JP2876226B2 - Resin composition with excellent impact resistance and heat stability - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having improved impact resistance and heat stability.

(Problems to be Solved by Conventional Techniques and Inventions) Polyamide resins have excellent properties such as chemical resistance, moldability, and abrasion resistance, and are therefore used in a wide range of fields such as automobile parts and electric and electronic parts. ing. However, their low impact resistance, especially the notched impact strength, has severely limited their applications. Therefore, research has been conducted on a resin composition for the purpose of improving the impact resistance of a polyamide resin. For example, a method of blending an ABS resin with a polyamide resin is disclosed in JP-B-38-234.
JP-A-51-36274 describes a method of blending a polymer obtained by graft copolymerizing acrylonitrile and styrene with an acrylic rubber. However, although these resins improve the impact resistance of the polyamide resin, they are inferior in either heat stability or impact resistance at low temperatures.

(Means for Solving the Problems) The inventors of the present invention have conducted intensive studies on methods for improving the impact resistance and heat resistance stability of a polyamide resin even at a low temperature, and as a result, a specific graft copolymer and, if necessary, a reinforcement. The present inventors have found that the initial purpose can be achieved by blending the filler for use in a specific ratio, and completed the present invention.

That is, the present invention provides (A) polyamide: 10 to 90 parts by weight, (B) 10 to 90% by weight of a polyorganosiloxane rubber component and 90 to 10% by weight of a polyalkyl (meth) acrylate rubber component. ) An acrylate rubber component-synthesizing monomer is impregnated into rubber particles of a polyorganosiloxane rubber latex and then polymerized. Rubber-based graft copolymer obtained by graft polymerization of a copolymer and an aromatic vinyl monomer: 90 to 10 parts by weight (C) vinyl cyanide monomer, aromatic vinyl monomer and (meth) acrylate monomer A polymer obtained by polymerizing at least one of the monomers: 0 to 80 parts by weight, a thermoplastic resin blended so that the total amount of the components (A), (B) and (C) becomes 100 parts by weight resin And Narubutsu, (D) a reinforcing filler: 0-100 parts by weight and impact resistance formulated is a thermoplastic resin composition having excellent heat stability.

Hereinafter, the present invention will be described in detail. First, each component constituting the thermoplastic resin composition of the present invention will be described.

(A) Polyamide The polyamide (A) constituting the thermoplastic resin composition according to the present invention is obtained by polycondensation of a lactam having three or more rings, a polymerizable ω-amino acid, or a diacid and a diamine. Can be used.

Specifically, polymers such as ε-caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminonananoic acid, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethyldiamine Diamines such as methylene diamine, meta-xylene diamine and terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid,
A polymer obtained by polycondensation with a dicarboxylic acid such as glutaric acid, or a copolymer thereof, for example, nylon 6,
Nylon 11, Nylon 12, Nylon 4.6, Nylon 6
6, nylon 6,10, nylon 6,12 and the like.

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

(B) Composite Rubber Graft Copolymer The composite rubber graft copolymer (B) used in the present invention.
Is 10 to 90% by weight of a polyorganosiloxane rubber component and 90 to 10% by weight of a polyalkyl (meth) acrylate rubber component.
(A total amount of each rubber component is 100% by weight), and a composite rubber in which a vinyl cyanide monomer and an aromatic vinyl monomer are graft-polymerized to a composite rubber having a structure in which both rubber components cannot be separated substantially. It is a rubber-based graft copolymer.

Even when 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 characteristics of the resin composition aimed at by the present invention are possessed. It is not possible to obtain the rubber, and it is the first time that a rubber composition obtained by combining and integrating a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component as a rubber source has excellent impact resistance even at low temperatures and heat stability. The resin composition which gives a molded article excellent in the above can be obtained.

An emulsion polymerization method is most suitable for producing the composite rubber used in the present invention. First, a latex of a polyorganosiloxane rubber is prepared, and then a monomer for synthesizing a polyalkyl (meth) acrylate rubber is converted to a polyorganosiloxane. It is produced by impregnating rubber particles of rubber latex and then polymerizing the synthesis monomer. This will be described in detail below.

(1) Polyorganosiloxane Rubber Component The polyorganosiloxane rubber component constituting the above composite rubber can be prepared by emulsion polymerization using the following organosiloxane and crosslinking agent (I), and in that case, graft crosslinking is further performed. The agent (I) can be used in combination.

Examples of the organosiloxane include various cyclic members having three or more membered rings, and preferably a three- to six-membered ring. For example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like, These may be used alone or as a mixture of two or more. These organosiloxanes are used in an amount of at least 50% by weight, preferably at least 70% by weight in the polyorganosiloxane rubber component.

Examples of the crosslinking agent (I) include trifunctional or tetrafunctional silane-based crosslinking agents, for example, trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and the like. Is used. Particularly, a tetrafunctional crosslinking agent is preferable, and among them, tetraethoxysilane is particularly preferable. The amount of the crosslinking agent used is 0.1 to 30% by weight in the polyorganosiloxane rubber component.

As the graft-linking agent (I), the following formula (In each formula, R ¹ is a methyl group, an ethyl group, a propyl group or a phenyl group, R ² is a hydrogen atom or a methyl group, n is 0, 1 or 2, and p is a number of 1 to 6.) A compound capable of forming a unit is used.
(Meth) acryloyloxysiloxane capable of forming the unit of the formula (I-1) has a high grafting efficiency and can form an effective graft chain, and is advantageous in terms of the development of impact resistance.

Note that methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of the formula (I-1). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane,
γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane, and the like. . The amount of the graft crosslinking agent used is 0 to 10 in the polyorganosiloxane rubber component.
% By weight.

The production of the latex of the polyorganosiloxane rubber component is described in, for example, U.S. Pat.
The method described in the specification of No. 25 can be used.
In the practice of the present invention, for example, a mixed solution of an organosiloxane, a crosslinking agent (I) and, if desired, a graft crosslinking agent (I) is mixed in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid. For example, it is preferably produced by a method of shear mixing with water using a homogenizer or the like. Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier for the organosiloxane and also serves as a polymerization initiator. At this time, it is preferable to use a metal salt of an alkyl benzene sulfonic acid, a metal salt of an alkyl sulfonic acid or the like in combination, since this is effective in maintaining the polymer stably during graft polymerization.

(2) Polyalkyl (meth) acrylate rubber component Next, the polyalkyl (meth) acrylate rubber component constituting the composite rubber includes the following alkyl (meth) acrylate, cross-linking agent (II) and graft cross-linking agent (II) Can be used for synthesis.

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

Examples of the crosslinking agent (II) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4
-Butylene glycol dimethacrylate and the like.

Examples of the graft crosslinking agent (II) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent. These crosslinking agents and graft crossing agents are 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, the composite rubber will be described. The composite rubber is produced by impregnating a polyalkyl (meth) acrylate rubber synthesis monomer into rubber particles of a polyorganosiloxane rubber latex and then polymerizing the synthesis monomer. That is, the latex of the polyorganosiloxane rubber component neutralized by the addition of an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, or sodium carbonate contains the alkyl (meth) acrylate, the crosslinking agent (II) and the grafting agent. After adding (II) and impregnating the polyorganosiloxane rubber particles, the polyalkyl (meth) acrylate rubber component is polymerized by the action of a usual radical polymerization initiator. As the polymerization proceeds, a polyalkyl (meth) acrylate rubber composited and integrated with the polyorganosiloxane rubber is formed, and a latex of a composite rubber of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component that cannot be substantially separated is obtained. Can be

In the practice of the present invention, as the composite rubber, the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the main skeleton of the polyalkyl (meth) acrylate rubber component has a repeating unit of n-butyl acrylate. The composite rubber having is preferably used.

The composite rubber thus prepared by emulsion polymerization can be graft-copolymerized with a vinyl monomer, and the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are compositely integrated. Therefore, extraction and separation cannot be carried out with ordinary organic solvents such as ascent and toluene. Incidentally, the composite rubber used in the present invention is described in JP-A-2-199109, a co-homopolymerized polymer substrate comprising a combination of at least one polymer based on an organosiloxane polymer and vinyl,
Not included.

Further, in the composite rubber used in the present invention, if the polyorganosiloxane rubber component exceeds 90% by weight, the appearance of the molded surface of the molded product from the obtained resin composition deteriorates, and the polyalkyl (meth) acrylate rubber component Is 90% by weight
If it exceeds, the impact resistance of a molded article from the obtained resin composition at low temperature tends to be particularly deteriorated, which is not preferable.
For this reason, both of the two types of rubber components constituting the composite rubber
It must be within the range of 10 to 90% by weight (however, the total amount of both rubber components is 100% by weight), and further 20 to 80% by weight.
It is particularly preferable that it is in the range of

The composite rubber preferably has an average particle diameter in the range of 0.08 to 0.6 μm. When the average particle size is less than 0.08 μm, the impact resistance of the molded product from the obtained resin composition deteriorates, and when the average particle size exceeds 0.6 μm, the impact resistance of the molded product from the obtained resin composition becomes poor. Along with the deterioration, the appearance of the molding surface deteriorates. 90 ° C of this composite rubber with toluene
The gel content measured by extraction for 12 hours is more than 80% by weight.

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

(4) Composite rubber-based graft polymer A vinyl cyanide monomer and an aromatic vinyl monomer are used for the graft polymerization to the composite rubber.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile and the like, and these can be used alone or in combination. The proportion of vinyl cyanide monomer in the graft monomer is 15
~ 40% by weight. If the amount is less than 15% by weight, the resulting resin composition has poor impact resistance, which is not preferable. On the other hand, if it exceeds 40% by weight, the resulting resin composition is undesirably colored when molded and the impact resistance is lowered.

As the aromatic vinyl monomer used for the graft polymerization,
Styrene, α-methylstyrene, 0-methylstyrene,
Examples thereof include 1,3-dimethylstyrene, P-methylstyrene, t-butylstyrene, halogenated styrene, and P-ethylstyrene, 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 is outside these ranges, at least one of the impact resistance and the moldability is inferior.

Further, another vinyl monomer copolymerizable for the graft polymerization can be used. These monomers include, but are not particularly limited to, maleimide monomers such as methyl methacrylate, ethyl methacrylate, 2-vinylpyridine, 4-vinylilipyridine and N-phenylmaleimide. The other copolymerizable vinyl monomer is used as needed in the range of up to 35% by weight in the graft monomer.

The composite rubber-based graft copolymer preferably has an average particle diameter of 0.1 to 0.7 μm.

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

The composite rubber-based graft copolymer (B) may be used alone or
Used as a mixture of more than one species.

(C) 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) acrylate monomer. It is a polymer. The vinyl cyanide monomer used here,
The aromatic vinyl monomer is the same as the monomer used in the composite rubber-based graft copolymer (B). The methacrylate monomer is not particularly limited, but preferably, ethyl methacrylate, ethyl methacrylate, propyl methacrylate, and the like are used. In addition, in the polymer (C), in addition to the above-mentioned monomers, other copolymerizable monomers in poor positions include acrylate monomers, maleimide monomers, pyridine monomers and the like. Examples include, but are not particularly limited to, these.

The polymer (C) is used as needed for the purpose of improving moldability, heat resistance and elastic modulus. The amount of the 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 of the components (A), (B) and (C). If the ratio is out of this range, the desired resin composition of the present invention cannot be obtained, which is not preferable. The intrinsic viscosity of the polymer (C) is preferably from 0.3 to 1.5 in view of moldability and impact resistance.

(D) Reinforcing filler In the present invention, the heat resistance, rigidity and thermal dimensional stability can be improved by further blending a reinforcing filler (D) as necessary. The reinforcing filler (D) is not particularly limited, but may be selected from, for example, inorganic fibers such as glass fiber and carbon fiber and inorganic fillers such as wollastonite, talc, mica powder, glass powder, and potassium titanate. Is more than one.

The compounding amount of the reinforcing filler is 0 to 100 parts by weight based on 100 parts by weight of the total amount of the components (A), (B) and (C). When the amount of the reinforcing filler (D) exceeds 100 parts by weight, the composition obtained as the object of the present invention is not obtained because the obtained composition has poor impact resistance.

Further, various additives such as a modifier, a release agent, a stabilizer against light or heat, and a dye or pigment may be appropriately 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, an apparatus such as a Henschel mixer or a tumbler which is usually used for blending resins can be used. As for shaping, a device used for normal shaping, such as a single-screw extruder, a twin-screw extruder, or an injection molding machine, can be used.

Examples Hereinafter, the present invention will be described in more detail with reference to Examples.

In the following Examples and Comparative Examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

In addition, the evaluation method of each physical property in each Example and Comparative Example was based on the following method.

(1) Izod impact strength Measured according to ASTM D-256. (Unit: kg · cm / cm) (1/4 inch thickness, using notched specimen) (2) Heat deformation temperature Measured according to ASTM D-648. (Unit: ° C) (Bending stress: 4.6 kg / cm ² ) (3) Heat resistance Stability After standing in an oven at 120 ° C for 72 hours, a color computer CSM-4-2 type suga test machine according to ASTM D-1925 ( ΔE was measured by the company.

The components used in the examples and comparative examples are as follows.

(A) Polyamide As the polyamide, nylon 6 manufactured by Mitsubishi Kasei Co., Ltd.
"Novamid 1010" was used.

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

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

Two 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. Sodium dodecylbenzenesulfonate and
100 parts of the above mixed siloxane was added to 200 parts of distilled water in which the parts were dissolved, and after preliminary stirring at 10,000 rpm with a homomixer,
The mixture was emulsified and dispersed with a homogenizer at a pressure of 300 kg / cm ² to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, and heated at 80 ° C. for 5 hours while stirring and mixing.
After standing for 48 hours, the pH of this latex was neutralized to 6.9 with an aqueous sodium hydroxide solution to complete the polymerization to obtain a polyorganosiloxane rubber latex. The polymerization rate of the obtained polyorganosiloxane rubber was 89.7%, and the average particle size of the polyorganosiloxane rubber was 0.16 μm.

100 parts of this polyorganosiloxane rubber latex (solid content: 30%) was collected and placed in a separable flask equipped with a stirrer.
37.5 parts of n-butyl acrylate, 2.5 parts of allyl methacrylate and 0.3 parts of tert-butyl hydroperoxide.
Parts of the mixture was charged and stirred for 30 minutes, and the mixture was permeated into the polyorganosiloxane rubber particles. Next, a mixture of ferrous sulfate (0.0003 parts), ethylenediaminetetraacetic acid disodium salt (0.001 part), Rongalit (0.17 part) and distilled water (3 parts) was charged to start radical polymerization. Thereafter, the polymerization was completed by maintaining the internal temperature at 70 ° C. for 2 hours. Thus, a composite rubber latex was obtained. A part of this latex was collected and the average particle diameter of the composite rubber was measured to be 0.19 μm. The latex was dried to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured to be 90.3%.

0.3 parts of tert-butyl hydroperoxide, 9 parts of acrylonitrile and 21 parts of styrene were added to this composite rubber latex.
Part of the mixture was dropped at 70 ° C. over 45 minutes, and then
It was kept at 70 ° C. for 4 hours to complete the graft polymerization to the composite rubber.

The polymerization rate of the obtained graft copolymer was 98.6%. The obtained graft copolymer latex is coagulated and separated by dropping into hot water of 5% calcium chloride,
After washing, the resultant 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) was a graft copolymer of a polyorganosiloxane rubber, and was produced as follows.

3.0 parts of tetraethoxysilane, 1.0 part of γ-methacryloyloxypropyldimethoxymethylsilane and 96.0 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of mixed siloxane. Dodecylbenzenesulfonic acid 1.0
100 parts of the mixed siloxane was added to 300 parts of distilled water in which 1 part of the polyorganosiloxane latex was added. The mixture was preliminarily stirred at 10,000 rpm with a homomixer, and then passed twice with a homogenizer at a pressure of 300 kg / cm ² to emulsify and disperse. I got The 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. Next, the pH of the latex was neutralized to 7.2 with an aqueous sodium hydroxide solution to complete the polymerization. The polymerization rate of the obtained polyorganosiloxane rubber was 91.2%, the solid content concentration was 22.74%, and the degree of swelling (the weight of toluene absorbed by the polyorganosiloxane when the polyorganosiloxane was saturated at 25 ° C in a toluene solvent) Ratio) was 7.4, and the particle diameter of the polyorganosiloxane rubber was 0.150 μm.

263.9 parts of this polyorganosiloxane rubber latex (solid content: 22.74%) was placed in a separable flask,
After replacing with nitrogen, the temperature was raised to 70 ° C and acrylonitrile 10
, 30 parts of styrene and 0.08 part of t-butyl hydroperoxide were charged and stirred for 30 minutes. 0.12 parts of Rongalite, 0.0002 parts of ferrous sulfate,
0.0006 parts of disodium ethylenediaminetetraacetic acid and water
10 parts of an aqueous solution was added to start radical polymerization, and after the heat generated by the polymerization was stopped, the reaction temperature was maintained for 2 hours to terminate the polymerization. The graft ratio of the obtained graft copolymer was 97%, the graft ratio was 48%, and the graft efficiency was 72%. The polymer was coagulated and separated by dropping the obtained latex into hot water in which 5 parts of calcium chloride and dihydrate were dissolved,
After drying to remove water, a graft copolymer (B-2) was obtained.

Production of graft copolymer (B-3).

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

N-acrylic acid was added to 60 parts (as solid content) of polybutadiene latex having a solid content of 33% and an average particle size of 0.08 μm.
1 part (as solid content) of a copolymer latex of 85% butyl unit and 15% methacrylic acid unit having an average particle size of 0.08 μm is added with stirring, and stirring is continued for 30 minutes, and an enlarged rubber having an average particle size of 0.28 μm is added. Latex was obtained.

The obtained enlarged rubber latex was added to the reaction vessel, and further 50 parts of distilled water, 2 parts of wood rosin emulsifier, Temol N
(Trade name, manufactured by Kao Corporation, naphthalenesulfonic acid formalin condensate) 0.2 part, sodium hydroxide 0.02 part, dextrose 0.35 part, butyl acrylate 5 parts and cumene hydroperoxide 0.1 part are added with stirring. When the temperature was raised and the internal temperature was 60 ° C, 0.05 parts of ferrous sulfate, 0.2 parts of sodium pyrophosphate and 0.03 part of sodium dithionite were added, and the mixture was maintained at the internal temperature of 60 ° C for 1 hour. After keeping for 1 hour, a mixture of 10 parts of acrylonitrile, 25 parts of styrene, 0.2 parts of cumene hydroperoxide and 0.5 parts of tert-dodecyl mercaptan was continuously dropped over 90 minutes, and then kept for 1 hour and cooled. After the obtained graft copolymer latex was coagulated with dilute sulfuric acid, it was washed, dried and dried to obtain a graft copolymer (B-3).

Production of graft copolymer (B-4).

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

Potassium oleate 1.0 part Disproportionated potassium rosinate 1.0 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.005 part Dextrose 0.3 part Anhydrous sodium sulfate 0.3 part Ion exchange water 190 parts was 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 thereto, and the following nitrogen-substituted monomer mixture was added to 2 parts.
It was dropped continuously over time.

N-Butyl acrylate 60 parts Allyl methacrylate 0.32 parts Ethylene glycol dimethacrylate 0.16 parts After the completion of dropping, the internal temperature was further raised to 80 ° C. and maintained for 1 hour. The conversion reached 98.8%. The swelling degree of this acrylic rubber was (the ratio of the swelling weight to the absolute dry weight after immersion in methyl ethyl ketone at 30 ° C. for 24 hours) and 6.4, and the gel content was 93.0
%, And the particle diameter was 0.22 μm.

This acrylic rubber was further mixed with a grafting monomer composed of 12 parts of acrylonitrile and 28 parts of styrene and 0.35 part of benzoyl peroxide, and then continuously dropped for 1 hour.
After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 30 minutes. The conversion is 99
%Met. Dilute sulfuric acid was added to a part of the latex, and the solidified and dried powder was extracted under reflux of methyl ethyl ketone. The 7sp / c of the extracted portion was measured at 25 ° C. using dimethylformamide as a solvent, and it was 0.67.

The latex produced as described above was replaced with 3% of the total latex.
Fold amount of aluminum chloride was (AlCl ₃ · 6H ₂ O) were charged with stirring into 0.15% aqueous solution (90 ° C.) coagulation. After cooling, the mixture was dewatered and washed with a centrifugal dehydrator 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
Was obtained by a suspension polymerization method.

The reduced viscosity ηsp / c at 25 ° C. of these polymers is also shown in Table 1. In addition, ηsp / c in Table 1 indicates the polymer (C-1)
Is a value measured with a 0.2% dimethylformamide solution, and the polymer (C-2) is a value measured with a 1% chloroform solution.

(D) Reinforcing filler As glass fiber, "ECS03T-" manufactured by NEC Corporation
34, carbon fiber "Pyrofil TR-06N" manufactured by Mitsubishi Rayon Co., Ltd., and talc as Pfizer MSP.
"MIC TANK 10.52" manufactured by KK was used.

Mixing of each component The above obtained polymer, glass fiber, carbon fiber, talc, etc. were mixed in the proportions shown in Table 2 and mixed with a Henschel mixer for 5 minutes. Pelletized in an extruder. Using these pellets, various physical properties were evaluated by the methods described above. The results are shown in Table 2.

(Effects of the Invention) According to the present invention, a polyamide resin having excellent properties such as chemical resistance, moldability, and abrasion resistance can be obtained by blending the specific composite rubber-based graft copolymer described above. Impact resistance and heat stability, and excellent appearance when formed into a molded product can be imparted. Therefore, the resin composition of the present invention is extremely useful for automobile parts, electric and electronic parts, and the like.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ identification symbol FI C08L 51/00 C08L 51/00 (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 77/00-77/12 C08L 51/08 C08L 25/04 C08L 33 / 20,33 / 06 C08K 3/00

Claims (1)

(57) [Claims] (A) Polyamide: 10 to 90 parts by weight (B) 10 to 90% by weight of a polyorganosiloxane rubber component and 90 to 10% by weight of a polyalkyl (meth) acrylate rubber component ) An acrylate rubber component-synthesizing monomer is impregnated into rubber particles of a polyorganosiloxane rubber latex and then polymerized. Rubber-based graft copolymer obtained by graft polymerization of a copolymer and an aromatic vinyl monomer: 90 to 10 parts by weight (C) vinyl cyanide monomer, aromatic vinyl monomer and (meth) acrylate monomer A polymer obtained by polymerizing at least one of the monomers: 0 to 80 parts by weight, a thermoplastic resin blended so that the total amount of the components (A), (B) and (C) becomes 100 parts by weight Resin group Objects and, (D) a reinforcing filler: 0-100 parts by weight and impact resistance that is blended is, the thermoplastic resin composition having excellent heat stability.