyed in brittleness (not being ductility-like) by a shock ] The reason and the resin which has good ductility are borne at the crack propagation which arises by a shock by "ductility" meaning that there is no tendency for a crack to grow from the zone of a shock. The ductility of a product can be measured by Izod examination ASTM D-256with Notch-73. In order to improve intensity and ductility conventionally, various kinds of additive agents are added by polyamide resin. For example, the shock strength by addition of the selected random copolymer pasted up on American JP,4174358,B of Ebstein, November 13, 1979 public notice, Is, and polyamide and a ductile improvement are described. However, generally the tendency of the polyamide destroyed by a shock in brittleness increases along with the fall of temperature. In this way, use of the forming products for low-temperature uses, such as an instrument of a winter sport and a bumper of a car, is decreasing. To have a blend thing for polyamide fabrication suitable for manufacture of the forming products for low temperature is desired. The present invention aims at such a blend thing for fabrication. The present invention provides the polyamide blend thing which has good shock strength and ductility in low temperature, for example, 0 degreeC. This blend thing, (a) 20~80% of the weight of 66 nylon, and 60~97% of the weight of the polyamide which is the mixtures of 80~20% of the weight of 6 nylon additionally -- and -- additional (b) 3~40 % of the weight, preferably 10~30 % of the weight, (i) the elastomer-like olefin system copolymer which has carboxyl or a carboxylate functional group -- or (ii) The third copolymerizable monomer can be contained and the acid portion is partially ionized at least with the metal ion, It is a polyamide blend thing containing the polymer-like strengthening agent chosen from either of ionicity copolymers , of at least 1 alpha olefin and the alpha-beta-unsaturated carboxylic acid of at least 1. The expression "the shape of an elastomer" means that the copolymer after fabrication recovers the first form substantially after removal of the pressure which produces modification. An "olefin system" means the end unsaturated monomer which includes Diene etc. A "copolymer" means the polymer which comprises two or more different monomer units. It was discovered that the best low-temperature toughness of the constituent containing polymer-like agent [ strengthening ] (b) (i) and (b) (ii) is attained when using the blend of 66 nylon and 6 nylon. If it says clearly, the blend thing must contain about 80% or less of 6 nylon about 20% or more. In this way, the constituent only containing 66 nylon or 6 nylon only receives comparatively low strengthening in low temperature by the given strengthening agent. Moreover, the action of the blend thing of 66 and 6 nylon is peculiar, in view of having the low-temperature toughness which is inferior to the constituent only containing one side in both the nylon ingredient in the constituent based on other nylon blend things like 6/612, or 66/612 nylon, for example. 66 nylon and 6 nylon are generally publicly known, and available. 6 nylon is the poly caprolactam to 66 nylon being polyhexamethylene adipamide. It is a polymer in which both have the amount of polymers, i.e., a membrane formation molecular weight. Strengthening ingredient (b) (i) is an elastomer-like olefin system copolymer which has carboxyl or carboxylate functionality. A Olefin portion originates, for example in the Al Kyren monomer of 2~8 carbon, such as ethylene and propylene. However, the Ole Huynh portion can also include Diene like butadiene, for example. Existing comonomer can be made into the copolymerizable ethylenic unsaturated monomer of the wide range. Generally, comonomer is Ole Huynh or those mixtures of acrylic acid or meta-acrylic acid low-grade Alkyl like methyl acrylate, ethyl acrylate, or isobutyl acrylate, or others, for example. Comonomer can also be made into methacrylic acid or acrylic acid, fumaric acid, a maleic anhydride, glycidyl methacrylate, etc. In a suitable embodiment, ingredient (b) (i)s are ethylene and C of at least 1.₃~C₆It is a polymer of an alpha olefin and at least 1 nonconjugated diene, and this polymer contains carboxyl or a carboxylate functional group. In manufacture of such a polymer, it is C.₃~C₆Propylene is usually chosen as an alpha olefin. In manufacture of an elastomer-like polymer, it adds to propylene instead of propylene, and they are other C.₃~C₆An alpha olefin, i.e., 1-Butene, 1-pentene, and 1-Hexane can be chosen. As for nonconjugated diene, it is preferred that it is single reactivity. The nonconjugated diene of single reactivity has the first double bond that participates in a polymerization reaction with ethylene and propylene easily, and the second double bond that does not participate in a polymerization reaction at the degree accepted. Role Diene of un-of single reactivity includes the cyclic diene in which the carbon-carbon double bond of line fatty series Diene of at least 6 carbon atoms which has end 2 polymerization combination of 1 and an internal double bond of 1 and one side, or both accomplishes the portion of a carbocyclic ring. Nonconjugated diene is a thing of 2 reactivity and its Then is also good. "2 Reactivity" means that both double bonds can be polymerized between manufactures of a polymer. Such Diene of 2 reactivity includes 2, 5-Norbonadiene, and 1 and 7-octadien. Carboxyl or carboxylate functionality is ordinarily supplied by using the ethylenic unsaturated comonomer containing carboxyl or a carboxylate machine as comonomer in a copolymer. And carboxyl or carboxylate functionality is ethylene/C. [ suitable ingredient (b) (i) ]₃~C₆It can supply by making an alpha olefin/nonconjugated diene react to the unsaturated compound chosen from the category which comprises the alpha-beta-ethylenic unsaturated dicarboxylic acid which has 4~8 carbon atom, or those derivatives. Such a derivative includes the monoester of dicarboxylic acid etc. which have the carboxylic acid group currently ionized 0~100% by neutralization by the monoester of the alcohol of 1~29 carbon atom, the anhydride of dicarboxylic acid, metal salt of acid, or metal basic salt. The examples of such acid and derivatives are maleic acid and maleic anhydride monoethyl ester, Metal salt of maleic acid monoester, fumaric acid, fumaric acid monoethyl ester, Itaconic acid, vinyl benzoic acid, vinyl phthalic acid, metal salt of fumaric acid monoethyl ester, Alcohol moieties are methyl, propyl, isopropyl, butyl, and isobutyl, Hexyl, cyclohexyl, octyl, 2-ethylhexyl, Decyl, stearyl, methoxy ethyl, ethoxyethyl, and hydroxy Also are monoester of the maleic acid in the case of being ethyl, fumaric acid, or itaconic acid, etc. The addition can mix unsaturated acid or its derivative without generation of a free radical to the extent that it can accept well, and can manufacture it by the graft method of heating a mixture behind simultaneous to the temperature which heat addition produces. Temperature to choose is made lower than about 450 degreeC in order to be referred to as at least 225 degreeC in order to attain generation of an addition generally at the speed which may be received, and to prevent decomposition of an excessive polymer. Although the suitable temperature range changes with specific polymers, it can be easily determined as the expert of this technical field. Mixture of acid or its derivative, and a polymer is mixture in an internal mixer or an extrusion machine, Or it can carry out by kneading the dry compound ground finely and a polymer by the often ventilated rubber roll on a plane, heating simultaneously, or heating succeedingly, for example in a hotpress or a metallic mold. For example, acid or a derivative does not block a grafting reaction too much, it is a basis like bromine or chlorine, and it replaces and its Then is also good. It is desirable to make the addition containing about 0.5~9 % of the weight, preferably about 1~4% of the weight of acid or a derivative form generally. Strengthening ingredient (b) (ii) is further guided from other copolymerizable comonomers depending on an alpha olefin, unsaturated carboxylic acid, and the case. An alpha olefin is ethylene and, as for acid, it is preferred that they are acrylic acid or methacrylic acid. Other copolymerizable comonomers can be made into acrylic ester or methacrylate ester. A metal ion can be made univalent [, such as Na, Zn, aluminum and K ], divalent, or trivalent, for example. Typical ingredient (b) strengthening agent, The ethylene / isobutyl acrylate / methacrylic acid neutralized 70% with zinc (80/10/10), The butadiene/acrylonitrile, the ethylene / methacrylate ester / maleic acid monoethyl ester (42/54/14) which has a carboxyl end group, Ethylene / acetic acid vinyl / glycidyl methacrylate (70/25/5), and the methacrylate ester / butyl acrylate / acrylic acid copolymer polymerized continuously are included. The blend thing of the present invention is prepared by mixing at a rate indicating each ingredient, and carrying out fusion blending of them to a uniform mixture. It is preferred to mix 6 nylon, 66 nylon and a strengthening polymer, or polymers by revolution in a drum first. Fusion blending can be performed at a temperature lower than decomposition temperature typically higher than the fusing point of each ingredient. These blend things with the preferred temperature range of about 260~330 degreeC are especially suitable to the use with important shock strength in the low temperature of the bumper of a car, an operation implement, a safe instrument, etc., for example. Stabilizer and a prevention agent; the usual additive agent more than kinds, such as colorant containing lubricant, a release agent, dye, and paints, fire retardant, a fiber type and a powdered bulking agent, a reinforcement agent, and a plasticizer, can also be contained. [ as opposed to / for example / oxidization, heat, and ultraviolet ray degradation in the blend thing of the present invention ] Generally these additive agents are added to a mixing stage. Typical oxidization and heat stabilizer which can be made to exist in the blend thing of the present invention, Fellows' metal halogenation thing, for example, sodium, potassium, lithium and the first copper of halogenation, for example, a chloride, a bromide, an iodide; they are various kinds of substitution things and those combination of hindered phenol, hydroquinone, and those categories. benzo[ the resorcins by which various kinds replaced typical ultraviolet stabilizer, ester salicylate, and ] -- doria -- Sole and benzophenones are included. Typical lubricant and release agent include stearic acid, stearyl alcohol, and Stale amide. Typical organic dyestuff includes nigrosine and typical paints include a titanium dioxide, a cadmium sulfide, cadmium selenide, phthalocyanines, ultra marine blue, carbon black, etc. Typical bulking agents are carbon textiles, glass fiber, formless silica, and asbestos, The typical fire retardant which includes silicic acid calcium, aluminum silicate, magnesium carbonate, kaolin, chalk, powder quartz, mica, feldspar, etc. includes organic halogenation compounds, such as decabromodiphenyl ether, for example. EXAMPLE Although the following specific examples illustrate the present invention further, into these examples, a part and percentage are based on weight, unless other notices can be found. In these examples, each ingredient is mixed by making it revolve in a drum. Subsequently, let a mixture be a pellet in the Werner And Pryderrer biaxial extrusion machine by carrying out fusion mixture with the barrel temperature of 310~320 degreeC, and the die temperature of 290 degreeC. Extrusion is performed under a vacuum, when using the mouth opened to air or you wish removal of a caprolactam monomer. Screw speed is 200 revolutions per minute. Strand who generates is cooled rapidly underwater, it cuts to a pellet type, sparging is carried out with nitrogen until it cools, and moisture is removed. the melting point of a polyamide matrix -- 10~30degreeC -- at high melting temperature, a specimen (1/2x5x1 / 4 inches) is fabricated in an injection molding machine (3 ozs and 6 ozs). Molding temperature is set to about 70 degreeC by rapid ejection, and uses 20/40 molding cycle (the advance second / maintenance second of rum). Izod toughness with Notch which examines the fabricated specimen in the state of the fabricated dryness using the following testing procedures: ASTM D-256-73. In this examination, specimens are 1/2x3x1 / 4 inches, and have 10 mil (radius) Notch in the center. Tensile strength: ASTM D-638-58T Growth: ASTM D-638-58T It bends and is modulus:ASTM D-790-58T. In the example, 66 nylon to be used has about 52 relative viscosity, and, on the other hand, 6-nylon to be used has the relative viscosity of 75~90. Such relative viscosity was measured with 8.4% of polymer solution in 90% formic acid. EPDM used in a table and an example expresses the copolymer which comprises 72% of ethylene, 24% of propylene, and 4% of 1 and 4-Hexadiene. This is used as an extender for a strengthening polymer. EPDM-FA comprises 68% of ethylene, 26% of propylene, 6% of 1 and 4-Hexadiene, and 0.06% of 2 and 5-norbornadiene, It has processed with fumaric acid so that the addition which measures by infrared rays (CPE671 spectrum photometer), and has 1.5~2.0% of functionality (acid and acid anhydride) may be given, And the copolymer for strengthening which has 1.2~4.8g/the melt flow for 10 minutes in 280 degreeC by an orifice 0.0825 inch in diameter is expressed. Examples 1 and 2 and example A of contrast 66 nylon, 6 nylon, EPDM, and EPDM-FA were mixed, and it was considered as the pellet type, and fabricated to the cylindrical specimen, and examined about the Izod value with Notch as mentioned above. The quantity and the test result of each ingredient are shown below: [Table]

In any case, when measuring resin containing 6 nylon and 66 nylon by this examination, it turns out that it has far bigger shock strength than contrast (6 nylon is not contained). Examples 3, 4, and 5, example B, C, and D of contrast, and E -- in the experiment of another series, 66 nylon, 6 nylon, EPDM, and EPDM-FA were blended, and it was considered as the pellet type, it fabricated as a cylindrical specimen, and examined about the Izod value with Notch as mentioned above. The quantity and the test result of an ingredient are shown below.

[Table]

It is clear not to give the resin which has the Izod strength with Notch in which only 66 nylon of each copolymer of 6 nylon or 66 nylon, and 6 nylon is as good to the same extent as the mixture of 66 nylon shown in Examples 3, 4, and 5 and 6 nylon. Example 6 and example F of contrast The resin described in the following table is based on the weight of resin, and is 20% of poly dibromo phenylene Oxide, and 8% of Sb.₂O₃The Flame retardant system was also added, and also it prepared like the above, and fabricated and examined.

[Table]

It turns out that existence of 6 nylon increases intensity also when fire retardant exists. The following resin is prepared like Example 7 and the example of contrast G above: [Table]

In a 21/2-inch sterling single axis extrusion machine, 67% was respectively mixed with the glass fiber which cut 33%, the Izod examination with Notch was done using the acquired specimen, and the following result was obtained: [Table]

It turns out that existence of 6 nylon increases intensity also when the cut glass fiber exists. Example 8 and examples H and I of contrast Like the above-mentioned general approach, the following resin was prepared and fabricated and was examined about the Izod toughness with Notch.

[Table]

Example 9 and examples J and K of contrast the above-mentioned general procedure -- therefore, the following resin was prepared and fabricated and it examined about the Izod toughness with Notch.

[Table]

Example 10 and examples L and M of contrast Follow was in the above-mentioned general procedure, and the following resin was prepared and fabricated, and it examined about the Izod toughness with Notch.

[Table]