JPH1180497A - Thermopiastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which shows excellent impact resistance and processability by using polymers comprising a diene-based rubber component onto which an aromatic vinyl monomer and a vinyl cyamide monomer are grafted and a non-grafted polymer component, a polyamide resin and a modified vinyl polymer. SOLUTION: A thermoplastic resin composition comprises 1-98 pts.wt. grafted polymer obtained by grafting 15-35 pts.wt. monomers comprising 50-99 wt.% (hereinafter referred to as %) aromatic vinyl monomer and 1-50% vinyl cyanide monomer onto 65-85 pts.wt. (herein after referred to as pts.) of a diene-based rubber polymer wherein the graft ratio of the grafted rubber component is not less than 10% and the ratio of the non-grafted polymer component having intrinsic viscosity of 0.3 dl/g (at 30 deg.C) is not less than 5 %, 1-98 pts. polyamide resin and 1-70 pts. modified vinyl polymer obtained by polymerizing 50-98.9% aromatic vinyl monomer, 1-49.9 % vinylcianide monomer and 0.1-20% α,β-unsaturated carboxylic acid (salt).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition excellent in impact resistance, molding processability, surface appearance characteristics of molded articles, chemical resistance, economy and productivity.

[0002]

2. Description of the Related Art An acrylonitrile-butadiene-styrene copolymer (ABS resin) is a matrix resin (AS).
The rubber particles dispersed in the resin improve the impact resistance of the resin. At this time, it is necessary to graft a component compatible with the matrix resin to the rubbery polymer in advance, and if this graft does not exist or is insufficient, the rubber particles aggregate and exhibit impact strength. Not only does it deteriorate the surface appearance of the molded article.

[0003] As a method for producing an ABS resin, a method of blending a graft rubber obtained by grafting a component compatible with an AS resin to a rubbery polymer and an separately produced AS resin is advantageous in terms of economy and productivity. Because it is, it is generally used.

Emulsion polymerization is preferably used for graft polymerization to a rubbery polymer from the viewpoints of polymerization stability, control of graft characteristics, heat removal, and the like. This emulsion polymerization includes a step of recovering the polymer and comprises an AS resin. Is disadvantageous in terms of cost. Therefore, as a technique for suppressing the amount of the graft rubber used, a technique for increasing the content of the rubbery polymer contained in the graft rubber has been studied, and the content of the practical rubbery polymer has been reduced to 45 to 60% by weight. Has been raised.

[0005] On the other hand, this ABS resin is used in a wide range of fields due to its excellent impact resistance, mechanical properties and moldability, but its chemical resistance and abrasion resistance are not sufficient, and severe conditions are required. Its use is restricted.

In order to compensate for chemical resistance and abrasion resistance, A
A blend of a BS resin and a polyamide resin is preferably used. At this time, a technique using a vinyl polymer modified with an α, β-unsaturated carboxylic acid or the like as a compatibilizer in order to bring out mechanical properties has been proposed.

[0007]

However, in the conventional blend of the ABS resin and the polyamide resin, the
There was a problem that the rubber content in the resin composition was greatly restricted. This is because, in the conventional ABS resin, when an attempt is made to increase the rubber content, the proportion of the ABS resin is greatly increased and the polyamide resin is relatively reduced.

Therefore, in order to improve the impact resistance without reducing the proportion of the polyamide resin, and to design a resin composition excellent in economic efficiency and productivity required for a general-purpose resin, it is necessary to design a resin composition in the graft polymer. There is a need for a technique for dramatically increasing the content of the rubbery polymer as compared with the conventional technique.

[0009]

Means for Solving the Problems As a result of intensive studies on solving the above problems, the inventors of the present invention have found that the graft properties of a graft polymer as a means for increasing the rubber content of an ABS resin in a blend of an ABS resin and a polyamide resin. Was found to be effective.

That is, the present invention relates to a method for producing a polymer comprising: (A) 50 to 99% by weight of an aromatic vinyl monomer and 50 to 85% by weight of a diene rubbery polymer; ~ 5
A graft polymer obtained by polymerizing 15 to 35 parts by weight of 0% by weight and 0 to 50% by weight of another vinyl monomer copolymerizable therewith; A graft rubber component obtained by graft-polymerizing a monomer comprising an aromatic vinyl monomer, a vinyl cyanide monomer, and another vinyl monomer copolymerizable therewith with the polymer,
A composition comprising a non-graft polymer component that is not grafted on a rubbery polymer, wherein the graft ratio of the graft rubber component is 10% or more, and the weight ratio of the non-graft polymer component to the graft polymer is 5% by weight or more. A methyl ethyl ketone solvent as a non-graft polymer component, 1 to 98 parts by weight of a graft polymer having an intrinsic viscosity of 0.3 dl / g or less measured at 30 ° C., (B) an aromatic vinyl monomer 50 to
Polymer 0-97 obtained by polymerizing a monomer comprising 99% by weight, 1-50% by weight of a vinyl cyanide monomer and 0-50% by weight of another vinyl monomer copolymerizable therewith. Parts by weight, (C) 1 to 98 parts by weight of a polyamide resin, and (D)
50 to 98.9% by weight of aromatic vinyl monomer, 1 to 49.9% by weight of vinyl cyanide monomer, α, β-unsaturated carboxylic acid and / or α, β-unsaturated carboxylate 0.
1 to 70 parts by weight of a modified vinyl polymer obtained by polymerizing 1 to 20% by weight and 0 to 50% by weight of another vinyl monomer copolymerizable therewith. Thermoplastic resin composition. ".

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. In the present invention, weight means mass.

Here, as the diene rubbery polymer used for the graft polymer (A), a polymer or copolymer containing a conjugated diene as a main component is preferable. Among them, the content of the conjugated diene is preferably at least 75% by weight, particularly preferably at least 85% by weight. Specifically, polybutadiene, styrene-
Butadiene copolymer, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, isoprene rubber and the like can be used.

The average particle diameter of these diene rubbery polymers can be generally 0.1 to 0.6 μm, and particularly preferably 0.2 to 0.4 μm. The gel content is preferably 60% by weight or more in consideration of the impact resistance when blended with a thermoplastic resin. Here, the gel content indicates the weight fraction of the toluene-insoluble component after coagulation and drying of the rubbery polymer latex.

In the present invention, the monomers graft-polymerized in the presence of the rubbery polymer include an aromatic vinyl monomer and a vinyl cyanide monomer, and if necessary, other monomers copolymerizable therewith. It is a mixture of monomers.

As the aromatic vinyl monomer, styrene,
α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-
Examples thereof include chlorostyrene and o, p-dichlorostyrene, and styrene is particularly preferably used. These may be used alone or in combination of two or more.

Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferred.

Other monomers copolymerizable therewith include unsaturated carboxylic acid monomers, unsaturated carboxylic acid anhydride monomers, unsaturated carboxylic acid ester monomers,
Alternatively, a maleimide-based monomer or the like can be used.
Specifically, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t- (meth) acrylate Butyl, n-hexyl (meth) acrylate, chloromethyl (meth) acrylate, maleic anhydride, itaconic anhydride, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-
Phenylmaleimide can be used.

Here, the graft polymer of the present invention is 65 to 85 parts by weight, preferably 70 to 8 parts by weight of a diene rubbery polymer.
It is obtained by graft polymerization of 15 to 35 parts by weight, preferably 20 to 30 parts by weight, of the monomer mixture with respect to 0 parts by weight. If the amount of the rubbery polymer exceeds 85 parts by weight, good physical properties of the thermoplastic resin cannot be obtained due to a relative decrease in a monomer to be grafted. Further, less than 65 parts by weight is not the object of the present invention.

Here, for all monomers to be grafted,
The proportion of the aromatic vinyl monomer is from 50 to 99% by weight, preferably from 60 to 90% by weight, more preferably from 70 to 80% by weight, and if it is less than 50% by weight, the amount of the rubbery polymer in the thermoplastic resin is reduced. It is not preferable because the dispersion state deteriorates.

The proportion of the vinyl cyanide monomer is from 1 to 50% by weight, preferably from 10 to 40% by weight, based on all monomers.
More preferably, it is 20 to 30% by weight.

If the other vinyl monomer copolymerizable therewith is used at 50% by weight or less, the object of the present invention can be achieved.

The graft polymer can be obtained by emulsion graft polymerization. Various methods can be adopted as a method for adding components such as a monomer mixture, an emulsifier, a polymerization initiator, and a chain transfer agent in the graft polymerization. That is, there are a method of adding the whole amount at the initial stage of polymerization, a method of adding a part at an initial stage and adding the remainder continuously, a method of adding the whole amount continuously, and a method of adding two or more times.

The types of the emulsifier, polymerization initiator and chain transfer agent used are not particularly limited, and reagents used in ordinary emulsion polymerization can be used. Typical emulsifiers include potassium rosinate, potassium stearate, potassium oleate, and the like, and polymerization initiators include a combination of organic hydroperoxide and sugar-containing pyrophosphate-ferrous sulfate and a peracid salt. Examples of the chain transfer agent include alkylthiol compounds.

The graft polymer obtained by emulsion polymerization is obtained by adding a rubbery polymer to an aromatic vinyl monomer, a vinyl cyanide monomer and another vinyl monomer copolymerizable therewith. It is a composition comprising a graft rubber component obtained by graft polymerization of a monomer and a non-graft polymer component that does not graft onto a rubber polymer. At this time, the graft ratio (weight ratio of the grafted polymer component to the rubbery polymer) of the graft rubber component is 10% or more, preferably 15% or more.
% Or more. If the graft ratio is less than 10%, the impact resistance of the resin composition and the surface appearance characteristics of the molded product are undesirably deteriorated. The weight ratio of the non-graft polymer component to the graft polymer (A) is 5% by weight or more, preferably 8% by weight.
% By weight or more. If the amount of the non-grafted polymer component is less than 5% by weight, aggregates appear on the surface of the molded article of the resin composition, and the appearance is remarkably deteriorated, and the physical properties such as impact resistance are also unfavorably reduced.

The intrinsic viscosity of the non-grafted polymer component measured at 30 ° C. in a methyl ethyl ketone solvent is 0.3 dl.
/ G or less, preferably 0.05 to 0.28 dl / g, more preferably 0.1 to 0.26 dl / g. If the intrinsic viscosity exceeds 0.3 dl / g, the rubber particles are not uniformly dispersed in the matrix, and the impact resistance and the surface appearance characteristics are deteriorated. Here, since the degree of polymerization of the non-grafted polymer component and the grafted polymer component is generally considered to be substantially equal, if the chain length of the grafted polymer component is long, another rubber Entangling with the polymer component grafted on the polymer and preventing uniform dispersion of the graft rubber causes a reduction in impact resistance and surface appearance characteristics. Therefore, the graft rubber is ozonolyzed to extract the grafted polymer component, and the intrinsic viscosity measured at 30 ° C. in a methyl ethyl ketone solvent is also 0.3 dl /.
g or less.

The graft ratio and intrinsic viscosity of the non-grafted polymer are controlled by adjusting the ratio of the rubbery polymer to the monomer mixture, the type and amount of the polymerization initiator, the type and amount of the chain transfer agent, and the type and amount of the emulsifier. Can be controlled.

The resin composition of the present invention is obtained by polymerizing the graft polymer (A) with an aromatic vinyl monomer, a vinyl cyanide monomer and another vinyl monomer copolymerizable therewith. By mixing the resulting polymer (B), the impact resistance and the moldability of the molded article can be adjusted in a well-balanced manner.

The aromatic vinyl monomers used herein include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene and o, p-methylstyrene. Examples thereof include dichlorostyrene, and styrene is particularly preferably used. These may be used alone or in combination of two or more.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, and ethacrylonitrile, and acrylonitrile is particularly preferable. These may be used alone or in combination of two or more.

As other monomers copolymerizable therewith, unsaturated carboxylic acid anhydride monomers, unsaturated carboxylic acid ester monomers, maleimide monomers and the like can be used. it can. Specifically, maleic anhydride, itaconic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid t-butyl, n-hexyl (meth) acrylate, chloromethyl (meth) acrylate, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like can be used.

The proportion of the aromatic vinyl monomer is from 50 to 99% by weight, preferably from 60 to 90% by weight, based on all monomers.
It is more preferably 70 to 80% by weight, and the ratio of the vinyl cyanide monomer is 1 to 50% by weight, preferably 10 to 50% by weight.
It is 40% by weight, more preferably 20 to 30% by weight.
Even if the proportion of the aromatic vinyl monomer exceeds 99% by weight, 5
If the amount is less than 0% by weight, the mechanical properties of the resin composition deteriorate, which is not preferable. Further, the object of the present invention can be achieved by using 50% by weight or less of other monomers copolymerizable with these.

The method for producing the polymer (B) is not particularly limited, and generally known solution polymerization, emulsion polymerization,
It can be obtained by suspension polymerization or bulk polymerization. The intrinsic viscosity of the polymer (B) measured at 30 ° C. in a methyl ethyl ketone solvent is 0.3 to 1 dl / g, preferably 0.4 to 0.1 dl / g.
8 dl / g. When the intrinsic viscosity exceeds 1 dl / g,
The fluidity of the entire resin composition is reduced, and if it is less than 0.3 dl / g, impact resistance and mechanical properties are significantly reduced, which is not preferable.

The polyamide resin (C) used in the present invention includes polyamides obtained by ring-opening polymerization of lactams such as ε-caprolactam and ω-dodecalactam;
Aminocaproic acid, 11-aminoundecanoic acid, 12-
Polyamides derived from amino acids such as aminododecanoic acid, ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 1, 3- and 1, 4
-Bis (aminomethyl) cyclohexane, bis (4
4'-aminocyclohexyl) aliphatic, alicyclic, aromatic diamines such as methane, meta and paraxylylenediamine and adipic acid, suberic acid, sebacic acid, dodecandioic acid, 1,3- and 1,4-cyclohexane Examples thereof include polyamide resins derived from aliphatic, alicyclic, and aromatic dicarboxylic acids such as dicarboxylic acid, isophthalic acid, terephthalic acid, and dimer acid, copolymerized polyamide resins thereof, and mixed polyamide resins. Of these, polycaproamide (nylon 6), polyundecaneamide (nylon 11), polydodecaneamide (nylon 12),
Polyhexamethylene adipamide (nylon 66) and copolymerized polyamide resins containing these as a main component are preferably used.

The above polyamide resins may be used alone or in combination of two or more.

As the polymerization method of the polyamide resin, generally known melt polymerization, solid phase polymerization and a method combining these can be adopted. In addition, polyamide resin, relative viscosity (1 g of polymer dissolved in 100 g of 98% concentrated sulfuric acid,
(Measured at ° C) in the range of 2 to 5 are preferably used.

When the ABS resin and the polyamide resin are blended, a compatibilizer is generally used, and the aromatic vinyl monomer and the vinyl cyanide monomer are also used in the resin composition of the present invention. (D) obtained by polymerizing a monomer comprising α, β-unsaturated carboxylic acid and / or α, β-unsaturated carboxylate and another vinyl monomer copolymerizable therewith Is included.

The aromatic vinyl monomers used herein include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene and o, p-methylstyrene. Examples thereof include dichlorostyrene, and styrene is particularly preferably used. These may be used alone or in combination of two or more.

Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferred. These may be used alone or in combination of two or more.

Examples of the α, β-unsaturated carboxylic acid and / or α, β-unsaturated carboxylate include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and Examples thereof include metal salts thereof, and among them, acrylic acid, methacrylic acid and metal salts thereof are preferable. These can be used in combination of two or more.

Examples of the metal salt include IA and I of the periodic table of the elements.
Group B, IIA, IIB, IIIA and VIII
Periodic metals such as Na, K, Cu, Mg, Ca, B
a, Zn, Cd, Al, Fe, Co, Ni, etc., among which Na, K, Mg, Ca, Ba, Zn are preferably used.

Further, as other copolymerizable monomers,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, Α, β-unsaturated carboxylic esters such as chloromethyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, and α, β-unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride Acid anhydrides, imide compounds of α, β-unsaturated dicarboxylic acids such as N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide are exemplified.

The proportion of the aromatic vinyl monomer is 50 to 98.9% by weight, preferably 60 to 90% by weight, based on all monomers, and the proportion of the vinyl cyanide monomer is 1 to 49.9. %, Preferably 9 to 39% by weight, the proportion of α, β-unsaturated carboxylic acid and / or α, β-unsaturated carboxylate is 0.1 to 20% by weight, preferably 1 to 10% by weight. is there.

When the content of the aromatic vinyl monomer is less than 50% by weight and more than 98.9% by weight, and when the content of the vinyl cyanide monomer is less than 1% by weight and exceeds 49.9% by weight, It is not preferable because the compatibility with the graft polymer (A) is reduced and the resin composition cannot obtain good mechanical properties. Α, β-unsaturated carboxylic acid and / or α, β-unsaturated carboxylic acid
When the proportion of the β-unsaturated carboxylate is less than 0.1% by weight, the impact strength of the resin composition is low. Further, other monomers copolymerizable therewith can be used in an amount of 50% by weight or less.

The method for producing the modified vinyl polymer (D) is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization are used. At this time, if the intrinsic viscosity of the modified vinyl polymer measured at 30 ° C. in a methyl ethyl ketone solvent is 0.3 to 1.5 dl / g, the object of the present invention can be sufficiently achieved.

The thermoplastic resin composition of the present invention comprises a graft polymer (A), a polymer (B), a polyamide resin (C),
It can be produced by a method of melt-kneading the modified vinyl polymer (D). The melt-kneading method is not particularly limited. For example, a resin composition having good physical properties can be obtained by using a twin-screw extruder or the like. The temperature at the time of melt kneading is not particularly limited, but a temperature of 200 to 250 ° C., preferably 210 to 230 ° C. is preferable because the kneading of the resin is good.

In the thermoplastic resin composition, the graft polymer (A) is 1 to 98 parts by weight, preferably 10 to 80 parts by weight, and the polymer (B) is 0 to 97 parts by weight, preferably 0 to 97 parts by weight.
50 parts by weight, the polyamide resin (C) is 1 to 98 parts by weight,
The object of the present invention can be achieved with a compounding amount of preferably 10 to 80 parts by weight, and the modified vinyl polymer (D) 1 to 70 parts by weight, preferably 2 to 50 parts by weight.

If the amount of the graft polymer (A) is less than 1 part by weight, the impact resistance of the obtained resin composition is insufficient, and if it exceeds 98 parts by weight, the chemical resistance is undesirably reduced.
Also, when the amount of the polymer (B) exceeds 97 parts by weight, the amount of the polyamide resin is similarly decreased, which is not preferable. When the amount of the polyamide resin (C) is less than 1 part by weight, the chemical resistance of the resin composition is insufficient, and when it exceeds 98 parts by weight, the impact resistance is insufficient, which is not preferable. If the modified vinyl polymer (D) is less than 1 part by weight, the impact resistance and mechanical properties of the resin composition are reduced,
If the amount exceeds 70 parts by weight, molding processability is inferior.

Further, pigments and dyes for giving carbon black, titanium compounds and various dyes according to the purpose, phosphorus-based and phenol-based stabilizers, flame-retardants such as halogen-based compounds, antimony compounds and metal hydroxides, Phenol, phosphite and sulfur antioxidants, hindered phenol, benzotriazole, benzophenone, benzoate and cyanoacrylate UV absorbers, waxes, higher fatty acids and acid esters and acid amides Further, lubricants and plasticizers such as higher alcohols, and fillers such as glass fibers, talc, and minerals can also be added.

[0049]

The present invention will be described in more detail with reference to the following examples.

The method for analyzing the graft polymer of the present invention is described below.

(1) Graft ratio G of graft polymer and weight ratio F of non-graft polymer F acetone is added to a predetermined amount M (g) of the graft polymer.
Refluxed for hours. After the solution was centrifuged at 9,000 rpm for 30 minutes, insoluble components were filtered. This insoluble matter was dried under reduced pressure at 60 ° C. for 5 hours, and the weight N (g) was measured. The graft ratio G (%) was calculated by the following equation. G = 100 × (N−M × L) / (M × L) Here, L represents the content (% by weight) of the rubbery polymer in the graft polymer.

The weight ratio F (% by weight) of the non-grafted polymer was calculated by the following equation. F = 100 × (M−N) / M

(2) Intrinsic viscosity of the non-grafted polymer After filtering the insoluble matter from the acetone solution used for the measurement of the graft ratio, acetone was evaporated from the filtrate, and methanol was added to the residue to remove the non-grafted polymer. Extracted. After the extract was dried under reduced pressure at 60 ° C. for 3 hours, 0.4 g of the non-grafted polymer was dissolved in methyl ethyl ketone and 100 cc
Was prepared. The intrinsic viscosity of this solution was measured in a thermostat at 30 ° C.

Next, various physical property evaluation methods used in the examples are shown below.

(1) Melt Viscosity The melt viscosity was measured using a Shimadzu flow tester (CFT-500) under the following conditions. Plunger area: 1 cm ² Die hole diameter: 1 mm φ × 2 mm length Measurement temperature: 230 ° C Load: 50 kg / cm ²

(2) 12.7 mm Notched Izod Impact (J / m) Measured according to ASTM D256-56.

(3) Drop weight impact strength (J) Measurement was performed according to JIS K6745.

(4) Fish Eye Approximately 10 g of resin pellets before molding were hot-pressed at 250 ° C. and stretched to form a 10 μm thick film. The number of rubber-like lumps (bubbles) contained in the film 100 × 200 mm was visually measured. A film with a smooth surface is a case where the number of spots is 1 or less per 100 mm ² , and at this time, the surface appearance of the molded product is good. On the other hand, if the number of bumps exceeds 5 per 100 mm ² , the appearance of the molded product is significantly impaired.

(5) Chemical resistance The injection molded square plate was placed in methanol and gasoline at 23 ° C.
After immersion for 24 hours, the surface of the square plate was visually observed.

[Production Method of Graft Polymer (A)] Table 1
A latex of a diene rubbery polymer (PBD) having the composition described in (1) was charged into a glass reaction vessel, and glucose, sodium pyrophosphate, and ferrous sulfate dissolved in ion-exchanged water were further charged with stirring. 65 ℃ inside temperature
Temperature.

To this mixture, a mixture of styrene (ST), acrylonitrile (AN) and t-dodecyl mercaptan shown in Table 1 and an aqueous solution of potassium oleate of cumene hydroperoxide were separately added for 3 hours. The polymerization was completed by continuous dropping over 4 hours. All conversions ranged from 95 to 99%.

The obtained graft polymer latex is coagulated with sulfuric acid, neutralized with sodium hydroxide, washed with water, dehydrated,
After drying, a graft polymer powder was obtained. Graft ratio G of each graft polymer, weight ratio F of non-graft polymer,
Table 1 summarizes the intrinsic viscosity η of the non-grafted polymer.

Polymers A-2 and A-5 are graft polymers within the range specified in the present invention, and the others are outside the specified range of the present invention.

[0064]

[Table 1]

[Production Method of Polymer (B)] A monomer composed of 70 parts by weight of styrene and 30 parts by weight of acrylonitrile was subjected to suspension polymerization in a polymerization tank equipped with a stirrer to obtain a SAN copolymer. After sufficiently drying the obtained bead-shaped resin, it was dissolved in methyl ethyl ketone, and the intrinsic viscosity was measured in a thermostat at 30 ° C. As a result, the intrinsic viscosity of the SAN copolymer was 0.5 dl / g.

[Method for producing modified vinyl polymer (D)]
A monomer comprising 70 parts by weight of styrene, 24 parts by weight of acrylonitrile and 6 parts by weight of acrylic acid was subjected to suspension polymerization in a polymerization tank equipped with a stirrer to obtain a modified vinyl polymer.

[Production methods of Examples 1 to 4 and Comparative Examples 1 to 8] The graft polymer (A), polymer (B), polyamide resin (C), and modified vinyl polymer (D) prepared above were prepared. ) Were mixed in the proportions shown in Table 2, 1 part of ethylenebisstearylamide and 0.1 part of diphenylisodecyl phosphite were added, and mixed with a Henschel mixer. Polycaproamide: CM1010 manufactured by Toray Industries, Inc. was used as the polyamide resin (C).
Next, the mixture was extruded at a kneading temperature of 230 ° C. using a 30 mmφ twin screw extruder to form pellets.

[0068]

[Table 2]

In order to evaluate physical properties, a molding temperature of 230 ° C.
Injection molding was performed under the condition of a mold temperature of 60 ° C. to prepare predetermined test pieces. The physical properties of it were evaluated.

In Comparative Example 1 in Table 2, good physical properties can be obtained as a blend of an ABS resin and a polyamide resin, but the amount of the graft polymer is large, which is disadvantageous in terms of economy and productivity. On the other hand, in Examples 1 and 2, physical properties equivalent to those of Comparative Example 1 are obtained, and the blending amount of the graft polymer can be reduced.

As in Comparative Examples 2, 3, and 4, the graft ratio <
If the content is 10%, the content of the non-grafted polymer is <5%, and the intrinsic viscosity of the non-grafted polymer is> 0.30 dl / g, the above effects cannot be obtained. Specifically, fish eyes occur,
The surface appearance of the molded product deteriorates and the impact strength also decreases. Further, when the rubbery polymer content of the graft polymer is 90% by weight, the relative shortage of the monomer components is large, and it is difficult to secure both the graft ratio and the non-graft polymer.

From Comparative Example 6, it can be seen that the use of the graft polymers of Examples 3 and 4 of the present invention can further increase the rubber content in the resin composition and increase the impact. .

Unless a polyamide resin is blended as in Comparative Example 7, it is difficult to obtain chemical resistance. Furthermore, when the modified vinyl polymer was not used as a compatibilizer, the impact strength was significantly reduced.

Therefore, the graft polymer of the present invention can provide a resin composition excellent in impact resistance, processability, surface appearance characteristics of a molded product, chemical resistance, economy and productivity.

[0075]

Industrial Applicability The thermoplastic resin composition of the present invention comprises ABS
A resin composition containing a graft polymer represented by a resin and a polyamide resin, and having excellent impact resistance, molding processability, molded product surface appearance characteristics, chemical resistance, economy, and productivity. Used as a wide range of molding materials for parts, home appliances, and daily necessities, this effect is exhibited by increasing the amount of rubbery polymer in the graft polymer and regulating the graft properties. It is.

Claims (4)

[Claims] (1) In the presence of 65 to 85 parts by weight of a diene rubbery polymer (A), 50 to 99% by weight of an aromatic vinyl monomer, 1 to 50% by weight of a vinyl cyanide monomer and It is a graft polymer obtained by polymerizing 15 to 35 parts by weight of a monomer comprising 0 to 50% by weight of another vinyl monomer copolymerizable therewith, and the graft polymer is aromatic to the rubbery polymer. A graft rubber component obtained by graft polymerization of a monomer comprising an aromatic vinyl monomer, a vinyl cyanide monomer, and another vinyl monomer copolymerizable therewith, and a non-grafted rubber polymer A composition comprising a graft polymer component, wherein the graft ratio of the graft rubber component is 10% or more, the weight ratio of the non-graft polymer component to the graft polymer is 5% by weight or more, and the non-graft polymer component Of methyl ethyl ketone 1 to 98 parts by weight of a graft polymer having an intrinsic viscosity of 0.3 dl / g or less at 30 ° C., 50 to 99% by weight of an aromatic vinyl monomer (B), and a vinyl cyanide monomer 1 0 to 97 parts by weight of a polymer obtained by polymerizing a monomer consisting of 0 to 50% by weight and 0 to 50% by weight of another vinyl monomer copolymerizable therewith; (C) 1 to 98% by weight of a polyamide resin And (D) 50 to 98.9% by weight of an aromatic vinyl monomer, 1 to 49.9% by weight of a vinyl cyanide monomer, and an α, β-unsaturated carboxylic acid and / or
Or 0.1 to 20% by weight of an α, β-unsaturated carboxylate
And other vinyl monomers copolymerizable therewith.
A thermoplastic resin composition comprising 1 to 70 parts by weight of a modified vinyl polymer obtained by polymerizing a monomer of 1% by weight. 2. Relative viscosity of polyamide resin (C) (1 g of polyamide resin is dissolved in 100 g of 98% concentrated sulfuric acid,
The thermoplastic resin composition according to claim 1, wherein (a) is 2 to 5. 3. A modified vinyl polymer (D) having a limiting viscosity of 0.3 to 1.5 dl at 30 ° C. in a solvent of methyl ethyl ketone.
The thermoplastic resin composition according to claim 1, wherein the ratio is / g. 4. The thermoplastic resin composition according to claim 1, which is obtained by melt-kneading the graft polymer (A), the polymer (B), the polyamide resin (C) and the modified vinyl polymer (D).