JPS63235349A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain the title resin composition excellent in heat resistance, weathering resistance, chemical resistance, mechanical properties and moldability, comprising a specified copolymer and a specified copolymer composition. CONSTITUTION:This resin composition is formed from 1-95wt.% component I and 99-5wt.% component II. [I]: A copolymer obtained by polymerizing a monomer A such as a maleimide monomer A-1 or an unsaturated carboxylic acid monomer A-2 with a monomer B such as an aromatic vinyl monomer B-1, an unsaturated nitrile monomer B-2 or an unsaturated carboxylic ester monomer B-3 and a monomer C copolymerizable therewith in the presence or absence of a thermoplastic resin and/or a rubbery polymer (hereinafter referred to as X) and having a composition (except component X) represented by the formulas I and II. [II]: A copolymer composition which comprises a copolymer obtained by polymerizing B-1, B-3 and monomer D copolymerizable therewith in the presence or absence of component X and having an average composition (except component X) of formula III and IV.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention has excellent heat resistance, weather resistance, chemical resistance, mechanical properties, and moldability, and is compatible with various non-polar and polar materials. The present invention also relates to a resin composition having good affinity.

<Prior Art> Styrene resins or methyl methacrylate resins have excellent moldability and appearance, and are widely used as vehicle parts, electrical parts, office equipment parts, and the like. However, these resins have the disadvantage of poor heat resistance, and in recent years, in order to improve their heat resistance, resins have been developed that incorporate maleimide monomers, maleic anhydride, methacrylic acid, etc. as heat resistance imparting ingredients. It is being actively progressed.

Furthermore, for the purpose of improving the impact strength of resins incorporating these heat resistance imparting components, for example, compositions of styrene-maleimide copolymers and polycarbonate (JP-A-53-1999) have been developed.
129245), styrene and/or methyl methacrylate-acrylonitrile-maleimide copolymer,
Compositions consisting of A B S m BM and polycarbonate (Japanese Patent Publication No. 61-50976), Compositions of styrene-maleimide copolymers, styrene-acrylonitrile-maleimide copolymers, and polyphenylene ether (Japanese Patent Publication No. 61-174249) ) or compositions of these with impact-resistant polystyrene or styrene-butadiene block copolymers (Japanese Patent Publication No. 60-58257) have been proposed.

<The problem that the invention is trying to solve> However,
Resins made by introducing maleimide monomers such as those mentioned above have very high polarity. Or it has poor compatibility with materials with low polarity. This tendency becomes more pronounced as the content of heat resistance-imparting components such as maleimide monomers in the resin increases.As a result, it is difficult to obtain a resin composition that has the characteristics originally possessed by each resin. The composition has the disadvantage of poor weather resistance.

The present inventors solved the above-mentioned problems and achieved excellent heat resistance, weather resistance, chemical resistance, mechanical properties, and moldability, as well as compatibility or affinity with various non-polar and polar materials. As a result of intensive studies to obtain a very good resin composition, a copolymer composition (1) consisting of a specific heat resistance imparting component and composition and a copolymer composition [II] having a specific composition distribution was found. A resin composition was discovered, leading to the present invention.

That is, the present invention provides a method for preparing a maleimide monomer (A-1) and an unsaturated carboxylic acid monomer (A-2) in the presence or absence of a thermoplastic resin and/or a rubbery polymer.
Any one or two monomers (A), an aromatic vinyl monomer (B-1), an unsaturated nidolyl monomer (
B-2) and one or more monomers (B) selected from unsaturated carboxylic acid ester type II polymers (B-3) and monomers copolymerizable therewith (C ), the composition (excluding thermoplastic resin and rubbery polymer) of formula (1) and (
Copolymer represented by 2) [■] 1 to 95% by weight and aromatic vinyl monomer (B-1) and non-alcoholic monomer (B-1) in the presence or absence of a thermoplastic resin and/or rubbery polymer. A composition consisting of a copolymer obtained by polymerizing a saturated carboxylic acid ester monomer ([3-3) and a monomer (D) copolymerizable with these, the average composition of which is (
Excludes thermoplastics and rubbery polymers. ) is the formula (3
) and (4), and the content of the unsaturated carboxylic acid ester monomer (B-3) exceeds 10% by weight. ■3 to 95% by weight. and a copolymer composition (II) consisting of 97 to 5% by weight of a copolymer (II) of 99 to 5% by weight or less of 10% by weight or less.

Q copolymer (1) (A) + (B) + (C) +1
)(A) + (B) + (C)
(
210 copolymer composition [II] (B-1)+ (B-3)+ (D) -3 to 80% by weight (3) (B-1)+ (B-3)+ (D) =■ ~50% by weight (4) The present invention will be explained in detail below.

Copolymer (1) Examples of the thermoplastic resin and/or rubber polymer that can constitute the copolymer (1) of the present invention include the following. Polyethylene, polypropylene, polythene-1, polyethylene-ethylene-1 copolymer, propylene-ethylene-1 copolymer, propylene-ethylene block copolymer,
゛#哄4髫禰ζEthylene-propylene rubber, maleic anhydride grafted polyolefin, N-phenylmaleimide grafted polyolefin, chlorinated polyolefin, ethylene-vinyl acetate copolymer,
Ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylic acid and its metal salt copolymer, ethylene-
(meth)acrylic acid ester copolymers such as methyl (meth)acrylate, ethyl, propyl, butyl, glycidyl, and dimethylaminoethyl; ethylene-(meth)acrylic acid alkyl ester-(meth)acrylic acid copolymers; Ethylene-(meth)acrylic acid alkyl ester-maleic anhydride copolymer, polytetrafluoroethylene,
Ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polyfluorotrifluoroethylene, polyvinyl layer tyral, polyvinyl chloride, polymethacrylic acid Methyl, polystyrene, rubber modified polystyrene, ABS resin, AES resin, AC3 resin,
AAS resin, acrylonitrile-styrene copolymer, ■Krylostril-α
- Methylstyrene copolymer, acrylonitrile-paramethylstyrene copolymer, methacrylonitrile-ru-styrene copolymer, butadiene rubber, styrene-butadiene random or block copolymer, hydrogenated styrene-butadiene random or block copolymer , acrylobnitrile-butadiene rubber, isozylene rubber, acrylic rubber, silicone resin, polycarbonate, polyester, polyamide, polyamideimide, polyetherimide, polyetherester, polyetheresteramide, polyetheramide, polyetheretherketone, polyphenylene sulfide , polysulfone, polyether sulfone, polyphenylene ether, styrene-rubber modified polyphenylene ether, polyoxymethylene and the like. In particular, those having a glass transition temperature of 0° C. or lower are preferred.

As the maleimide monomer (A-1), maleimide,
N-Methishimaleimide, N-ethylmaleimide, N-
Isopropylmaleimide, N-tylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-
2,3 or 4-methylphenylmaleimide, N-2,
3 or 4-ethylphenylmaleimide, N-2,3 or 4-butylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-2,3 or 5-dichlorophenylmaleimide, N-3,4-dichlorophenyl Maleimide, N-2,5-i'romophenylmaleimide N
-2,4,,6-trichlorophenylmaleimide, N-
2,4゜glotri-10mophenylmaleimide, N-2゜3 or 4-hydroxyphenylmaleimide, N-2,3 or 4-methoxyphenylmaleimide, N-2,3 or 4
-Carboxyphenylmaleimide, N-4-nitrophenylmaleimide, N-4-diphenylmaleimide, N-
1-naphthylphenylmaleimide, N-4-cyanophenylmaleimide, N-4-phenoxyphenylmaleimide, N-4-benzylphenylmaleimide, N-2-methyl-5chlorophenylmaleimide, N-2-methoxy-5-chloro Particularly preferred are N-aryl substituted maleimides.

Examples of the unsaturated carboxylic acid monomer (A-2) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and himic anhydride. Among these, methacrylic acid and maleic anhydride are particularly preferred.

Any one or two of the above maleimide monomer (A-1) and unsaturated carboxylic acid monomer (A-2) constitute the copolymer (i) as the monomer (A) .

As the aromatic vinyl monomer (B-1), styrene,
α-methylstyrene, α-chlorostyrene, pt-butylstyrene, p-methylstyrene, 0-chlorostyrene, p-chlorostyrene, 2,5-dichlorostyrene,
3.4-dichlorostyrene, p-bromostyrene, o-
Bromostyrene, 2-5-dipromostyrene, 3.4-
Examples include dipromostyrene, cyanostyrene, 2-isopropenylnaphthalene, etc., and one or more types can be used. Among these, styrene or α-methylstyrene is usually preferred.

Examples of the unsaturated nitrile monomer (B-2) include acrylonitrile, methacrylonitrile, maleonitrile, and fumaronitrile, and one type or two or more of them can be used. Among these, acrylonitrile is usually preferred.

Examples of the unsaturated carboxylic acid ester monomer (B-3) include methyl, aethyl, propyl, lintyl, lauryl, cyclohexyl, 2-hydroxyethyl, bornyl, glycidyl, and dimethylaminoethyl of (meth)acrylic acid. Examples include (meth)acrylic acid ester monomers, and mono- and dialkyl esters of unsaturated dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, and hymic acid. One or more types of these can be used.

Among these, methyl methacrylate is usually preferred.

1 selected from the above-mentioned aromatic vinyl monomer (B-1), unsaturated nitrile monomer (B-2) and unsaturated carboxylic acid ester monomer (B-3) The species or two or more species constitute the copolymer (1) as the monomer (B).

In addition, as is clear from the second fil, the above monomer (
Monomer (C) is a monomer copolymerizable with A) and (B).
It can be used as As the monomer (C), ethylene, propylene, butene-1, pentene-1,4-
Methylpentene-1, vinyl chloride, vinylidene chloride, tetrafluoroethylene, monochlorotrifluoroethylene,
Examples include hexafluoropropylene, butadiene, acrylamide, methacrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinyl ether, vinyl ketone, coumaron, indene and acenaphthylene.

Any one or two monomers (A) of maleimide monomer (A-1) and unsaturated carboxylic acid monomer (A-2), and aromatic vinyl monomer (B -1), one or two selected from unsaturated nitrile monomers (B-2) and unsaturated carboxylic acid ester monomers (B-3)
A copolymer obtained by polymerizing at least one monomer (B) and a monomer (C) copolymerizable with these monomers, the composition of which (excluding thermoplastic resins and rubbery polymers) is Formula (1
This is a copolymer represented by 1 and (2).

(A) + (B) + (C) 1
)(A)+CB)+(C)
(2) Here, in formula +11, the amount of monomer (A) is 1
If the amount is less than 70% by weight, it is difficult to obtain a resin composition with high heat resistance. On the other hand, if the amount exceeds 70% by weight, the mechanical strength and processability of the resin composition tend to decrease, which is undesirable. A more preferable amount of monomer (A) in 1) is 3 to 60% by weight; if it exceeds this amount, the weather resistance deteriorates, which is not preferable. A preferable amount of monomer (C) is 0 to 30% by weight.

The composition shown in Formula Ill and (2) (excluding thermoplastic resin and rubbery polymer) means the average composition of copolymer (1), and the content of monomer (A) Although a mixture of a copolymer with a large amount of A and a copolymer with a small amount may be used, from the viewpoint of compatibility with the copolymer composition [II], the monopolymer (A ) is preferably added in a stepwise or continuous manner to widen the composition distribution.

In addition, a copolymer (Tl is a copolymer obtained by polymerizing the above monopolymer in the presence or absence of a thermoplastic resin and/or a rubbery polymer; 1) The upper limit of the thermoplastic resin and/or rubbery polymer in the composition is preferably 80% by weight. In particular, when the above monomers are polymerized in the presence of the rubbery polymer, impact strength is improved. The structure of this graft copolymer is not particularly limited, but the graft copolymer has a weight average particle size of 0.05 to 10 μm and a grafting rate of 10 to 150% by weight. Copolymer (1) preferably has an intrinsic viscosity of 0.2 to 1.5 d.
l/g is preferred. Here, when the above-mentioned monomers are graft-polymerized in the presence of a thermoplastic resin and/or rubbery polymer, generally all the monomers are not graft-polymerized to the thermoplastic resin or rubbery polymer, and monomers are not graft-polymerized to the thermoplastic resin or rubbery polymer. Some of the polymers form free copolymers. Therefore, the intrinsic viscosity of the copolymer in this case means the intrinsic viscosity of the free copolymer. In addition, the intrinsic viscosity is a dimethylformamide solution, 30
Measured values are in °C.

The copolymer (I) used in the present invention is a copolymer obtained by polymerizing the above monomers in the absence of a thermoplastic resin and/or a rubbery polymer, and a thermoplastic resin and/or a rubbery polymer. Alternatively, it may be a mixture of copolymers obtained by polymerizing the above monomers in the presence of a rubbery polymer.

Copolymer (1) can be produced by various methods.

That is, it can be produced by bulk polymerization, suspension polymerization, bulk-suspension polymerization, emulsion polymerization, solution polymerization, and combinations thereof.

In addition, a copolymer containing a maleimide monomer component, which is one of the constituent components of copolymer (1), can be obtained by directly copolymerizing a maleimide monomer and a copolymerizable monomer. Of course, it is possible to imidize a copolymer containing maleic anhydride with ammonia, a primary amine, an isocyanate ester, etc. The copolymer containing
It may be heat-treated in the presence or absence of ammonia, a primary amine, etc., and converted into a copolymer containing a glutaric anhydride group or a glutarimide group.

0 Copolymer composition (n) Thermoplastic resin and/or rubbery polymer, aromatic vinyl monomer (B-1) that can constitute the copolymer composition [II] of the present invention And as the unsaturated carboxylic acid ester monomer (B-3), the above-mentioned copolymer (1
) The glass transition temperature mentioned in the section above is preferably 0°C or lower.

In addition, the copolymerizable monomer (D) is the same as the monomer (C) and unsaturated nitrile monomer (B-2) exemplified in the above copolymer (1) section. Things can be mentioned.

The copolymer composition (n) in the present invention is prepared by combining an aromatic vinyl monomer (B-1) and an unsaturated carboxylic acid ester monomer in the presence or absence of a thermoplastic resin and/or a rubbery polymer. A composition consisting of a copolymer obtained by polymerizing monomer (B-3) and a monomer (D) copolymerizable with these, whose average composition (thermoplastic resin and rubbery polymer) ) is within the range represented by formulas (3) and (4), and the content of the unsaturated carboxylic acid ester monomer (B-3) is different, that is,
A copolymer consisting of 03-95% by weight of a copolymer with an unsaturated carboxylic acid ester monomer (B-3) content of more than 10% by weight and 097-5% by weight of a copolymer with an unsaturated carboxylic acid ester monomer (B-3) content of 10% by weight or less It is a composition.

(B-1)+ (B-3)+ (D) -3 to 80% by weight (3) (B-1)+ (B-3)+ (D) -0 to 50% by weight (4) Formula ( The contents of monomers (B-3) and (D) shown in 3) and (4) are the average contents in the entire copolymer composition [■].

Unsaturated carboxylic acid ester monomer in formula (3) (
If the content of B-3) is less than 3% by weight, chemical resistance will be poor;
On the other hand, if it exceeds 80% by weight, the compatibility with polystyrene, polyolefin, etc. will be poor. Particularly preferred is 5 to 60% by weight.

In addition, other copolymerizable monomers (D) in formula (4)
If the content exceeds 50% by weight, weather resistance will be poor. Especially 0~
30% by weight is preferred.

In addition, as described above, the copolymer composition (ff) includes copolymers 03 to 95% by weight and 10% by weight, in which the content of the unsaturated carboxylic acid ester monomer (B-, 3) exceeds 10% by weight.
It consists of 0.97% to 5% by weight of the copolymer, and outside this range, weather resistance, compatibility and affinity, and chemical resistance are poor. The content of the unsaturated carboxylic acid ester monomer (B-3) in the copolymer is preferably 10 to 80% by weight. In particular, copolymer ■5-80ffi
Preference is given to copolymer compositions consisting of 0.95% to 20% by weight of copolymer.

Further, the copolymer composition [II] is a thermoplastic resin and/or a copolymer composition [II].
Or a composition consisting of a copolymer obtained by polymerizing the above monomers in the presence or absence of a rubbery polymer; in this case, the heat occupied in the copolymer composition (n) is The upper limit of the plastic resin and/or rubbery polymer is preferably 80% by weight, and especially when the above monomer is polymerized in the presence of the rubbery polymer, the graft copolymer has high impact strength. is obtained. There is no particular restriction on the structure of this graft copolymer, but the weight average particle size of the graft copolymer (particle size of the graft copolymer in the molded article) is 0.05.
~10 μm and a graft ratio of 10 to 150% by weight are preferred.

Further, the intrinsic viscosity of the copolymer composition [II] is usually 0.2
~1.5 dl/g is preferred. Here, when the above-mentioned monomers are graft-polymerized in the presence of a thermoplastic resin and/or rubbery polymer, generally all the monomers are not graft-polymerized to the thermoplastic resin or rubbery polymer, and monomers are not graft-polymerized to the thermoplastic resin or rubbery polymer. Some of the polymers form free copolymers. Therefore, the intrinsic viscosity of the copolymer in this case means the intrinsic viscosity of the free copolymer. Note that the intrinsic viscosity is a value measured in a dimethylformamide solution at 30°C.

The copolymer composition [II] used in the present invention is a copolymer obtained by polymerizing the above monomers in the absence of a thermoplastic resin and/or a rubbery polymer, and a thermoplastic resin. and/or a mixture of copolymers obtained by polymerizing the above monomers in the presence of a rubbery polymer.

The copolymer composition (n) can be prepared in various ways, namely by bulk polymerization, suspension polymerization, bulk-suspension polymerization, emulsion polymerization, solution polymerization and combinations thereof.

can.

Here, the copolymer composition [II] is prepared by manufacturing the monomer (B
-3) Copolymers having different component compositions, that is, copolymers ① and ② may be mixed together, but in particular, in the process of producing the copolymers, the above-mentioned copolymers A copolymer composition obtained by polymerizing while changing the addition ratio of monomer (B-3) stepwise or continuously so as to satisfy the constituent requirements of composition C11) is preferable. A copolymer composition obtained by continuously changing the addition ratio of polymer (B-3) is suitable.

O Resin Composition The resin composition of the present invention consists of the above-mentioned copolymer [131 to 95% by weight and copolymer composition (n) 99 to 5% by weight, and if a composition within this range is used, heat resistance is improved. In addition to being well-balanced in terms of moldability, moldability, etc., a resin composition can be obtained that has good affinity or compatibility with other non-polar and polar materials. The amount of copolymer (1) is 5 to 90!11% (
The amount of copolymer composition [II] is 95-101t%)
It is particularly preferable that

The resin composition of the present invention consists of the above-mentioned copolymer [■] and copolymer composition [■], and can be obtained by mixing the separately produced products. Also,〔! It can also be obtained by introducing the monomer [II] in the presence of [II] or the monomer (1) in the presence of [II].

In the present invention, each component of the resin composition may be selected from among the following colorants, organic stabilizers, lubricants, fillers or reinforcing agents, plasticizers, flame retardants, foaming agents, and antistatic agents, as required. One or more compounding agents can be added. Moreover, these various compounding agents can be added during the manufacturing process of the resin composition or in the subsequent processing process, depending on the purpose of use.

The colorant that can be used in the resin composition of the present invention is preferably one or more selected from the following from the viewpoint of thermal stability. That is, the colorant color index (The 5ociety
of Dyers and Co1-Mat s t
s (UK) and The American^5so
ciacio.

of Textile Chimists and C
Pigment Red 101, Pigment Red 102, Pigment Red 108, Pigment Red 122, Pigment Red 149, Truben Trend 111, Solvent Red 151, Solvent Red 179, Pigment Orange 20. Solvent Orange 60, Pigment Yellow 37, Pigment Yellow 53, Pigment Yellow 183, Solvent Yellow 33, Pigment Brown 6, Pigment Brown 7, Pigment Brown 11. Pigment brown 24, pigment green 1
4, Pigment Green 19, Pigment Green 36
, Pigment Blue 15, Pigment White 4, Pigment White 6, Pigment White 7, Pigment White 21. Pigment black 10. Disvaal Violet 26 and number 77500 are preferably used.

Among these colorants, in particular, when Pigment White 4 and/or Pigment White 7 are used in combination with one or more colorants other than these, a product that is even more resistant to discoloration due to heat can be obtained.

Note that the particle size of the colorant is preferably fine particles of 0.5 μm or less.

There is no limit to the amount of the colorant added, but it is usually preferably in the range of 0.0001 to 20 parts by weight per 100 parts by weight of the resin composition. These can be colored in various tones. Further, the coloring agent can be in various forms such as powdered paste, master bunch, dry color, and moisturizing coloring agent.

There are no particular restrictions on the type of organic stabilizer that can be blended into the resin composition of the present invention; One or more types selected from epoxy and epoxy systems are used. Particularly effective against heat and light when one or more of phenol, sulfur, and phosphorus types are used in combination with one or more of amine, benzophenone, salicylate, hydrazine, and benzotriazole types. is large. The total amount of these additives varies depending on the composition and components of the resin composition, but is generally 0.01 to 3 parts by weight per 100 parts by weight of the resin composition.

As the lubricant, the following are preferably used.

Paraffin having 12 to 70 carbon atoms and molecular weight 1.00
0-3,000 low molecular weight polyethylene, carbon number 8-3
0 fatty acids, fatty acid amides with 8 to 30 carbon atoms, 8 carbon atoms
Alkylene bis fatty acid amide synthesized from ~30 fatty acids and alkylene diamines such as methylene diamine and ethylene diamine, fatty acids with 8 to 30 carbon atoms and alcohol esters with 1 to 20 carbon atoms, and 2 to 4 fatty acids with 8 to 30 carbon atoms.
C8-C30 fatty alcohol, C8-30 naphthenic acid and its di- to tetravalent metal salts,
Examples include polyethylene glycol-based, polyglycerol-based, and silicone-based lubricants.

From the viewpoint of physical property balance of the final resin composition, alkylene bis fatty acid amides, divalent metal salts of fatty acids having 12 to 30 carbon atoms, and silicone-based lubricants are particularly preferred. One or more types of these lubricants can be used.

The amount added is usually 0.01 to 3 parts by weight per 100 parts by weight of the resin composition.

As fillers or reinforcing agents, asbestos, alumina,
Attapulgite, kaolin clay, silicic acid, calcium silicate, diatomaceous earth, slate powder, sericite, quartz powder, zirconia, boron nitride, silicon nitride, calcium carbonate, magnesium carbonate, talc, boron carbide, silicon carbide, titanium Potassium acid, feldspar powder, molybdenum disulfide, pallite, vermiculite, gypsum, quartzite, glass powder, glass bulbs, glass fibers, nickel chromium, chromium alloy, stainless steel metal, tungsten alloy, beryllium, molybdenum, aluminum , lead, tin, copper, gold, silver, platinum, and alloys of these metals (including low-melting point alloys), as well as fibers, alumina fibers, carbon fibers, and the like. Among these, the powdered ones have a particle size of 0.
Those with a fiber diameter of 0.01 to 100 μm are used, or fibrous materials with a fiber diameter of 0.5 to 30 μm are used. Furthermore, these are preferably surface-treated with an organic titanate, an aminosilane compound, an epoxysilane compound, or a graft of the various monomers mentioned above.The upper limit of the amount of these added is based on 100 parts by weight of the resin composition. Although it depends on the difference in their specific gravity, the amount of -II is 200 parts by weight.

Examples of the plasticizer include phosphoric acid ester, adipic acid ester, sepatic acid ester, azelaic acid ester, glycolic acid ester, trimellitic acid ester, and the like.

Flame retardants include phosphate esters, halogen-containing phosphate esters, various halogen-substituted organic compounds, antimony dioxide, barium metaborate, zinc borate, titanium phosphate,
Examples include tin oxide, calcium phosphite, calcium hypophosphite, and red phosphorus.

Examples of blowing agents include evaporative foaming agents of organic solvents, inorganic blowing agents such as ammonium bicarbonate, sodium bicarbonate, sodium borohydride, and water, and organic blowing agents such as azo-based, nitrone-based, and hydrazide-based foaming agents. .

Examples of antistatic agents include cationic activators such as primary alkylamine salts, tertiary alkylamine salts, and quaternary alkyl ammonium salts; monovalent metal salts of fatty acids, sulfate ester salts of fatty alcohols, and ethyl fatty acids. sulfonate, alkyl sulfonate, alkylbenzene sulfonate,
Anion activators such as alkylnaphthalene sulfonates, succinate sulfonates, phosphate ester salts;
Partial fatty acid esters of polyhydric alcohols such as polyoxypropylene glycerol esters, ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty aminos or amides, ethylene oxide adducts of alkylphenols, polyhydric alcohols Nonionic surfactants such as ethylene oxide adducts of partial fatty acid esters; hydroxyethylimidacillin sulfate, zinc methylstearyldithiocarbamate, polyoxyethylene bisphenol A
Examples include.

The resin composition of the present invention can be produced by any method depending on the method for producing the copolymer. For example, latex, suspension,? It can be blended in the form of liquid, powder, beads, pellets, etc. These compositions can be directly molded into powder coatings, foamed materials, and other molded products, but generally they are melt-mixed using a Banbury mixer, a Nigu, or a single-screw or twin-screw extruder. It can be kneaded to form a uniform resin composition.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Note that all parts and percentages shown in the examples are based on weight.

Copolymer (I) 0.1 part of sodium sylbenzenesulfonate was charged, the inside of the reactor was purged with nitrogen gas, and the temperature was raised while stirring.
When the internal temperature reaches 70℃, N-phenylmaleimide 2
0 parts, styrene 60i! ”: A mixed solution consisting of 20 parts of cliconitrile and 0.2 parts of t-dodecylmercapdan, and an aqueous solution consisting of 0.1 part of potassium persulfate, 0.5 part of sodium dodecylbenzenesulfonate, and 50 parts of pure water were each mixed into 25 parts. Polymerization was carried out by raising the temperature to 77°C over 30 minutes while continuously adding at a rate of 12.5 parts/hour and 12.5 parts/hour.After the continuous addition of these solutions was completed, the solution was further maintained at 77°C for 1 hour. A calcium chloride aqueous solution was added to the obtained polymer latex to coagulate it, and the copolymer was recovered.

Table 1 shows the composition and intrinsic viscosity [η] of the obtained copolymer.

1 − +21 to I −[51 Copolymer 1 − (according to the production method of No. 11, each I1
Copolymers 1-(21 to I-(51) having different compositions were obtained.

Table 1 shows the composition and intrinsic viscosity [η] of the obtained copolymer.

Add 80% pure water to the reactor used in the production of copolymer 1- +11.
After charging 1 part of sodium dodecylbenzenesulfonate and o and s parts of potassium alkenylsuccinate,
The pH of the aqueous phase was adjusted to 7°2 with an aqueous solution of potassium dihydrogen phosphate and disodium hydrogen phosphate. After purging the inside of the reactor with nitrogen gas, 3 parts of acrylonitrile and α
- 50 parts of methylstyrene was charged and the temperature was raised to 75°C. To this was added a solution consisting of 15 parts of N-phenylmaleimide, 10 parts of acrylonitrile, 18 parts of α-methylstyrene, and 0.3 parts of t-dodecylmercaptan, 0.5 parts of sodium dodecylbenzenesulfonate, 0.3 parts of potassium persulfate, and An aqueous solution consisting of 50 parts of pure water was continuously added over 5 hours.

Then 4 parts of acrylonitrile were added over 1 hour. Thereafter, it was held at 75°C for 2 hours.

The obtained latex was coagulated with calcium chloride water/8 liquid, and the copolymer was recovered. The copolymer analysis results are shown in the second
Table 1 shows the composition and intrinsic viscosity [η].

r - (71 Maleic anhydride-styrene copolymer manufactured by CARCO, Dylark 0332, maleic anhydride content 114.2%)
was used. The composition and intrinsic viscosity [η] of the copolymer are shown in Table 1.

Copolymer 1- (30% pure water was added to the reactor used in the production of 11.
part, 0.002 parts of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate and 0.2 parts of dextrose,
Next, styrene-butadiene copolymer Terrax (rubber weight average particle diameter 0.47 μm, gel content 72%, styrene content 24 x'? gel content 42%, emulsifier sodium dodecylbenzenesulfonate, pH 5,7) 60 After charging the reactor with nitrogen gas, the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 70° C. with stirring. To this, a mixed solution each consisting of 5 parts of N-phenylmaleimide, 9 parts of styrene, 3 parts of acrylonitrile, 23 parts of methyl methacrylate, and 0.3 parts of t-dodecylmercaptan, 0.2 parts of cumene hydroperoxide, and dodecylbenzene. 1.0 part of sodium sulfonate and 30 parts of pure water
of the aqueous solution was added continuously over a period of 3 hours. Thereafter, the temperature was raised to 75°C and held for 2 hours. An aqueous magnesium sulfate solution was added to the obtained polymer latex to coagulate it, and a copolymer with a graft ratio of 36% was recovered.

Table 1 shows the composition and intrinsic viscosity [η] of the obtained copolymer.

Copolymer 1- (Into the reactor used in the production of 11 were added 5 parts of N-phenylmaleimide, 85 parts of styrene, 5 parts of Acfu0 rylonitrile, 0.2 parts of t-dodecylmercaptan, and ethylene (40%)-acrylic. Methyl acid (55%
) - 10 parts of glycidyl methacrylate (5%) copolymer was charged, and after purging the inside of the reactor with nitrogen gas, 1.
The temperature was raised to 00°C and bulk polymerization was carried out until the polymerization rate of the monomers reached 20%.

Aqueous solution containing 0.2 part of partially saponified polyvinyl alcohol and 0.1 part of hydroxypropyl methyl cellulose in this? Add a solution consisting of 1200 parts of FF, 0.2 parts of hensyl peroxide, 0.1 part of t-butylperoxide dibenzoate, 0.2 parts of t-dodecyl mercatritan, and 5 parts of styrene, and
Suspension polymerization was carried out at 115°C for 4 hours and then at 115°C for 3 hours to obtain a copolymer.

Table 1 shows the composition and intrinsic viscosity [η] of the obtained copolymer.

■-Fiber Copolymer 1-(70 parts of pure water, 0.1 part of potassium persulfate, and 0.2 parts of sodium lauryl sulfate were charged into the reactor used in the production of 11, and the inside of the reactor was purged with nitrogen gas. Thereafter, the temperature was raised to 70°C while stirring.

The following monomer solutions (containing t-dodecyl mercaptan) (11 to (3)) were successively added to this reactor over a period of 5 hours. At the same time as the addition of this monomer solution started, the following emulsifier and polymerization were added. The initiator aqueous solution was continuously added over 5 hours.Then, the temperature was raised to 80°C and maintained for 2 hours until the polymerization rate was 99.
．． A 1% latex was obtained. A calcium chloride aqueous solution was added to the obtained polymer latex to coagulate it, and the copolymer was recovered.

Table 1 shows the composition and intrinsic viscosity [η] of the obtained copolymer.

○ Monomer solution +1+ +21 [3] N-phenylmaleimide (%) 40 20 5 Acrylonitrile (%) 15 20 t.

Styrene (%) 45 60 85 Total addition (parts) 30 30 400 Emulsifier-polymerization initiator solution Pure water 50 parts Sodium lauryl sulfate 1 part Potassium persulfate 0.2 parts 26924),
Maleic anhydride-styrene copolymer (copolymer 1- (
71) was reacted with aniline in the presence of triethylamine in an extruder to form the N-
A phenylmaleimide-containing copolymer was obtained.

Table 1 shows the composition and intrinsic viscosity [η] of the obtained copolymer.

Table 1 *)! Copolymer (&lI product) [■] II-(1) 70 parts of pure water, 0.1 part of potassium persulfate, and dehydroabietic acid were added to the reactor used in the production of copolymer 1-+11 at the end of 1st reaction. After charging 0.3 parts of sodium and purging the reactor with nitrogen gas, the following monomer solution (11) was added under stirring, 0.3 parts of potassium persulfate, and 1.5 parts of dehydroabietic acid.
While continuously adding an aqueous solution consisting of 5 parts and 50 parts of pure water at a rate of 12.5 parts/hour, the temperature of the zero-order monomer solution was raised to 70°C. After the addition, 2 monomer solutions (3) to (5) were added in sequence.
Continuous addition was made at a rate of 5 parts/hour. Note that t-dodecyl mercaptan was used as a chain transfer agent. Then 75℃
and held for 2 hours. The obtained polymer latex was coagulated with an aqueous magnesium sulfate solution, and the product was recovered.

The polymerization results and product analysis results are shown in Tables 3 and 6.

The product consisted of a copolymer with a methyl methacrylate (including methyl acrylate) content of 10% or less and a copolymer with a methyl acrylate content of 10% or more.

0xLN body solution full (21(3) (41+51 added parts 10 20 20 20 30n -(
21 Copolymer 1- (70% pure water was added to the reactor used in the production of 1+)
After charging 0.1 part of potassium persulfate and 0.3 part of sodium dehydroabietate, and purging the inside of the reactor with nitrogen gas, 10 parts of methyl methacrylate solution (containing 3% methyl acrylate) was added with stirring. The temperature was raised to 70°C over 1 hour. Using 50 parts of styrene and 40 parts of methyl methacrylate solution, the ratio of methyl methacrylate solution/styrene was 10:10 at the beginning of addition.
The addition was continued over a period of 6 hours while changing the ratio so that the ratio was O/100 at the end of the addition and the addition ratio of the methyl methacrylate solution decreased linearly. In addition, t-bododecyl merca was used as a chain transfer agent. Further, at the same time as the addition of these monomers was started, an aqueous solution consisting of 0.3 parts of potassium persulfate, 1.5 parts of dehydroabietic acid, and 50 parts of pure water was continuously added over 5 hours. Thereafter, the temperature was raised to 75°C and held for 2 hours.

The obtained latex was coagulated with an aqueous calcium chloride solution, and the product was collected. The analysis results of the products are shown in Tables 4 and 6. Note that the MMA content shown in each table also includes methyl acrylate.

The product consisted of a copolymer with a methyl methacrylate (including methyl acrylate) content of 10% or less and a copolymer with a methyl acrylate content of 10% or more.

II -+31 Copolymer 1- (70% pure water was added to the reactor used in the production of 11.
After adding 0.2 parts of potassium persulfate, 0.3 parts of sodium dodecylbenzenesulfonate, and 0.3 parts of potassium alkenylsuccinate, the aqueous phase was diluted with an aqueous solution of potassium dihydrogen phosphate and disodium hydrogen phosphate. pH 7.2
Then, the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 70° C. while stirring. First, 1.5 parts of methyl methacrylate and 25 parts of styrene were added to this, and the addition ratios of methyl methacrylate/styrene at the start and end of addition were 50%, 150%, and 25%/75%, respectively. , and the addition ratio of methyl methacrylate was continuously added over 2 hours so that the addition ratio decreased linearly. Next, using 3.75 parts of methyl methacrylate and 16.25 parts of styrene, the addition ratio of methyl methacrylate/styrene at the start and end of addition was 25%/75% and 12°5%/87.5, respectively. % and the addition ratio of methyl methacrylate decreased linearly over 1 hour. Then, using 2.5 parts of methyl methacrylate and 37.5 parts of styrene, the addition ratio of methyl methacrylate/styrene at the start and end of addition was 12.5%/87.5% and O%, respectively.
/100% and the addition ratio of methyl methacrylate was continuously added over 2 hours so that the addition ratio decreased linearly. Thereafter, the temperature was raised to 75°C and held for 2 hours. Note that terpircin was used as a chain transfer agent. Also,! f
At the same time as the addition of the fi form, 50 parts of pure water, 0.1 part of potassium persulfate, 0.1 part of sodium dodecylbenzenesulfonate.
An aqueous solution consisting of 2 parts and 0.3 parts of potassium alkenylsuccinate was added continuously over a period of 4 hours. The obtained latex was coagulated with magnesium sulfate and the product was collected.

The analysis results of the product are shown in Tables 5 and 6.

The product consisted of a copolymer with a methyl methacrylate (including methyl acrylate) content of 10% or less and a copolymer with a methyl acrylate content of 10% or more.

■-(4) Except for polymerization by continuously adding a mixed solution of 60 parts of methyl methacrylate and 40 parts of styrene over 5 hours.
-(A product was obtained according to the method of 31. The analysis results are shown in Table 6.

The product consisted of methyl methacrylate (acrylic acid).

■-(5) II-
The product was obtained according to the method of +31. The results of this analysis are shown in Table 6.

It was made up of.

n −+61 Copolymer 1− (Pure water 30% in the reactor used in the production of 11
0 parts of ferrous sulfate heptahydrate, 0.1 part of OO2aWO sodium phosphate and 0.3 parts of dextrose, and then polybutadiene latex (rubber weight average particle size 0.42 μm 1 gel content 77%, solid content 41%) 6
After charging 0 parts (in terms of solid content), the inside of the reactor was purged with nitrogen gas, and the temperature was raised to 70° C. while stirring. To this, t-
The following monomer 0 body solution containing dodecyl mercapkun (
Solutions 11 to (5) were successively added over 4 hours for polymerization. On the other hand, simultaneously with the start of addition of the monomer solution, the following emulsifier-polymerization initiator aqueous solution was continuously added over 4 hours.

Thereafter, it was held at 75°C for 2 hours. The obtained polymer latex was coagulated with calcium chloride, and the grafting rate was 3.
9% product was recovered.

The analysis results of the product are shown in Table 6.

It consisted of 10% or more of copolymer.

■ Ethylene-propylene-cyclopentadiene rubber (propylene content 142%, Mooney viscosity 56, iodine value 15) Graft polymerizing a mixture of 50 parts of styrene, 20 parts of styrene, and 25 parts of methyl methacrylate,
A product with a grafting rate of 48% was obtained.

The analysis results of the product are shown in Table 6.

The product consisted only of a copolymer with a methyl methacrylate (including methyl acrylate) content of 10% or more.

II-(81 Butyl acrylate rubber latex (weight average particle size 0.4
The above n-(
Polymerization was carried out in accordance with the production method of No. 61, and a product with a graft ratio of 47% was obtained.

The analysis results of the product are shown in Table 6.

It was made up of.

Table 3 *) m-unit 4 winter 71 Table 5 The abbreviations in Tables 1 to 6 represent the following, respectively. In addition, the composition of the copolymer is C-11@N and 0
It was determined from elemental analysis and material balance in the copolymer manufacturing process.

NPMI: N-phenylmaleimide MAH: Maleic anhydride MA) I: Methacrylic acid S: Styrene AMS: α-Methylstyrene AN: Acrylonitrile MMA: Methyl methacrylate BR: Polyfridiene rubber SBR: Styrene-butadiene copolymer rubber EMA
: Ethylene-methyl acrylate-glycidyl methacrylate copolymer BAR butyl diacrylate rubber EPDM: Ethylene-propylene-cyclopentadiene rubber [η] Value measured using dimethylformamide. Unit (Li1/g) Examples 1 to 9 and Comparative Examples 1 to 2 I and ■ obtained above were blended in the proportions shown in Table 7, and triethylene glycol was added as a stabilizer per 100 parts of these blends. -bis(3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propione-)) 0.1 part, dilauryl-3,3'-thiodipropionate 0.1 part and (2,4 -di-t-butylphenyl)pentaerythritol diphosphite 0.2 parts and ethylene bisstearamide 0.3 as a lubricant.
2 parts with a vent and 0.1 part of silicone oil.
Kneaded at 250 to 300°C while devolatilizing in a shaft extruder,
Pelleted. The total amount of residual monomer in these pellets was molded into test pieces, and the physical properties were measured.

The results are shown in Table 7.

In addition, the physical properties were measured by the following method.

Izont impact strength with O-notch (abbreviated as Nl): Measured value on z-inch thickness test piece at 23°C.

○Heat distortion temperature (abbreviated as HDT): Value measured using an A-inch thickness test piece, 264 psi load, and no annealing.

○Solvent resistance: After immersing the test piece in gasoline at 30°C for 24 hours,
The state of rough skin etc. on the surface was observed with the naked eye.

Examples 10 to 14 I and ■ obtained above were blended in the proportions shown in Table 8, and the following compounding agents (the amount added is the number of parts based on 100 parts of the resin composition) were added to each composition. After mixing in a Henschel mixer, the mixture was pelletized by the method described in Examples 1 to 9, and test pieces were prepared to measure physical properties.

The results are shown in Table 8.

O compounding agent 1) 2-1-butyl-6-(3° -t-butyl-5'
-Methyl-2-hydroxybenzyl) = 4-methylphenylacrylate... 0.2 parts 2) Trisnonylphenyl phosphite...
0.2 parts 3) Dilauryl-3,3°-thiodipropionate.
...0.1 part 4) Ethylene bisstearamide... 0.2 part 5)
Magnesium stearate... 0.3 part 6) Big Men Trend 122... 0.1 part 7) Big Men Trend 149... 0.2 part 8)
Solvent red 151... o, 2
s9) Solvent yellow 33... o, x
Part 10) Pigment White 6...0.5 Part 11) Pigment White 7...0.2
Example 15 and Comparative Example 3 were blended with I and ■ obtained above at the proportions shown in Table 9, and both compositions were prepared using the following compounding agents (the amount added is the number of parts per 100 parts of the resin composition). ) was added and mixed in a Henschel mixer, and then pelletized by the method described in Examples 1 to 9 above to prepare test pieces and tested for light resistance.

The light resistance was evaluated by testing for 500 hours using a light resistance tester (manufactured by Suga Test Instruments Co., Ltd., Dual Panel Light Control Weather Mail Return Cycle).The results are shown in Table 9.Yellowness I, which is an indicator of discoloration.
ndex (YI value) is ASTM D-1925
Spectrophotometer (Murakami Color Technology Research Institute model, CA-
This is a value measured using a Model 35 high-speed spectrophotometer).

O compounding agent 1) Triethylene glycol-bis(3-(3-1-butyl-5-methyl-4-hydroxyphenyl)propionate)...0.2 part2) 2-(3,5-di- t-Butyl-4-hydroxyhensyl)-2-n-butylmalonic acid bis(1,2,2,6-bentamethyl-4
-piperidyl) 0.3 parts 3)
Di(2,4-di-t-butylphenyl) 4) Ethylene bisstearamide... 0.3 part 5) Pigment White 7... 0.1 part Table 9 Examples 16-17 and Comparative Example 4 Glass fiber (approximately 7 μm in diameter and approximately 6 mm in length, whose surface was treated with an aminosilane compound) was added to I and ■ obtained above, and a test piece was prepared according to the method of the above example. death,
Physical properties were measured.

The results are shown in Table 10.

Table 10 <Effects of the Invention> In the present invention, the resin composition using a copolymer having a specific composition distribution has heat resistance, chemical resistance (solvent resistance)
Not only does it have excellent mechanical strength, but it also has excellent weather resistance, so it can be used for vehicle parts, ship parts, aircraft parts, electrical/
It can be widely used in many fields such as electronic parts, building materials, electric tools, office equipment, agricultural machinery parts, packaging materials, household goods, sports and leisure goods, etc.

Claims (1)

[Scope of Claims] Any of the mailemide monomer (A-1) and the unsaturated carboxylic acid monomer (A-2) in the presence or absence of a thermoplastic resin and/or a rubbery polymer. one or two monomers (A) and an aromatic vinyl monomer (B-1
), one or more monomers (B) selected from unsaturated nitrile monomers (B-2) and unsaturated carboxylic acid ester monomers (B-3), and these A copolymer obtained by polymerizing a monomer (C) copolymerizable with and whose composition (excluding thermoplastic resin and rubbery polymer) is represented by formulas (1) and (2) Copolymer [I
] 1 to 95% by weight, and aromatic vinyl monomer (B-1) and unsaturated carboxylic acid ester monomer (B-1) in the presence or absence of a thermoplastic resin and/or rubbery polymer. -3) and a copolymer obtained by polymerizing a monomer (D) copolymerizable with these, the average composition (excluding thermoplastic resin and rubbery polymer) of , a copolymer composition represented by formulas (3) and (4), and the content of the unsaturated carboxylic acid ester monomer (B-3) is 1
A copolymer composition consisting of a copolymer exceeding 0% by weight [1] 3 to 95% by weight and a copolymer not exceeding 10% by weight [2] 97 to 5% by weight [II] consisting of 99 to 5% by weight A resin composition characterized by: 〇Copolymer [I] (A)/[(A)+(B)+(C)]×100=1-7
0% by weight (1) (C)/[(A)+(B)+(C)]×100=0-5
0% by weight (2) Copolymer composition [II] (B-3)/[(B-1)+(B-3)+(D)]×1
00=3-80% by weight (3) (D)/[(B-1)+(B-3)+(D)]×100
=0 to 50% by weight (4)