JPH0711096A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition remarkably excellent in chemical resistance and impact resistance and, therefore, useful for a vehicle component, etc., coming into contact with various kinds of oils, detergents, etc., by blending two kinds of specified graft copolymers with a rigid thermoplastic resin. CONSTITUTION:This resin composition is composed of (A) a graft copolymer synthesized by conducting a seed polymerization of an alkyl acrylate and a copolymerizable monomer in the presence of a conjugated diene-based rubbery polymer latex (to form the following (i)) and graft-polymerizing (ii) an unsaturated cyanogen compound and (iii) an aromatic vinyl compound in the presence of (i) the resultant rubbery composite polymer latex, (B) another graft copolymer synthesized by conducting an emulsion polymerization of a conjugated diene, using the obtained conjugated diene-based rubbery copolymer latex (i) in combination with an oxygen-containing copolymer latex and graft-polymerizing the components (ii) and (iii) in the presence of (iv) the resultant enlarged rubbery copolymer latex and (C) a rigid thermoplastic resin synthesized by copolymerizing two or more kinds of monomers selected from the components (ii) and (iii), an unsaturated ester compound and a maleimide compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent chemical resistance and impact resistance.

[0002]

2. Description of the Related Art Rubber-reinforced styrenic resins represented by ABS resins are used in a wide range of fields as parts for household products and vehicles because of their excellent impact strength development. Therefore, in some cases, it may be used under the condition that it is exposed to chemicals. For example, resin products such as washbasins and shower heads in a wash basin or bathroom are exposed to detergents, and resin parts used in automobiles come into contact with machine oil or wax remover. Moreover, the resin used for the handle and door cap of the refrigerator is exposed to CFC, which is a urethane foaming agent, during the manufacturing of the heat insulating material of the refrigerator. Under such circumstances, the resin product often cracks or fine cracks may occur on the resin surface. This phenomenon is called cracking under environmental stress, and the strain remaining inside the molded rubber-reinforced styrenic resin product is caused by partial release due to contact with chemicals, resulting in solubility in resin. Notable in contact with low chemicals.
As a means for improving the chemical resistance of rubber-reinforced styrenic resins (ease of cracking under environmental stress), there is a method of using a crosslinked alkyl acrylate rubber as a rubber component. For example, it is an AAS resin obtained by graft-copolymerizing acrylonitrile and styrene on crosslinked butyl acrylate rubber. However, since the AAS resin has a drawback of low impact strength development, its use as a resin product is greatly limited. In order to obtain high impact strength manifestation, it is possible to take measures to increase the rubber content, but it is not preferable because the surface hardness and rigidity are lowered and scratches and deformation occur. Therefore, a rubber-reinforced styrene-based resin having excellent chemical resistance and impact strength development has been desired.

[0003]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made diligent studies in order to obtain a resin composition having an excellent physical property balance between chemical resistance and impact strength development. As a result, an alkyl acrylate ester and a conjugated diene rubber are used. Graft copolymer, a graft copolymer using a rubber obtained by seed-polymerizing an alkyl acrylate ester with a conjugated diene rubber, and a graft copolymer using a rubber obtained by seed-polymerizing an alkyl acrylate ester with a polyorganosiloxane rubber One or more graft copolymers selected from the following, and a graft copolymer using a conjugated diene rubber as essential components,
If necessary, a hard thermoplastic resin is blended so that the ratio of the rubber component in the thermoplastic composition becomes a specific composition, thereby providing an excellent physical property balance between chemical resistance and impact strength development. Found that a resin composition can be obtained,
The present invention has been reached.

[0004]

The gist of the present invention is to provide a graft copolymer (I) and a graft copolymer (II) containing the following graft copolymer (I) and graft copolymer (II) as essential components. And a hard thermoplastic resin (III), wherein the rubber-like copolymer accounts for 15% by weight of 100% by weight of the thermoplastic resin composition.
To 30% by weight and the proportion of alkyl acrylate ester units forming the rubbery polymer is 10
A thermoplastic resin composition is characterized in that it is 30 to 85% by weight with respect to 0% by weight. (I) The following graft copolymers (A), (B), (C)
One or more graft copolymers (I) selected from the group (A) Alkyl acid alkyl ester 35 to 85% by weight, conjugated diene and / or acrylic acid alkyl ester copolymerizable monomer 15 to 65% by weight, and copolymerizable monomer 0 to 20% by weight The gel content obtained by emulsion polymerization of and exceeds 70% by weight, and the average particle size is 0.03 to
0.2 μm rubber-like copolymer (a) latex with acid group-containing copolymer latex (i) or, if necessary, the acid group-containing copolymer latex (i) with metal salt of oxygen acid (ii) The average particle diameter obtained by using
In the presence of 20 to 80 parts by weight (as a solid content) of the enlarged rubber-like copolymer (a ') latex of 5 to 0.5 μm, 15 to 45% by weight of the unsaturated cyanide compound and 55 to 85 of the aromatic vinyl compound. Graft copolymer (20% to 80% by weight of a monomer mixture consisting of 80% by weight of a methacrylic acid alkyl ester and 0 to 20% by weight of an alkyl acrylate ester). A) (B) Conjugated diene rubbery polymer (b) Latex 5
In the presence of 65% by weight (as solid content), 35 to 95% by weight of a monomer mixture consisting of an acrylic acid alkyl ester and a monomer copolymerizable therewith is seed-polymerized to obtain a gel content of 20-80 parts by weight of composite rubber-like polymer (b ') latex exceeding 70% by weight (as solid content)
Graft copolymer (B) (C) obtained by graft-polymerizing 20 to 80 parts by weight of a monomer mixture consisting of 15 to 45% by weight of an unsaturated cyan compound and 55 to 85% by weight of an aromatic vinyl compound in the presence of ) Polyorganosiloxane rubber-like polymer (b-
2) Seed-polymerized in the presence of 5 to 65% by weight (as solid content) of a latex, 35 to 95% by weight of a monomer mixture consisting of an alkyl acrylate and a monomer copolymerizable therewith. The unsaturated cyanide compound 15 in the presence of 20 to 80 parts by weight (as solid content) of the composite rubbery polymer (c ') latex having a gel content of more than 70% by weight.
Graft copolymer (C) (II) conjugated diene 70-100% by weight obtained by graft-polymerizing 20-80 parts by weight of a monomer mixture consisting of -45% by weight and aromatic vinyl compound 55-85% by weight. To the conjugated diene rubbery copolymer (d) latex having an average particle size of 0.03 to 0.2 μm, which is obtained by emulsion polymerization of 0 to 30% by weight of a copolymerizable monomer. Enlarged rubber-like copolymer (d ') latex 30 obtained by adding polymer latex (i) or, if necessary, said acid group-containing copolymer latex together with metal salt (ii) of oxygen acid ~
In the presence of 70 parts by weight (as solid content), 15 to 45% by weight of an unsaturated cyan compound and 55 to 8 of an aromatic vinyl compound.
Graft copolymer (II) obtained by graft-polymerizing a monomer mixture of 5% by weight. (III) A hard thermoplastic resin (III) obtained by copolymerizing two or more kinds of monomers selected from unsaturated cyan compounds, aromatic vinyl compounds, unsaturated ester compounds and maleimide compounds.

The present invention will be described in more detail below. Alkyl acrylate rubber-based copolymer (a) used for the graft copolymer (A) used in the present invention
Is obtained by emulsion-copolymerizing 35 to 85% by weight of alkyl acrylate, 15 to 65% by weight of conjugated diene, and 0 to 20% by weight of a monomer copolymerizable therewith. The acrylic acid alkyl ester used herein refers to an acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms, a phenyl group, an acrylic acid aromatic ester having a benzene ring such as a benzyl group. Examples thereof include n-butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, etc., and one kind or two or more kinds can be used. If the amount used is 30% by weight or less, an acrylic ester compound having a functional group such as glycidyl acrylate, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, dimethylaminoethyl acrylate is used in combination with the above. It is also possible to do so.

As the conjugated diene, 1,3-butadiene, isoprene, chloroprene and the like are listed as preferable examples, and it is particularly preferable to use 1,3-butadiene. Further, as the monomer copolymerizable with the acrylic acid alkyl ester, allyl acrylate, allyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate, butylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trichloride are used. Polyfunctional monomers such as acrylate and pentaerythritol tetraacrylate, unsaturated cyan compounds such as acrylonitrile, aromatic vinyl compounds such as styrene, methacrylic acid alkyl esters such as methyl methacrylate, unsaturated carboxylic acid compounds such as methacrylic acid And the like, and one or more of them can be used. When the amount of conjugated diene used is small, one or more polyfunctional monomers are usually used.

The proportion of the alkyl acrylate in the acrylic acrylate rubber copolymer (a) is 3 in view of the performance balance of impact strength development and chemical resistance.
5 to 85% by weight. If the blending amount is less than 35% by weight, the chemical resistance of the resin composition will be poor, and if it is more than 85% by weight, the impact strength developability of the resin composition will be impaired. Further, the gel content of the rubbery copolymer (a) is 70 from the viewpoint of impact strength development.
It is necessary to exceed the weight percentage.

The average particle diameter of the rubbery copolymer (a) is
The range of 0.03 to 0.2 μm is preferable. The rubbery copolymer (a) is an acid group-containing copolymer latex (i).
Alternatively, if necessary, by adding a metal salt of oxyacid (ii) to the acid group-containing copolymer latex (i),
0.15-0.5 μm, preferably 0.2-0.4 μm
Is enlarged to the size of. By using the enlargement operation, a rubber having a large particle size can be stably obtained in a short time. It is preferable that all the rubber-like copolymers (a) become the enlarged rubber-like copolymer (a ') by the enlargement operation, but such a case is usually rare. However, even if a small amount of unenlarged particles (enlarged rubber-like copolymer (a)) remains, the physical properties of the molded product obtained from the resin composition of the present invention are at a level with almost no problem. To be

The acid group-containing copolymer latex (i) is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid, sorbic acid and p-styrenesulfonic acid. 3 to 40% by weight of one or more unsaturated acids, the number of carbon atoms of the alkyl group is 1 to 12
It can be obtained by emulsion polymerization of 97 to 35% by weight of at least one kind of the acrylic acid alkyl ester and 0 to 40% by weight of another monomer copolymerizable therewith. Of these, a copolymer of methacrylic acid and butyl acrylate is a good example.

Metal salt of oxygen acid used in the present invention (ii)
Is an alkali metal salt or alkaline earth metal salt of oxyacid mainly containing an element selected from the group of elements belonging to the second and third periods of Groups IIIA to VIA in the periodic table of elements. ,
One or more oxyacid salts selected from salts of zinc, nickel and aluminum, specifically, salts of sulfuric acid, nitric acid, phosphoric acid with potassium, sodium, magnesium, calcium, zinc and aluminum, Preferred examples include potassium sulfate, sodium sulfate, and sodium phosphate. The metal salt of oxyacid (ii) is added in the form of an aqueous solution.

The amount of the above-mentioned thickening agent added is 100 parts by weight of the acrylic acid alkyl ester rubber copolymer (a) (as a solid content), and the acid group-containing copolymer latex (i) of 0. 5 to 8 parts by weight (as solid content), and 0.5 to 5 parts by weight (as solid content) of the acid group-containing copolymer latex (i) when the metal salt of oxygen acid (ii) is used in combination.
And 0.05 to 2 parts by weight (as solid content) of an aqueous solution of a metal salt of oxyacid (ii).

The enlarged rubber-like copolymer (a ') latex thus obtained is subsequently subjected to graft polymerization. Graft polymerization is carried out by using the enlarged rubber-like copolymer (a ')
In the presence of 20 to 80 parts by weight of latex (as solid content), a monomer mixture consisting of 15 to 45% by weight of an unsaturated cyan compound and 55 to 85% by weight of an aromatic vinyl compound or 80 to 100% by weight of a methacrylic acid alkyl ester. % And 20 to 80 parts by weight of a monomer mixture consisting of 0 to 20% by weight of alkyl acrylate. The monomer used for graft polymerization is 2
If the amount is less than 0 parts by weight, coarse particles may be generated in the coagulation step after graft polymerization or the appearance of the resin composition may be impaired, which is not preferable. Further, when it is used in an amount of more than 80 parts by weight, a large amount of emulsifier is required in order to stably carry out the graft polymerization, and this causes coloring of the resin composition during thermal processing, which is not preferable.

Examples of the unsaturated cyan compound used in the graft polymerization include acrylonitrile, methacrylonitrile, ethacrylonitrile, maleonitrile and fumaronitrile, and acrylonitrile is preferably used. As the aromatic vinyl compound, styrene,
α-Methylstyrene, o-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-ethylstyrene, p-tert-butylstyrene, halogenated styrene and the like are exemplified, and styrene or α-methylstyrene is used. Is preferred.

The ratio of the unsaturated cyan compound to the aromatic vinyl compound used is 15 to 45% by weight of the unsaturated cyan compound and 55 to 85% by weight of the aromatic vinyl compound, and more preferably 20 to 35 of the unsaturated cyan compound. % By weight and 65-80% by weight of aromatics. 15 unsaturated cyanide compounds
If it is less than 5% by weight, the impact strength developability will be poor, and if it exceeds 45% by weight, the molding processability will be impaired and the heat coloring will be deteriorated.

The methacrylic acid alkyl ester used in the graft polymerization has an alkyl group of 1 to 1 carbon atoms.
8 is a methacrylic acid ester such as a chain-like or cyclic alkyl group, a phenyl group, a benzyl group, a glycidyl group, and a 2-hydroxyethyl group of 8, and one kind or two or more kinds can be used. Preferred is methyl methacrylate.

For the purpose of improving the thermal decomposability at the time of molding, the acrylic acid alkyl ester may be substituted at a ratio of 20% by weight or less of 100% by weight of the alkyl methacrylate used for graft polymerization. Methyl acrylate or ethyl acrylate is mentioned as a preferable example of the alkyl acrylate used here.

As the graft polymerization method, a known emulsion polymerization method can be adopted. It is possible to carry out a method in which the monomers are collectively charged and then polymerized, a method in which a part is charged first and the rest is dropped, and a method in which the entire amount is dropped and optionally polymerized, in one step or in two or more steps. It is also possible to change the kind and composition ratio of the monomer in each stage. The obtained graft copolymer latex is coagulated by a known method and is obtained as a graft copolymer (A) through steps such as dehydration, washing and drying.

The composite rubbery polymer (b ') latex used in the graft copolymer (B) used in the present invention is a conjugated diene rubbery polymer (b) latex 5 to 5.
It is obtained by seed polymerization of 35 to 95% by weight of a monomer mixture consisting of an alkyl acrylate and a monomer copolymerizable therewith in the presence of 65% by weight (as solid content). If the amount of the conjugated diene-based rubbery polymer (b) used is out of the above range, the impact strength manifestation or chemical resistance of the resin composition deteriorates, which is not preferable.

The conjugated diene rubbery polymer (b) used here is a copolymer comprising 50% by weight or more of a conjugated diene and 50% by weight or less of a monomer copolymerizable therewith. Examples of the conjugated diene include 1,3-butadiene, isoprene and chloroprene, and examples of the copolymerizable monomer include unsaturated cyan compounds such as acrylonitrile and aromatic vinyl compounds such as styrene. A good example of the conjugated diene rubber polymer is polybutadiene,
Acrylonitrile-butadiene copolymer rubber, styrene-
Examples thereof include butadiene copolymer rubber, and polybutadiene is most preferable. These are obtained by emulsion polymerization.

The conjugated diene rubbery polymer (b) latex is preferably large particles having an average particle size of 0.2 to 1.0 μm. Such a large particle rubber may be obtained by slowly performing seed polymerization in several steps, but is preferably obtained by an enlargement operation. That is, by adding the acid group-containing copolymer latex (i) used in the graft copolymer (A) and, if necessary, a metal salt of oxygen acid to a base rubber latex of 0.03 to 0.15 μm. It can be obtained stably and efficiently. In order to obtain a large-particle enlarged rubber as shown here, it is necessary to adjust the pH of the base rubber latex to 9 or more and use an acid group-containing copolymer latex having a high unsaturated acid content. In the bloat operation, it is rare that all the base rubbers become bloated rubbers, and usually a certain amount of unbloated base rubber remains. Therefore, the enlarged rubber has a two-dispersion particle size distribution. The preferred average particle size range of the conjugated diene rubber is 0.2 to 1.0 μm, but when focusing on only the large particle size side in the expanded rubber excluding the unexpanded base rubber, the average particle size is 0. The preferred range is from 0.4 to 1.2 μm.

The composite rubbery polymer (b ') latex is
It can be obtained by seed polymerization of a monomer mixture containing an alkyl acrylate and a monomer copolymerizable therewith in the presence of the latex of the conjugated diene rubbery polymer (b).

Examples of the alkyl acrylate include those similar to those used in the graft copolymer (A). Examples of the monomer copolymerizable with the acrylic acid alkyl ester include monofunctional monomers such as acrylonitrile, styrene, n-hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate, and crosslinking agents and grafts shown below. Examples include polyfunctional monomers such as crossing agents. Of these, it is preferable to use a cross-linking agent and a graft crossing agent in combination in terms of impact strength development.

Examples of the cross-linking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate, and examples of the graft crossing agent include allyl methacrylate. , Triallyl cyanurate, triallyl isocyanurate and the like. These crosslinking agents and graft crossing agents may be used alone or in combination of two or more.

The total amount of the cross-linking agent and the graft crossing agent used is 0.01 to 10% by weight in the monomer mixture containing alkyl acrylate as a main component, and the monofunctional monomer is 0 to 0% by weight. It is preferably 30% by weight.

A preferable example of the monomer mixture used for seed polymerization is 95 to 99.95% by weight of butyl acrylate.
And a mixture of 0.02 to 4.97% by weight of a crosslinking agent and 0.03 to 4.98% by weight of a graft crossing agent (total 1
00% by weight).

Further, the composite rubber-like polymer (b ') needs to have a gel content of more than 70% by weight in view of impact strength development.

The method of seed polymerization of the monomer mixture containing the acrylic dialkyl ester as the main component in the presence of the conjugated diene rubbery polymer (b) latex is a method in which the monomer mixture is added dropwise while being polymerized at any time. , A method in which a base rubber-like polymer is impregnated with a monomer mixture in advance, and then an initiator or the like is added to perform polymerization, and an operation of impregnating the monomer mixture and then performing polymerization are performed for each step of the monomer mixture. Examples include a method of continuously changing the composition several times. Of these, the method of preliminarily impregnating the base rubber-like polymer with the monomer mixture and then polymerizing is preferred. In addition, during seed polymerization, an emulsifier may be newly added for the purpose of improving polymerization stability, but the amount thereof is preferably as small as possible.

As a result of the seed polymerization, in some cases, the core conjugated diene rubbery polymer (b) is not seeded, and the rubbery polymer consisting only of the monomer mixture containing the alkyl acrylate as a main component is not seeded. Coalescence may occur as a by-product, but this does not hinder the intended performance of the present invention. However, when the amount thereof is large, the appearance of a molded article using the resin composition may be impaired, so the amount of the rubber-like polymer consisting only of a monomer mixture containing by-product alkyl acrylate as a main component is It is preferable to reduce it as much as possible.

The resulting composite rubbery polymer (b ') latex is subsequently subjected to graft polymerization. Graft polymerization is carried out by using a composite rubber-like polymer (b ') latex 20-8.
In the presence of 0 parts by weight (as solid content), 15-45% by weight of an unsaturated cyan compound and 55-85 of an aromatic vinyl compound.
It is carried out by graft-polymerizing 20 to 80 parts by weight of a monomer mixture consisting of 10% by weight.

The types and amounts of the unsaturated cyanide compound and the aromatic vinyl compound, which are the monomers used in the graft polymerization, and the method of the graft polymerization are the same as in the graft copolymer (A). The obtained latex is obtained as a graft copolymer (B) through steps such as coagulation, dehydration, washing and drying.

The polyorganosiloxane rubber-like polymer (c) used in the graft copolymer (C) used in the present invention comprises an organosiloxane, a crosslinking agent and, if necessary, a graft crossing agent. It is a rubbery polymer. Examples of the organosiloxane include various cyclic compounds having a 3-membered ring or more, and a 3- to 6-membered ring is preferably used. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. These may be used alone or in combination of two or more.

As the crosslinking agent, a trifunctional or tetrafunctional silane type crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane,
Tetrabutoxysilane or the like is used. Particularly, a tetrafunctional crosslinking agent is preferable, and tetraethoxysilane is particularly preferable. The amount of the cross-linking agent used is 0.1 to 30% by weight in the polyorganosiloxane rubber-like polymer (b).

Examples of the graft crossing agent include the following formula: CH ₂ = C (R ² ) -COO- (CH ₂ ) _p- SiR ¹ _n O _{(3-n) / 2} --- (I) CH ₂ = CH- ^{_{SiR 1 n O (3-n}} ) / 2 --- (II) HS- (CH 2) p -SiR 1 n O (3-n) / 2 --- (III) ( the formulas R ¹ is methyl Group, ethyl group, propyl group or phenyl group, R ² is a hydrogen atom or a methyl group, n is 0,
1 or 2, and p represents a number of 1 to 6. And a compound capable of forming a unit represented by the formula (1) is used. The (meth) acryloyloxysiloxane capable of forming the unit of the formula (I) has a high grafting efficiency and thus can form an effective graft chain, which is advantageous in terms of impact resistance expression. Methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of formula (I). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-
Examples thereof include methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, and δ-methacryloyloxybutyldiethoxymethylsilane. The amount of the graft crossing agent used is 0 to 0 in the polyorganosiloxane rubber-like polymer (c).
It is 10% by weight.

The polyorganosiloxane rubber-like polymer (c) latex has an average particle size of 0.08 to 0.6 μm.
It is preferably in the range of. Average particle size is 0.08μ
When the average particle size is less than m, the impact resistance of the molded product from the resin composition is deteriorated, and when the average particle size exceeds 0.6 μm, the impact resistance of the molded product from the resin composition is deteriorated. The appearance of the molded surface is unfavorably deteriorated.

The production of the polyorganosiloxane rubber-like polymer (c) latex is described in, for example, US Pat. No. 2,891.
The methods described in Japanese Patent No. 920, No. 3294725 and the like can be used, but an organobenzene, a cross-linking agent and, if necessary, a mixed solution of a graft crossing agent, an alkylbenzene sulfonic acid, an alkyl sulfonic acid. It is preferably produced by shear mixing with water using a homogenizer in the presence of a sulfonic acid emulsifier such as Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier of the organosiloxane and at the same time serves as a polymerization initiator. At this time, it is preferable to use a metal salt of alkylbenzene sulfonic acid, a metal salt of alkyl sulfonic acid and the like in combination because it is effective in maintaining the polymer stably during the graft polymerization.

The polyorganosiloxane rubber-like polymer (c) latex is neutralized by adding an alkaline aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate or the like, and then the following alkyl acrylate is used as a main component. It is used for seed polymerization of the monomer.

The composite rubbery polymer (c ') latex is
Monoorganic mixture 35 consisting of alkyl acrylate ester and a monomer copolymerizable therewith in the presence of 5 to 65% by weight (as solid content) of the polyorganosiloxane rubbery polymer (c) latex. Obtained by seed polymerization of 95% by weight.

The type and amount of the alkyl acrylate used in the seed polymerization and the monomer copolymerizable therewith,
The seed polymerization method is the same as that described in the description of the graft copolymer (B). Further, the composite rubber-like polymer (c ') needs to have a gel content of more than 70% by weight from the viewpoint of impact strength development.

The obtained composite rubbery polymer (c ') latex is subsequently subjected to graft polymerization. Graft polymerization is carried out by using a composite rubber-like polymer (c ') latex 20 to 8
In the presence of 0 parts by weight (as solid content), 15-45% by weight of an unsaturated cyan compound and 55-85 of an aromatic vinyl compound.
It is carried out by graft-polymerizing 20 to 80 parts by weight of a monomer mixture consisting of 10% by weight.

The types and amounts of the unsaturated cyan compound and the aromatic vinyl compound, which are the monomers used in the graft polymerization, and the method of the graft polymerization are the same as those of the graft copolymer (A). The obtained latex is obtained as a graft copolymer (C) through steps such as coagulation, dehydration, washing and drying.

The latex of the conjugated diene rubbery copolymer (d) used for the graft copolymer (II) comprises 70 to 100% by weight of the conjugated diene and 0 to 3 monomers copolymerizable therewith.
It is obtained by emulsion polymerization with 0% by weight. The conjugated diene used here is 1,3-butadiene, isoprene,
Chloroprene is mentioned as a good example, and it is preferably used in an amount of 70% by weight or more in terms of impact strength development. Also,
Examples of the monomer copolymerizable with the conjugated diene include unsaturated cyan compounds such as acrylonitrile, aromatic vinyl compounds such as styrene, methacrylic acid alkyl esters such as methyl methacrylate, unsaturated carboxylic acid compounds such as methacrylic acid, and the like. Examples thereof include monomers, and one kind or two or more kinds can be used. Preferable examples of the conjugated diene rubber polymer (d) include polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber.

The average particle size of this conjugated diene rubbery copolymer (d) latex is preferably in the range of 0.03 to 0.2 μm. The conjugated diene rubbery copolymer (d) latex is the acid group-containing copolymer latex (i) of the type and amount described in the description of the graft copolymer (A) or, if necessary, a metal salt of oxygen acid. Addition of (ii) up to 0.15-0.5 μm, preferably 0.2-0.
Enlarged to 4 μm. By this bloat operation,
An enlarged rubber-like copolymer (d ') latex having a large particle size suitable for impact strength development can be stably obtained in a short time.

The enlarged rubber-like copolymer (d ') latex is subsequently subjected to graft polymerization. Graft polymerization is carried out by using an enlarged rubber-like copolymer (d ') latex 20 to 8
It is carried out by graft-polymerizing 20 to 80 parts by weight of one or more kinds of monomers selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds in the presence of 0 parts by weight (as solid content). .

Preferred examples of the monomer used in the graft polymerization include those described in the description of the graft copolymer (A). As for the graft polymerization method, a known emulsion polymerization method can be adopted as in the case of the graft copolymer (A). The obtained graft copolymer latex is coagulated by a known method, and is subjected to steps such as dehydration, washing and drying to obtain a graft copolymer (II).

The hard thermoplastic resin (II
I) is obtained by copolymerizing two or more kinds of monomers selected from unsaturated cyan compounds, aromatic vinyl compounds, unsaturated ester compounds and maleimide compounds.

Here, examples of the unsaturated cyan compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, maleonitrile and fumaronitrile, and of these, acrylonitrile is a preferable example.
Aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-ethylstyrene, p-tert-butylstyrene, 2,4.
-Dimethyl styrene, halogenated styrene, etc. are exemplified, and among these, styrene and α-methyl styrene are preferable. Unsaturated ester compounds include methyl methacrylate, ethyl methacrylate, butyl methacrylate, phenyl methacrylate, benzyl methacrylate,
Examples thereof include methacrylic acid ester compounds such as glycidyl methacrylate and 2-hydroxyethyl methacrylate, and of these, methyl methacrylate is a preferable example. Maleimide compound means maleimide, carbon number 1
N-alkylmaleimides substituted with an alkyl group of 1 to 12, N-phenylmaleimide, and an alkyl group having 1 to 6 carbon atoms, a halogen, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and a carbosyl group in the benzene nucleus thereof. , Nitro group,
Examples thereof include N-phenylmaleimide derivatives having one or more substituents selected from the group consisting of amino groups and cyano groups. Of these, N-phenylmaleimide and N-
Cyclohexylmaleimide is a good example.

The hard thermoplastic resin (III) is composed of two or more kinds of the above-exemplified monomers, but preferably one or more kinds of unsaturated cyan compounds. If specifically illustrated, acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, acrylonitrile-styrene-methyl methacrylate copolymer,
Acrylonitrile-styrene-N-phenylmaleimide copolymer, acrylonitrile-α-methylstyrene-N
-Phenylmaleimide copolymer etc. are mentioned. The hard thermoplastic resin (III) may be used alone or in combination of two or more. The method for producing the hard thermoplastic resin (III) is not particularly limited, but it is preferable to adopt a method capable of maximizing the performance of the resin.

The following are preferable for more specific examples. A copolymer consisting of 20 to 45% by weight of acrylonitrile, preferably 25 to 40% by weight, and 55 to 80% by weight of styrene or α-methylstyrene, more preferably 60 to 75% by weight. Consists of 10-40% by weight of acrylonitrile, 30-50% by weight of styrene and 30-50% by weight of methyl methacrylate (total 100% by weight)
Copolymer. A copolymer comprising 10 to 40% by weight of acrylonitrile, 40 to 80% by weight of styrene, and 5 to 40% by weight of N-phenylmaleimide or N-cyclohexylmaleimide.

The hard thermoplastic resin (III) may be used alone or in combination of two or more kinds. There is no particular limitation on the method for producing the hard thermoplastic resin (III), but it is preferable to adopt the method capable of maximizing the performance of the resin.

The thermoplastic resin composition of the present invention comprises at least one graft copolymer (a) selected from the group consisting of graft copolymer (A), graft copolymer (B) and graft copolymer (C). It is obtained by using I) and the graft copolymer (II) as essential components and, if necessary, incorporating a hard thermoplastic resin (III). The graft copolymer (I) is essential for developing the chemical resistance of the resin composition. Further, the graft copolymer (II) is essential in terms of impact resistance manifestation of the resin composition.

The blending ratio of the graft copolymer (I), the graft copolymer (II) and the hard thermoplastic resin (III) is such that the proportion of the rubber-like polymer in the thermoplastic resin composition is in a preferable range. To be decided. That is, the proportion of the rubber-like polymer in 100% by weight of the thermoplastic resin composition is 15 to 30% by weight, more preferably 20 to 28.
% By weight, and the proportion of the alkyl acrylate unit constituting the rubbery polymer in 100% by weight of the rubbery polymer is 30 to 85% by weight.

When the proportion of the rubber-like polymer in the thermoplastic resin composition is less than 15% by weight, the impact strength manifestation becomes poor, and when it exceeds 30% by weight, the surface hardness and rigidity are low. It is not preferable because the use is limited due to the decrease of the value. In addition, 30% by weight of alkyl acrylate unit forming a rubber-like polymer
If it is less than 85, it is not preferable because it has poor chemical resistance.
When the content exceeds the weight%, it becomes difficult to obtain excellent impact strength manifestation, which is not preferable.

Even from the resin composition comprising the graft copolymer (I) alone or the graft copolymer (I) and the hard thermoplastic resin (III), the rubber-like polymer occupying the specific resin composition according to the present invention can be obtained. It is possible to obtain a thermoplastic resin composition satisfying the combined ratio and the ratio of alkyl acrylate ester units in the rubber-like polymer. However,
Although these thermoplastic resin compositions have excellent chemical resistance, their impact resistance manifestation is slightly inferior and their use is limited. In order to obtain excellent impact resistance manifestation, it is necessary to increase the amount of the rubber-like polymer used, which is not preferable in terms of surface hardness and rigidity as described above in detail. Therefore, in order to obtain the excellent impact resistance manifestation, in order to obtain the effect of blending the graft copolymer (II) sufficiently, it is preferable to blend 5 parts by weight or more of the graft copolymer (II). .

In order to blend the graft copolymer (I), the graft copolymer (II) and the hard thermoplastic resin (III), they are usually mixed by a V-type blender, a Henschel mixer, etc. Various stabilizers, lubricants, plasticizers, release agents, dyes, pigments, inorganic fillers, metal fine particles, antistatic agents and the like can be added depending on the type. These mixtures are melt-kneaded using a mixing roll, a screw type extruder or the like, and then pelletized by a pelletizer.

[0055]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, "part" in the following Examples and Comparative Examples represents parts by weight. Further, the average particle size of the rubber-like polymer latex was measured from an image photographed with a transmission electron microscope after being immobilized with osmium tetroxide or the like. The gel content of the rubbery polymer was determined as follows. The dried rubber-like polymer was immersed in toluene at 30 ° C. for 24 hours, and the gel residue obtained by drying the residue on the 200-mesh wire mesh was dried. I asked.

Synthesis of alkyl acrylate rubber copolymer (a-1) n-butyl acrylate 50 parts 1,3-butadiene 50 parts diisopropylbenzene hydroperoxide 0.2 parts tert-dodecyl mercaptan 0.4 parts Potassium oleate 1 part Sodium N-lauroyl sarcosinate 1 part Rongalit 0.5 part Distilled water 195 parts For the substances other than 1,3-butadiene in the above composition, the oxygen contained therein is replaced with nitrogen. , So that the reaction was virtually not hindered. After that, add all substances to 5
A 0 liter autoclave was charged and the temperature was raised to 55 ° C with vigorous stirring. Add the following mixture to this,
Polymerization was carried out at 55 ° C. for 8 hours. As a result, an acrylic acid alkyl ester rubbery copolymer (a-1) latex having a monomer conversion rate of 99% and a particle size of 0.07 μm was obtained. Further, the gel content was determined to be 82% by weight. Ethylenediaminetetraacetic acid disodium salt dihydrate 0.012 parts Ferrous sulfate heptahydrate 0.004 parts Distilled water 5 parts

Synthesis of alkyl acrylate rubber copolymer (a-2) n-butyl acrylate 99 parts allyl methacrylate 0.8 parts divinylbenzene 0.2 parts diisopropylbenzene hydroperoxide 0.02 parts potassium oleate 1.2 parts Sodium N-lauroyl sarcosinate 0.8 parts Rongalit 0.4 parts Distilled water 198 parts The above composition was charged into a 50 liter polymerization vessel, and oxygen in the vessel was completely removed with nitrogen, and then up to 50 ° C. The temperature was raised. The following mixture was added thereto, and polymerization was carried out at 50 ° C. for 5 hours. As a result, an acrylic acid alkyl ester rubbery copolymer (a-2) latex having a monomer conversion rate of 98%, a particle size of 0.14 μm and a gel content of 78% by weight was obtained. Ethylenediaminetetraacetic acid disodium salt dihydrate 0.000015 parts Ferrous sulfate heptahydrate 0.000005 parts Distilled water 2 parts

Synthesis of conjugated diene rubbery copolymer (d-1) 1,3-butadiene 100 parts diisopropylbenzene hydroperoxide 0.2 part tert-dodecyl mercaptan 0.5 part potassium oleate 1 part disproportionation Potassium rosinate 1 part Dextrose 0.3 part Anhydrous sodium sulfate 0.18 part Sodium hydroxide 0.02 part Distilled water 195 parts and sodium pyrophosphate / 10-hydrate 0.5 part Ferrous sulfate heptahydrate 0. 005 parts Distilled water 5 parts The above composition was polymerized for 9 hours by the same operation as in the synthesis of the alkyl acrylate rubber polymer (a-1). As a result, a conjugated diene rubbery copolymer (d-1) latex having a monomer conversion rate of 97%, a particle size of 0.08 μm and a gel content of 80% by weight was obtained.

Synthesis of acid group-containing copolymer (i-1) latex 2.5 parts potassium oleate 2.5 parts potassium dioctylsulfosuccinate 2.5 parts ethylenediaminetetraacetic acid disodium dihydrate 0.012 parts ferrous sulfate 7-hydrate salt 0.004 parts Rongalit 0.5 parts distilled water 200 parts The above composition was charged into a 5 liter glass separable flask, and oxygen in the system was replaced with nitrogen while stirring, and then the temperature was raised to 70 ° C. . The following monomer mixture, which had been subjected to nitrogen substitution, was added dropwise to the mixture over 4 hours for polymerization. n-Butyl acrylate 85 parts Methacrylic acid 15 parts Cumene hydroperoxide 0.5 parts After that, by holding at 70 ° C. for 1 hour, an acid group-containing copolymer (i-1) latex having a monomer conversion of 97% was obtained. Was obtained.

Synthesis of acid group-containing copolymer (i-2) Synthesis of acid group-containing copolymer (i-1) latex except that the composition of the monomer mixture to be dropped is changed as follows. Polymerization was performed by the same operation. As a result, an acid group-containing copolymer (i-2) latex having a monomer conversion rate of 96% was obtained. n-Butyl acrylate 80 parts Methacrylic acid 20 parts Cumene hydroperoxide 0.5 parts

50 parts of synthetic rubber-like copolymer (a-1) latex of graft copolymer (A-1) (as solid content) was charged into a 20 liter separable flask,
After adding 0.4 parts of a 10% aqueous solution of sodium sulfate in solid content with stirring, the acid group-containing copolymer (i-1) is further added.
The latex was added in an amount of 1.3 parts by solid content, and the mixture was kept as it was for 30 minutes while stirring, and then 95 parts of distilled water was added.
As a result, an enlarged rubber-like copolymer (a'-1) latex having an average particle diameter of 0.27 µm was obtained. Sodium N-lauroyl sarcosinate 1.25 parts Ethylenediaminetetraacetic acid disodium dihydrate 0.003 parts Ferrous sulfate heptahydrate 0.001 part Rongalit 0.5 parts Enlarged rubbery copolymer (a ' -1) The above composition was added to the latex, and the temperature was raised to 75 ° C with stirring. Graft polymerization was carried out by dropwise adding the following monomer mixture over 120 minutes. Acrylonitrile 15 parts Styrene 35 parts tert-Butyl hydroperoxide 0.3 parts n-Octyl mercaptan 0.1 parts After the dropping of the monomer mixture, the graft copolymer latex was obtained by further holding for 1 hour. The graft copolymer latex was put into a dilute sulfuric acid aqueous solution to coagulate, and then dehydrated, washed, and dried to obtain a graft copolymer (A-1).

Synthesis of Graft Copolymer (A-2) Up to the point of obtaining a bloated rubbery copolymer, the same procedure as in the synthesis of graft copolymer (A-1) was carried out. Enlarged rubbery copolymer (a'-1) latex (as solid content) 60 parts Sodium N-lauroyl sarcosinate 0.75 parts Ethylenediaminetetraacetic acid disodium dihydrate 0.0015 parts Ferrous sulfate-7 Water salt 0.0005 parts Rongalit 0.4 parts The above composition was charged into a 20 liter separable flask, heated to 75 ° C. with stirring, and then the following monomer mixture was added dropwise over 90 minutes. Graft polymerization was performed. Methyl methacrylate 36 parts Ethyl acrylate 4 parts Cumene hydroperoxide 0.15 parts n-octyl mercaptan 0.05 parts After the dropping of the monomer mixture, the graft copolymer latex was obtained by further holding for 1 hour. The graft copolymer latex was put into a dilute sulfuric acid aqueous solution to coagulate, and then dehydrated, washed and dried to obtain a graft copolymer (A-2).

Synthesis of Graft Copolymer (A-3) The rubber-like copolymer (a-2) is used as the rubber-like polymer, and the acid group-containing copolymer is used as the bloating agent used in the bloat-up operation. (I-1) Graft copolymer (A) except that acid group-containing copolymer (i-2) was used instead of latex.
-1) is carried out in the same manner as in the synthesis of the graft copolymer (A-
3) was obtained. At this time, the enlarged rubber-like copolymer (a'-
The average particle diameter of 2) was 0.31 μm.

Synthesis of composite rubbery polymer (b'-1) The rubbery copolymer (d) was placed in a 20 liter separable flask.
-1) Charge 20 parts of latex in solid content. To this, 0.5 part of the acid group-containing copolymer (i-2) latex was added as a solid content while stirring, and the mixture was kept for 30 minutes as it was, and then 160 parts of distilled water was added to carry out the enlargement operation. .
As a result, an enlarged rubber-like copolymer having an average particle diameter of 0.37 μm was obtained. n-Butyl acrylate 79.55 parts Allyl methacrylate 0.3 parts Ethylene glycol dimethacrylate 0.25 parts tert-Butyl hydroperoxide 0.2 parts To this, after adding the above monomer mixture and stirring sufficiently,
0.5 part of sodium N-lauroyl sarcosinate is dissolved, and the system is replaced with nitrogen to remove oxygen. Internal temperature 45
At the time when the temperature was raised to ° C, the following composition was added. Rongalit 0.5 parts Ferrous sulfate heptahydrate 0.0003 parts Ethylenediaminetetraacetic acid disodium dihydrate 0.0009 parts Distilled water 10 parts As a result, polymerization started and the internal temperature rose to about 70 ° C.
Then, the composite rubber-like polymer (b′-1) latex was obtained by holding the mixture at 75 ° C. for 90 minutes while stirring. The gel content was found to be 84% by weight.

Synthesis of composite rubbery polymer (b'-2) In the synthesis of the composite rubbery polymer (b'-1), 0.2 part of n-octyl mercaptan was added to the monomer mixture used for seed polymerization. Compound rubber-like polymer (b'-
It was synthesized in the same manner as 1). The gel content of the obtained composite rubbery polymer (b'-2) was 47% by weight.

Synthesis of graft copolymer (B-1) Composite rubbery polymer (b'-1) latex (as solid content) 50 parts Sodium N-lauroyl sarcosinate 1.2 parts Rongalit 0.4 parts Sulfuric acid No. Monoiron / heptahydrate 0.001 part Ethylenediaminetetraacetic acid disodium / dihydrate 0.003 part Distilled water 100 parts The above composition was charged in a 20 liter separable flask and heated to 75 ° C with stirring. . Graft polymerization was carried out by dropwise adding the following monomer mixture over 120 minutes. Acrylonitrile 15 parts Styrene 35 parts tert-Butyl hydroperoxide 0.3 parts n-Octyl mercaptan 0.1 parts After completion of dropping the monomer mixture, the mixture is kept for 1 hour while stirring to give a graft copolymer latex. Was obtained. The graft copolymer latex was obtained as a powdery graft copolymer (B-1) by adding it to a dilute sulfuric acid aqueous solution to coagulate it, followed by dehydration, washing and drying.

Synthesis of Graft Copolymer (B-2) In the synthesis of graft copolymer (B-1), composite rubber polymer (b'-) is used instead of composite rubber polymer (b'-1). 2) was used except that the graft copolymer (B
In the same manner as in the synthesis of -1), the graft copolymer (B-
2) was obtained.

Synthesis of composite rubbery polymer (c'-1) Dodecylbenzene sulfonic acid 1 part Sodium docecilbenzene sulfonate 1 part Distilled water 200 parts To the above composition, a siloxane mixture having the following composition is added and a homomixer is used. After premixing at 10,000 rpm with a homogenizer, the mixture was emulsified and dispersed at a pressure of 300 kg / cm ^{2 with} a homogenizer to obtain an organosiloxane latex. Tetraethoxysilane 1.0 part γ-methacryloyloxypropyldimethoxymethylsilane 0.25 part Octamethylcyclotetrasiloxane 48.75 parts This mixed solution was transferred to a 20 liter separable flask and heated at 80 ° C. for 5 hours while stirring. After that, the mixture was allowed to stand at 20 ° C. for 48 hours, and then the pH of this latex was neutralized to 7.5 with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane rubber-like polymer (c-1) latex. The average particle diameter was 0.16 μm. To this, 70 parts of distilled water was added, and the following monomer mixture was added to the mixture while stirring and mixed sufficiently. n-Butyl acrylate 48.6 parts Allyl methacrylate 1.05 parts Ethylene glycol dimethacrylate 0.35 parts tert-Butyl hydroperoxide 0.3 parts After replacing the system with nitrogen to remove oxygen, the internal temperature is 50 ° C. The temperature was raised to and the polymerization was started by adding the following mixture. Rongalit 0.3 part Ferrous sulfate heptahydrate 0.002 part Ethylenediaminetetraacetic acid disodium dihydrate 0.006 part Distilled water 10 parts As a result, the internal temperature was raised to about 65 ° C. Then 70
The composite rubbery polymer (c'-2) latex was obtained by holding it at 2 ° C for 2 hours. Gel content is 95% by weight
Met.

Synthesis of composite rubber-like polymer (c'-2) In the synthesis of composite rubber-like polymer (c'-1), a monomer mixture for seed polymerization was added to n-butyl acrylate 49.7 parts allyl methacrylate. 0.35 parts tert-butyl hydroperoxide 0.3 parts n-octyl mercaptan 0.3 parts In the same manner except that 0.3 parts was used.
2) was obtained. The gel content was 63% by weight.

Synthesis of graft copolymer (C-1) Composite rubber-like polymer (c'-1) latex (as solid content) 60 parts Sodium dodecylbenzenesulfonate 0.3 parts Distilled water 80 parts , 20 liter separable flask, and heated to 70 ° C. with stirring. The following monomer mixture was added dropwise to this over 60 minutes for graft polymerization. Acrylonitrile 12 parts Styrene 28 parts Cumene hydroperoxide 0.2 part tert-Dodecyl mercaptan 0.1 part After the dropwise addition, the graft copolymer latex was obtained by holding for 2 hours with stirring. This graft copolymer latex was put into a calcium chloride aqueous solution to coagulate, dehydrated, washed, and dried to obtain a powdered graft copolymer (C-1).

Synthesis of Graft Copolymer (C-2) In the synthesis of graft copolymer (C-1), composite rubbery polymer (c'- is used instead of composite rubbery polymer (c'-1). A graft copolymer (C-2) was obtained in the same manner except that 2) was used.

Synthesis of Graft Copolymer (D-1) Conjugated Diene Rubber Copolymer (d-1) Latex 60
Parts (as solid content) were placed in a 20 liter separable flask, and the acid group-containing copolymer (i-1) was stirred with stirring.
The latex was added in an amount of 1.2 parts by solid content, and the mixture was kept for 30 minutes while stirring, and then 80 parts of distilled water was added. As a result, an enlarged rubber-like copolymer (d'-1) latex having an average particle diameter of 0.28 μm was obtained. Disproportionated potassium rosinate 0.4 parts Sodium pyrophosphate decahydrate 0.02 parts Ferrous sulfate heptahydrate 0.005 parts Dextrose 0.4 parts Sodium hydroxide 0.02 parts Enlarged rubbery co- The above composition was added to the polymer (d′-1) latex, and the temperature was raised to 60 ° C. with stirring. Graft polymerization was carried out by dropwise adding the following monomer mixture over 120 minutes. Acrylonitrile 12 parts Styrene 28 parts Cumene hydroperoxide 0.2 parts tert-Dodecyl mercaptan 0.4 parts After completion of dropping the monomer mixture, the mixture was kept for 1 hour to obtain a graft copolymer latex. The graft copolymer latex was put into a dilute sulfuric acid aqueous solution to coagulate, and then dehydrated, washed and dried to obtain a graft copolymer (D-1).

Synthesis of hard thermoplastic resin (III-1) Acrylonitrile 30 parts Styrene 70 parts Azobisisobutyronitrile 0.15 parts tert-dodecyl mercaptan 0.4 parts Calcium phosphate 0.5 parts Distilled water 150 parts The above composition Was charged into a 100 liter autoclave and vigorously stirred. After confirming the dispersion in the system, the temperature was raised to 75 ° C. and polymerization was performed for 3 hours. Then, it heated up to 110 degreeC and aged for 30 minutes. By cooling, dehydration, washing and drying after cooling, the powdery hard thermoplastic resin (III-
1) was obtained.

Synthesis of hard thermoplastic resin (III-2) acrylonitrile 20 parts styrene 40 parts methyl methacrylate 40 parts azobisisobutyronitrile 0.15 parts tert-dodecyl mercaptan 0.2 parts calcium phosphate 0.5 parts distilled water 150 Parts A powdery hard thermoplastic resin (III-2) was obtained by polymerizing the above composition by the same operation as in the synthesis of the hard thermoplastic resin (III-1).

Synthesis of hard thermoplastic resin (III-3) potassium oleate 3 parts dextrose 0.5 part ferrous sulfate heptahydrate 0.005 part sodium pyrophosphate decahydrate 0.5 part anhydrous sodium sulfate 0.15 parts Distilled water 200 parts Acrylonitrile 10 parts α-Methylstyrene 70 parts tert-Dodecyl mercaptan 0.1 parts The above composition was charged in a glass-lined 100 liter polymerization kettle and heated to 60 ° C. with stirring. . After adding 0.5 parts of cumene hydroperoxide,
20 parts of acrylonitrile was added dropwise over 120 minutes for polymerization. During this time, the internal temperature gradually rises to about 80
It became ℃. Subsequently, the copolymer latex was obtained by keeping it at 80 ° C. for 2 hours. This latex was put into an aqueous magnesium sulfate solution to coagulate, dehydrated, washed, and dried to obtain a powdery hard thermoplastic resin (III-3).

Synthesis of Hard Thermoplastic Resin (III-4) Styrene 40 parts Ethylmethylketone 10 parts Glass-lined 50 liter complete mixing type polymerization kettle was decompressed with a vacuum pump, and then nitrogen gas was introduced into the equipment. After repeating the operation of introducing into the reactor several times, the above mixture was charged into the vessel under a nitrogen atmosphere. This was heated to 100 ° C., and the following mixture was added dropwise into the vessel over 60 minutes to carry out solution polymerization. Acrylonitrile 20 parts N-phenylmaleimide 10 parts 1,1-dibutylperoxy-3,3,5-trimethylcyclohexane 0.07 parts Ethylmethylketone 20 parts After completion of dropping supply, aging is continued for 1 hour at 100 ° C. to obtain N. -Significantly reduced the residual amount of phenylmaleimide.
Then, after the polymerization inhibitor was charged and rapidly cooled, the polymerization reaction product was quantitatively supplied to the devolatilizing extruder using a gear pump.
After removing residual monomers and organic solvents with a devolatilizing extruder, the copolymer was extruded in a strand form. The pelletized hard thermoplastic resin (III-4) was obtained by treating this with a pelletizer.

Production of Thermoplastic Resin Composition Predetermined amounts of the graft copolymer (I), the graft copolymer (II) and the hard thermoplastic resin (III) were put into a Henschel mixer together with the following substances and blended. ADEKA STAB Mark AO-20 (manufactured by Asahi Denka) 0.3 parts ADEKA STAB Mark AO-412S (manufactured by Asahi Denka) 0.3 parts Ethylene bis-stearamide 1 part Magnesium stearate 0.3 parts Silicon Oil SH200 (Toray Dow Corning Silicone) Manufacture) 0.03 parts The above mixture was melt-kneaded at 220 ° C to 260 ° C using a screw extruder, and then pelletized by a pelletizer. The pellets were molded into various test pieces using an injection molding machine or a press molding machine.

The resin composition thus obtained was evaluated by the following methods. (1) Izod impact strength (Iz): ASTM D-2
It was measured by 56 (unit: kg · cm / cm). (2) Rockwell hardness (R): ASTM D-785
(R scale). (3) Vicat softening temperature (VST): ISO R-30
6 (unit: ° C). (4) Chemical resistance: A test piece of 35 × 120 mm was cut out from a 2 mm thick press-molded plate of the resin composition, and the major axis was 120 m.
It is attached to a 1/4 elliptical jig with a diameter of m and a short diameter of 40 mm. After the chemical was applied to the surface of the test piece, it was covered with a polyethylene film and exposed to the chemical at 25 ° C. for 4 hours. For low boiling point chemicals, the jig was placed in a desiccator with an opening / closing cock and exposed to the chemicals at 25 ° C. for 24 hours while being filled with the chemical vapor. After the exposure, the surface condition of the test piece was observed, and the maximum stress-strain value at which cracks did not occur was used as an index of chemical resistance. The following chemicals were used.・ 1,1-Dichloro-1-fluoroethane ・ Brake oil (Toyota 2400G) ・ Wax remover (Yushiro Kagaku ST-7) ・ Salad oil (Nisshin Oil) ・ Dioctyl phthalate

[0079]

[Table 1]

Description of Tables It can be seen that Examples 1 to 4 according to the present invention can provide thermoplastic resin compositions having excellent impact strength development and chemical resistance. On the other hand, in Comparative Example 1, the amount of the alkyl acrylate unit in the rubber-like polymer is smaller than that of the present invention, so that the chemical resistance is poor. In Comparative Example 2, the rubber-like polymer occupied in the thermoplastic resin composition was larger than that of the present invention, so that the Rockwell hardness was less than 80 and the surface was soft. On the other hand, in Comparative Example 3, the impact strength is poor because the rubber-like polymer is small. In Comparative Example 4, although the amount of the rubber-like polymer and the amount of the alkyl acrylate ester unit are both in accordance with the present invention, a general AAS (the rubber-like polymer is a simple polybutyl acrylate rubber) is used as the graft copolymer (I). Since it is used, the impact strength development is poor. In Comparative Examples 5 and 6, since the graft copolymer (I) uses a composite rubber-like polymer having a low gel content,
Poor impact strength development. Heat-resistant hard thermoplastic resin (II
Even when I) is used, the thermoplastic resin composition using the graft copolymer (I) of the present invention has a higher impact strength developing property than Comparative Example 7 using the AAS resin. I understand.

[0081]

EFFECT OF THE INVENTION According to the present invention, a graft copolymer obtained by graft-polymerizing an acrylic acid alkyl ester rubber, a graft copolymer obtained by graft-polymerizing a conjugated diene rubber, and a hard thermoplastic resin are mixed at an optimum ratio. It is a plastic resin composition and has extremely excellent chemical resistance and impact resistance. Therefore, the thermoplastic resin composition of the present invention is extremely useful as a component for home electric appliances, vehicles, etc. that come into contact with urethane foaming agents, various oils, detergents and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08L 35/00 LJW 51/00 LKS 51/08 LLT

Claims (1)

[Claims] 1. (I) The following graft copolymer (A),
At least one graft copolymer (I) selected from the group consisting of (B) and (C). (A) Alkyl acid alkyl ester 35 to 85% by weight, conjugated diene and / or acrylic acid alkyl ester copolymerizable monomer 15 to 65% by weight, and copolymerizable monomer 0 to 20% by weight The gel content obtained by emulsion polymerization of and exceeds 70% by weight, and the average particle size is 0.03 to
0.2 μm rubber-like copolymer (a) latex with acid group-containing copolymer latex (i) or, if necessary, the acid group-containing copolymer latex (i) with metal salt of oxygen acid (ii) The average particle diameter obtained by using
In the presence of 20 to 80 parts by weight (as a solid content) of the enlarged rubber-like copolymer (a ') latex of 5 to 0.5 μm, 15 to 45% by weight of the unsaturated cyanide compound and 55 to 85 of the aromatic vinyl compound. Graft copolymer (20% to 80% by weight of a monomer mixture consisting of 80% by weight of a methacrylic acid alkyl ester and 0 to 20% by weight of an alkyl acrylate ester). A) (B) Conjugated diene rubbery polymer (b) Latex 5
In the presence of 65% by weight (as solid content), 35 to 95% by weight of a monomer mixture consisting of an acrylic acid alkyl ester and a monomer copolymerizable therewith is seed-polymerized to obtain a gel content of 20-80 parts by weight of composite rubber-like polymer (b ') latex exceeding 70% by weight (as solid content)
Graft copolymer (B) (C) obtained by graft-polymerizing 20 to 80 parts by weight of a monomer mixture consisting of 15 to 45% by weight of an unsaturated cyan compound and 55 to 85% by weight of an aromatic vinyl compound in the presence of ) Polyorganosiloxane rubber-like polymer (b-
2) Seed-polymerized in the presence of 5 to 65% by weight (as solid content) of a latex, 35 to 95% by weight of a monomer mixture consisting of an alkyl acrylate and a monomer copolymerizable therewith. The unsaturated cyanide compound 15 in the presence of 20 to 80 parts by weight (as solid content) of the composite rubbery polymer (c ') latex having a gel content of more than 70% by weight.
Graft copolymer (C) (II) conjugated diene 70-100% by weight obtained by graft-polymerizing 20-80 parts by weight of a monomer mixture consisting of -45% by weight and aromatic vinyl compound 55-85% by weight. To the conjugated diene rubbery copolymer (d) latex having an average particle size of 0.03 to 0.2 μm, which is obtained by emulsion polymerization of 0 to 30% by weight of a copolymerizable monomer. Enlarged rubber-like copolymer (d ') latex 30 obtained by adding polymer latex (i) or, if necessary, said acid group-containing copolymer latex together with metal salt (ii) of oxygen acid ~
In the presence of 70 parts by weight (as solid content), 15 to 45% by weight of an unsaturated cyan compound and 55 to 8 of an aromatic vinyl compound.
Graft copolymer (II) obtained by graft-polymerizing a monomer mixture of 5% by weight. (III) A hard thermoplastic resin (III) obtained by copolymerizing two or more kinds of monomers selected from unsaturated cyan compounds, aromatic vinyl compounds, unsaturated ester compounds and maleimide compounds. The above graft copolymer (I) and the graft copolymer (I
A thermoplastic resin composition comprising I) as an essential component, and a graft copolymer (I), a graft copolymer (II) and a hard thermoplastic resin (III) blended therein, said thermoplastic resin composition The proportion of the rubbery copolymer in 100% by weight is 15 to 30% by weight, and the proportion of the alkyl acrylate unit forming the rubbery polymer is 30 to 100% by weight with respect to 100% by weight of the rubbery polymer. 85% by weight of a thermoplastic resin composition.