JPH03153751A - Resin composition excellent in impact resistance and thermal stability - Google Patents

Abstract

PURPOSE:To prepare the title resin compsn. useful for an automotive part, etc., by compounding a polyamide with a specified amt. of a specific graft- copolymerized composite rubber. CONSTITUTION:The title resin compsn. comprises: 100 pts.wt. thermoplastic resin compsn. consisting of 10-90 pts.wt. polyamide, 90-10 pts.wt. graft copolymerized composite rubber, and, as an optional component, 0-80 pts.wt. polymer obtd. by polymerizing at least one monomer selected from the group consisting of a vinyl cyanide, arom. vinyl, and (meth)acrylic ester monomer; and optionally 0-100 pts.wt. reinforcing filler. The graft copolymerized composite rubber is prepd. by grafting a vinyl cyanide (e.g. acrylonitrile) and an arom. vinyl monomer (e.g. styrene) onto a composite rubber comprising 10-90wt.% polyorganosiloxane rubber component (e.g. a rubber component obtd. from tetraethoxysilane, gamma-methacryloyloxypropyldimethoxymethylsilane, and octamethylcyclotetrasiloxane) and 90-10wt.% polyalkyl (meth)acrylate rubber component (e.g. a rubber component obtd. from n-butyl acrylate and allyl methacrylate), both rubber components having been combined with each other into an inseparable structure.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermoplastic resin composition with improved impact resistance and thermal stability.

(Prior art and problems to be solved by the invention) Polyamide resins have excellent properties such as chemical resistance, moldability, and abrasion resistance, so they are used in a wide range of fields such as automobile parts and electrical and electronic parts. ing. However, its use is severely limited by its low impact resistance, especially notched impact strength. Therefore, research was carried out on resin compositions aimed at improving the impact resistance of polyamide resins.
76, and JP-A-51-36274 describes a method of blending a polymer obtained by graft copolymerizing acrylonitrile and styrene with acrylic rubber. However, although these improve the impact resistance of polyamide resins, they are inferior in either heat resistance stability or impact resistance at low temperatures.

(Means for Solving the Problems) As a result of extensive research into methods for improving the impact resistance and thermal stability of polyamide resins, including those at low temperatures, the present inventors have developed a specific graft copolymer and, if necessary, reinforcement. The present invention was completed based on the discovery that the initial objective could be achieved by blending fillers in specific proportions.

That is, the present invention comprises (A) polyamide: 10 to 90 parts by weight, (B) polyorganosiloxane rubber component 10 to 90% by weight, and polyalkyl (meth)agelylate rubber component 90 to 90% by weight.
Composite rubber has a structure in which 10% by weight cannot be separated.
Composite rubber-based graft copolymer obtained by graft polymerization of vinyl cyanide monomer and aromatic vinyl monomer: 90-10
Part by weight (C) Polymer obtained by polymerizing at least one of a vinyl cyanide monomer, an aromatic vinyl monomer, and a (meth)acrylic acid ester monomer: 0 to 80 parts by weight ( A) A thermoplastic resin composition blended so that the total amount of components (B) and (C) is 100 parts by weight, and (D
) A thermoplastic resin composition containing 0 to 100 parts by weight of a reinforcing filler and having excellent impact resistance and heat resistance stability.

The present invention will be explained in detail below. First, each component constituting the thermoplastic resin composition of the present invention will be explained.

(A) Polyamide The polyamide (A) constituting the thermoplastic resin composition according to the present invention includes a lactam having three or more membered rings, a polymerizable ω
- Polyamides obtained by polycondensation of amino acids or dibasic acids and diamines can be used.

Specifically, ε-caprolactam, aminocaproic acid,
Polymers such as enantholactam, 7-aminohbutanoic acid, 11-aminoundecanoic acid, and 9-aminanoic acid, diamines such as hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, metaxylene diamine, and terephthal. Polymers obtained by polycondensation with acids, dicarboxylic acids such as isophthalic acid, adipic acid, sepatic acid, dodecane dibasic acid, and geltaric acid, or copolymers thereof, such as nylon 6, nylon 11, nylon 12, and nylon 4.・6, nylon 6.6, nylon 6.1O, nylon 6.12, etc.

The amount of polyamide used is 10 to 90 parts by weight out of 100 parts by weight of the total amount of components (A), (B) and (C),
Preferably it is 30 to 80 parts by weight. If it is outside this range, a resin composition having the properties expected in the present invention cannot be obtained.

(B) About the composite rubber-based graft copolymer The composite rubber-based graft copolymer (B) used in the present invention comprises 10 to 90% by weight of a polyorganosiloxane rubber component and 90 to 10% by weight of a polyalkyl (meth)acrylate rubber component. % (the total amount of each rubber component is 100% by weight) and has a structure in which both rubber components are virtually inseparable, and a vinyl cyanide monomer and an aromatic vinyl monomer are graft-polymerized. It is a composite rubber-based graft copolymer.

Even if any one of a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component or a simple mixture thereof is used as a rubber source instead of the above composite rubber, the resin composition of the present invention has the same characteristics. However, only when a composite and integrated polyorganosiloxane rubber component and polyalkyl (meth)acrylate rubber component is used as a rubber source, it has excellent impact resistance even at low temperatures and has excellent heat resistance stability. It is possible to obtain a resin composition that gives molded products with excellent properties.

The emulsion polymerization method is most suitable for producing the composite rubber used in the present invention. First, a latex of polyorganosiloxane rubber is prepared, and then monomers for synthesizing alkyl (meth)acrylate rubber are added to the polyorganosiloxane rubber. Preferably, the synthetic monomer is polymerized after being impregnated into latex rubber particles. This will be explained in detail below.

(1) Polyorganosiloxane rubber component The polyorganosiloxane rubber component constituting the above composite rubber can be prepared by emulsion polymerization using the organosiloxane and crosslinking agent (I) shown below. Agent (1) can also be used in combination.

The organosiloxane includes various cyclic bodies having 3 or more membered rings, and 3- to 6-membered rings are preferably used. For example, hexamethylcyclotrisiloxane, octamethyldiglotitrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
Examples include trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenyldiglotitrasiloxane, which may be used alone or in combination of two or more.

The amount of these organosiloxanes used is 50% by weight or more, preferably 70% by weight or more in the polyorganosiloxane rubber component.

Examples of the crosslinking agent (1) include trifunctional or tetrafunctional silane crosslinking agents, such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. is used. Particularly preferred are tetrafunctional crosslinking agents, and among these, tetraethoxysilane is particularly preferred. The amount of crosslinking agent used is 0.1 to 30% by weight in the polyorganosiloxane rubber component.

The graft cross-agent (1) has the following formula % () ) (13) (In each formula, R' is a methyl group, an ethyl group, a buqvyl group, or a phenyl group, and R' is a hydrogen atom or a methyl group. , n is 0,
1 or 2, p represents a number from 1 to 6. ) are used. (Meth)acryloyloxysiloxane that can form the unit of formula (1-1) has a high grafting efficiency, so it is possible to form an effective graft chain and is advantageous in terms of impact resistance.

Note that methacryloyloxysiloxane is particularly preferred as a material capable of forming the unit of formula (1-1).

A specific example of methacryloyloxysiloxane is β-
methacryloyloxyethyldimethoxymethylsilane,
γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyljethoxymethylsilane, δ-methacryloyloxy Examples include butyljethoxymethylsilane. The amount of the grafting agent used is 0 to 10% by weight in the polyorganosiloxane rubber component.

The latex of this polyorganosiloxane rubber component can be produced using, for example, the methods described in US Pat. No. 2,891,920 and US Pat. No. 3,294,725. In the practice of the present invention, for example, a mixed solution of organosiloxane, crosslinking agent (1), and optionally grafting agent (1) is mixed in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid, For example, it is preferable to manufacture by a method of shear mixing with water using a homogenizer or the like. Alkylbenzenesulfonic acid is suitable because it acts as an emulsifier for organosiloxane and also serves as a polymerization initiator. At this time, it is preferable to use an alkylbenzenesulfonic acid metal salt, an alkylsulfonic acid metal salt, or the like in combination, since this is effective in maintaining the polymer stably during graft polymerization.

(2) Polyalkyl (meth)acrylate rubber component The polyalkyl (meth)acrylate rubber component constituting the above composite rubber in the coating consists of the following alkyl (meth)acrylate, crosslinking agent (II), and grafting agent (II). It can be synthesized using

Examples of alkyl (meth)acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and hexyl methacrylate, 2-ethylhexyl methacrylate, n-
Examples include alkyl methacrylates such as alkyl methacrylates such as - lauryl methacrylate, and use of n-butyl acrylate is particularly preferred.

Examples of the crosslinking agent (n) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1.3-butylene gelicold dimethacrylate, 1.
Examples include 4-butylene gelicoldimethacrylate.

Examples of the grafting agent (II) include allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate. Allyl methacrylate can also be used as a crosslinking agent.

These crosslinking agents and grafting agents may be used alone or in combination of two or more. The total amount of these crosslinking agents and grafting agents used is 0.1 to 20% by weight in the polyalkyl (meth)acrylate rubber component.

(3) Composite rubber Next, we will explain about composite rubber. The composite rubber is preferably produced by impregnating rubber particles of polyorganosiloxane rubber latex with a monomer for synthesis of alkyl (meth)acrylate rubber, and then polymerizing the monomer for synthesis. That is, the alkyl (meth)acrylate, crosslinking agent (II), and grafting agent are added to the latex of the polyorganosiloxane rubber component that has been neutralized by adding an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, or sodium carbonate. After (II) is added and impregnated into the polyorganosiloxane rubber particles, a conventional radical polymerization initiator is applied to polymerize the polyalkyl (meth)acrylate rubber component. As the polymerization progresses, a polyalkyl (meth)acrylate rubber is formed which is compositely integrated with the polyorganosiloxane rubber, and a composite rubber latex of the polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component, which is virtually inseparable, is obtained. It will be done.

In addition, when carrying out the present invention, the main skeleton of the polyorganosiloxane rubber component has repeating units of dimethylsiloxane as this composite rubber, and the main skeleton of the polyalkyl (meth)acrylate rubber component has repeating units of n-butyl acrylate. Composite rubber having the following properties is preferably used.

The composite rubber thus prepared by emulsion polymerization is
It can be graft copolymerized with vinyl monomers, and since the polyorganosiloxane rubber component and polyalkyl (meth)acrylate rubber component are integrated into a composite, they cannot be extracted and separated using ordinary organic solvents such as ascent and toluene. .

In addition, in the composite rubber used in the present invention, if the polyorganosiloxane rubber component exceeds 90% by weight, the molded surface appearance of the molded product from the resulting resin composition will deteriorate, and the polyalkyl (meth)acrylate rubber component will deteriorate. If it exceeds 90% by weight, the impact resistance of molded products from the resulting resin composition at low temperatures tends to particularly deteriorate, which is undesirable. Therefore, the two types of rubber components that make up the composite rubber are both 10 to 90% by weight (however, the total amount of both rubber components is 1% by weight).
00% by weight), and further 20% by weight).
A range of 80% by weight is particularly preferred.

The average particle diameter of the composite rubber is preferably in the range of 0.08 to 0.6 μm. If the average particle size is less than 0.08 μm, the impact resistance of the molded product from the resin composition will deteriorate, and if the average particle size exceeds 0.6 μm, the impact resistance of the molded product from the resin composition will deteriorate. In addition to deteriorating the properties, the appearance of the molded surface also deteriorates. The gel content measured by extracting this composite rubber with toluene at 90°C for 12 hours was 80.
% by weight or more.

The above composite rubbers can be used alone or in combination of two or more.

(4) Composite Rubber Graft Polymer A vinyl cyanide monomer and an aromatic vinyl monomer are used for graft polymerization to the above composite rubber.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylaterile, ethacrylonitrile, and fumaronitrile, which can be used alone or in combination. The ratio of vinyl cyanide monomer in the graft monomer is 1
It is 5 to 40% by weight.

If it is less than 15% by weight, the resulting resin composition will have poor impact resistance, which is not preferable. Moreover, if it exceeds 40% by weight, the resulting resin composition will be significantly colored during molding and the impact resistance will also decrease, which is not preferable.

Aromatic vinyl monomers used for graft polymerization include styrene, α-methylstyrene, 0 to methylstyrene, 1
．． Examples include 3-dimethylstyrene, P-methylstyrene, thi-butylstyrene, halogenated styrene, P-ethylstyrene, and the like, and these can be used alone or in combination. The ratio of the aromatic vinyl monomer to the graft monomer is 60 to 85% by weight, and if it deviates from this range, it is not preferable because at least one of impact resistance and moldability will be poor.

Further, other copolymerizable vinyl monomers can also be used in graft polymerization. These monomers include, but are not limited to, methyl methacrylate, ethyl methacrylate, 2-vinylpyridine, 4-vinylpyridine, and maleimide monomers such as N-phenylmaleimide. .

The other copolymerizable vinyl monomer is used in an amount of up to 35% by weight of the graft monomer, if necessary.

As for the particle size of this composite rubber-based graft copolymer, it is particularly preferable that the average particle size is 0.1 to 0.7 μm.

The amount of composite rubber graft copolymer (B) used is (A),
1 out of 100 parts by weight of the total amount of components (B) and (C)
It is 0 to 90 parts by weight. If it is less than 10 parts by weight, the resulting composition will have poor impact resistance, and if it exceeds 90 parts by weight, it will have poor chemical resistance, which is not preferred.

The composite rubber graft copolymer (B) may be used alone or in combination of two or more.

(C) About the polymer The polymer (C) in the present invention is obtained by polymerizing at least one of a vinyl cyanide monomer, an aromatic vinyl monomer, and a (meth)acrylic acid ester monomer. It is a polymer that can be used. The vinyl cyanide monomer used here,
The aromatic vinyl monomer is the same as the monomer used in the composite rubber graft copolymer (B). The methacrylic acid ester monomer is not particularly limited, but methyl methacrylate, ethyl methacrylate, propyl methacrylate, etc. are preferably used. Note 1. Polymer (
In addition to the above monomers, examples of C) include minor amounts of other copolymerizable monomers such as acrylic acid ester monomers, maleimide monomers, and pyridine monomers. ,
It is not particularly limited to these.

Polymer (C) is used as necessary for the purpose of improving moldability, heat resistance, and elastic modulus. The amount of polymer (C) used is 0 to 80 parts by weight, preferably 0 to 60 parts by weight, based on 100 parts by weight of the total amount of components (A), (B), and (C). If it deviates from this range, the resin composition that is the object of the present invention cannot be obtained, which is not preferable.

Further, the intrinsic viscosity of the polymer (C) is preferably 0.3 to 1.5 from the viewpoint of moldability and impact resistance.

(D) Reinforcing filler In the present invention, if necessary, reinforcing filler (D)
By blending, heat resistance, rigidity, and thermal dimensional stability can be improved. As the reinforcing filler (D),
Although not particularly limited, examples include inorganic fibers such as glass fiber and carbon fiber, wollastonite, talc,
It is one or more types of inorganic fillers selected from mica powder, glass powder, potassium titanate, and the like.

The blending amount of the reinforcing filler is 0 to 100 parts by weight based on 100 parts by weight of the total amount of components (A), (B), and (C).

If the amount of the reinforcing filler (D) exceeds 100 parts by weight, the resulting composition will have poor impact resistance and will not be the desired composition of the present invention.

Furthermore, various additives such as a modifier, a mold release agent, a stabilizer against light or heat, and dyes and pigments can be added to the thermoplastic resin composition of the present invention, if necessary.

As a method for preparing the thermoplastic resin composition of the present invention, devices such as a Henschel mixer and a tumbler that are commonly used for blending resins can be used. Also, for shaping, devices commonly used for shaping, such as a single-screw extruder, a twin-screw extruder, and an injection molding machine, can be used.

Example The present invention will be explained in more detail with reference to Examples below.

In the Examples and Comparative Examples below, "1 part" and "%J" mean "parts by weight" and "% by weight," respectively.

In addition, the following method was used to evaluate each physical property in each Example and Comparative Example.

(1) Izot impact strength Measured according to ASTM D-256. (Unit: kg-
cm/cm) (l/4 inch thickness, using a notched specimen) (2) Heat distortion temperature Measured according to ASTM D-648. (Unit: °C) (
Bending resistance: 4.6 kg/cnJ) (3) Heat resistance stability: Leave in an oven at 120°C for 72 hours, ASTM D
-1925 compliant color computer C5M-4-
ΔE was measured using a Type 2 manufactured by Suga Test Instruments Co., Ltd.

The components used in the Examples and Comparative Examples are as follows.

(A) Polyamide As polyamide, nylon 6 manufactured by Mitsubishi Kasei Corporation is used.
Tsubamitsudo 10IOJ was used.

(B) Graft copolymer Production of graft copolymer (B-1).

The graft copolymer (B-1) is a composite rubber-based graft copolymer in the present invention, and was produced as follows.

2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane, and 97.5 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. Add 100 parts of the above mixed siloxane to 200 parts of distilled water in which 1 part each of sodium dodecylbenzenesulfonate and dodecylbenzenesulfonic acid were dissolved, and mix with a homomixer at 10,000 rpm.
After pre-stirring at m, 300kg was
The mixture was emulsified and dispersed at a pressure of /cot to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and stirring blades, heated at 80°C for 5 hours while stirring, and then left at 20°C. After 48 hours, the pH of this latex was adjusted with an aqueous sodium hydroxide solution.
was neutralized to 6.9 to complete polymerization to obtain polyorganosiloxane rubber latex. The polymerization rate of the obtained polyorganosiloxane rubber was 89.7%, and the average particle diameter of the polyorganosiloxane rubber was 0.16 μm.

100 parts of this polyorganosiloxane rubber latex (
Solid content: 30%) was collected, placed in a separable flask equipped with a stirrer, added with 120 parts of distilled water, replaced with nitrogen, heated to 50°C, and mixed with 37.5 parts of loubutyl acrylate and 2 parts of allyl methacrylate. A mixed solution of 0.5 parts of tert-butyl hydroperoxide and 0.3 parts of tert-butyl hydroperoxide was charged and stirred for 30 minutes to allow this mixed solution to penetrate into the polyorganosiloxane rubber particles. Next, a mixture of 0.0003 parts of ferrous sulfate, 0.001 part of ethylenediaminetetraacetic acid disodium salt, 0.17 parts of Rongalite, and 3 parts of distilled water was charged to start radical polymerization, and then the mixture was heated at an internal temperature of 70°C for 2 hours. The polymerization was completed by holding for a certain period of time to obtain a composite rubber latex. A portion of this latex was sampled and the average particle size of the composite rubber was measured and found to be 0.19 μm. Further, this latex was dried to obtain a solid substance, which was extracted with toluene at 90°C for 12 hours, and the gel content was measured and found to be 90.3%.

A mixture of 0.3 parts of tert-butyl hydroperoxide, 9 parts of acrylonitrile, and 21 parts of styrene was added dropwise to this composite rubber latex at 70°C for 45 minutes, and then kept at 70°C for 4 hours to form a composite rubber. Graft polymerization was completed.

The polymerization rate of the obtained graft copolymer was 98.6%. The obtained graft copolymer latex was coagulated and separated by dropping it into hot water of calcium chloride 5z,
After washing, it was dried at 75°C for 16 hours to obtain a composite rubber-based graft copolymer (B-1).

Production of graft copolymer (B-2).

The graft copolymer (B-2) is a graft copolymer of polyorganosiloxane rubber, and was produced as follows.

Mixing 3.0 parts of tetraethoxysilane, 1.0 parts of γ-methacryloyloxypropyldimethoxymethylsilane and 96.0 parts of octamethylcyclotetrasiloxane,
100 parts of mixed siloxane were obtained. Add 100 parts of mixed siloxane to 300 parts of distilled water in which 1.0 part of dodecylbenzenesulfonic acid has been dissolved, and mix with a homomixer to 11,000 Or
After pre-stirring with p, 300kg was added using a homogenizer
Emulsify and disperse by passing twice at a pressure of /cnl,
A polyorganosiloxane latex was obtained. This liquid mixture was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 85° C. for 4 hours while stirring and mixing, and then cooled at 5° C. for 24 hours.

This latex was then diluted with an aqueous sodium hydroxide solution.
H was neutralized to 7.2 to complete the polymerization. The polymerization rate of the obtained polyorganosiloxane rubber was 91.2%, the solid content concentration was 22.74%, and the swelling degree (when the polyorganosiloxane was saturated at 25°C in a toluene solvent, the polyorganosiloxane absorbed The weight ratio of toluene) is 7.
4, and the particle size of the polyorganosiloxane rubber is 0.
It was 150 μm.

This polyorganosiloxane rubber latex 263.9
(solid content concentration 22.74%) was placed in a separable flask, and the temperature was raised to 70°C after purging with nitrogen. The monomer mixture was charged and stirred for 30 minutes. Additionally, 0.12 parts of Rongalit, 0.0002 parts of ferrous sulfate, and 0.00 parts of ethylenediaminetetraacetic acid disodium salt. An aqueous solution of 6 parts of QOO and 10 parts of water was added to start radical polymerization, and after the exotherm of polymerization disappeared, the reaction temperature was maintained for 2 hours to complete the polymerization. The resulting graft copolymer had a polymerization rate of 97%, a grafting rate of 48%, and a grafting efficiency of 72%. The obtained latex was dropped into hot water in which 5 parts of calcium chloride and dihydrate were dissolved to coagulate and separate the polymer, which was then dried to remove moisture and form a graft copolymer (B-2). I got it.

Production of graft copolymer (B-3).

The graft copolymer (B-3) is a graft copolymer of enlarged polybutadiene latex, and was produced as follows.

A copolymer with an average particle size of 0.08 μm consisting of 85% n-butyl acrylate units and 15% methacrylic acid units was added to 60 parts (as solid content) of polybutadiene latex with a solid content of 33% and an average particle size of 0.08 μm. 1 part of polymer latex (as solid content) was added with stirring and continued stirring for 30 minutes to obtain enlarged rubber latex with an average particle size of 0.28 μm.

The obtained enlarged rubber latex was added to a reaction vessel, and further 50 parts of distilled water, 2 parts of wood rosin emulsifier, and thymol N (
Product name, manufactured by Kao Corporation, naphthalene sulfonic acid formalin condensate) 0.2 parts, sodium hydroxide 0.02 parts, dextrose 0.35 parts, butyl acrylate 5 parts, and cumene hydroperoxide 0.1 parts was added with stirring, and the temperature was raised to 60°C.
5 parts of sodium birophosphate, 0.2 parts of sodium birophosphate, and 0.03 parts of sodium dithionite were added, and the internal temperature was maintained at 60° C. for 1 hour. After holding for 1 hour, 10 parts of acrylonitrile, 25 parts of styrene
part, 0.2 parts of cumene hydroperoxide and ter
A mixture of 0.5 parts of t-dodecyl mercaptan was continuously added dropwise over 90 minutes, and then kept for 1 hour to cool.

The obtained graft copolymer latex was coagulated with dilute sulfuric acid, washed, filtered, and dried to obtain a graft copolymer (B-3).
) was obtained.

Production of graft copolymer (B-4).

The graft copolymer (B-4) is polyalkyl (meth)
It is a graft copolymer of acrylate rubber and was produced as follows.

Potassium oleate 1.0 part Disproportionated potassium rosinate 1. O part Sodium birophosphate 0.5 part Ferrous sulfate
0.005 parts dextrose
0.3 parts anhydrous sodium sulfate
0.3 parts ion exchange water
190 parts were replaced with nitrogen, and the temperature was raised to 70°C. A solution prepared by dissolving 0.12 parts of potassium peroxide (KPS) in 10 parts of ion-exchanged water was added to this, and the following nitrogen-substituted monomer mixture was continuously added dropwise over 2 hours.

n-Butyl acrylate 60 parts Allyl methacrylate 0.32 parts Ethylene glycol dimethacrylate 0.16 parts After completion of the dropwise addition, the internal temperature was further raised to 80° C. and maintained for 1 hour. The polymerization rate was 98.
It reached 8%. The degree of swelling of this acrylic rubber is 6.4 (ratio of swollen weight to absolute dry weight after immersion in methyl ethyl ketone at 30°C for 24 hours), gel content is 93.0%,
The particle size was 0.22 μm.

A grafting monomer consisting of 12 parts of acrylonitrile and 28 parts of styrene and 0.35 parts of benzoyl peroxide were further mixed with this acrylic rubber, and the mixture was continuously added dropwise for 1 hour. After the dropwise addition was completed, the temperature was raised and maintained at 80° C. for 30 minutes.

The polymerization rate was 99%. Dilute sulfuric acid was added to a portion of the latex and the powder was coagulated and dried, and the powder was extracted under refluxing methyl ethyl ketone, and the 7 sp/c of the extracted portion was measured at 25° C. using dimethylformamide as a solvent and found to be 0.67.

The latex produced as above was mixed with aluminum chloride (A Q C9, .6H, O) in an amount three times that of the whole latex.
．． It was poured into a 15% aqueous solution (90°C) with stirring and solidified. After cooling, the mixture was dehydrated using a centrifugal dehydrator, washed, and dried to obtain a graft copolymer (B-4).

(C) Polymer Production of polymers (C-1) and (C-2).

Polymers (C-1) and (C-2) having the compositions shown in Table 1 were obtained by a suspension polymerization method.

The reduced viscosities η sp/c of these polymers at 25° C. are also shown in Table 1. In addition, ηsp/c in Table 1 is the polymer (
C-1) was measured using a 0.2% dimethylformamide solution, and polymer (C-2) was measured using a 1% chloroform solution.

(D) As the reinforcing filler glass fiber, rEcsO3 manufactured by Nippon Electric Glass Co., Ltd.
T-34J was used, the carbon fiber was Pyrofil TR-06NJ manufactured by Mitsubishi Rayon Co., Ltd., and the talc was ``Microtank IO-52'' manufactured by Pfizer MSP Co., Ltd.

Blend of each component The obtained polymers, glass fibers, carbon fibers, talc, and other components were blended in the side combinations shown in Table 2, mixed for 5 minutes in a Henschel mixer, and then mixed with a screw with a diameter of 30 mm.
It was pelletized using a twin-screw extruder.

Using these pellets, various physical properties were evaluated by the methods described above. The results are also shown in Table 2.

(Effects of the Invention) According to the present invention, by blending the above-mentioned specific composite rubber-based graft copolymer, polyamide resin having excellent properties such as chemical resistance, moldability, and abrasion resistance can be improved. It can provide impact resistance and heat resistance stability as well as an excellent appearance when molded. Therefore, the resin composition of the present invention is extremely useful for automobile parts, electrical and electronic parts, and the like.

Claims (1)

[Claims] 1. (A) polyamide: 10 to 90 parts by weight (B) polyorganosiloxane rubber component 10 to 90% by weight and polyalkyl (meth)acrylate rubber component 90 to 90% by weight
Composite rubber has a structure in which 10% by weight cannot be separated.
Composite rubber-based graft copolymer obtained by graft polymerization of vinyl cyanide monomer and aromatic vinyl monomer: 90-10
Part by weight (C) Polymer obtained by polymerizing at least one of a vinyl cyanide monomer, an aromatic vinyl monomer, and a (meth)acrylic acid ester monomer: 0 to 80 parts by weight ( A) A thermoplastic resin composition blended so that the total amount of components (B) and (C) is 100 parts by weight, and (D
) A thermoplastic resin composition with excellent impact resistance and heat resistance stability, containing 0 to 100 parts by weight of a reinforcing filler.