JPS63235350A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in heat resistance, weathering resistance, chemical resistance, mechanical properties and moldability, comprising a specified copolymer, a specified copolymer composition and a third component. CONSTITUTION:This resin composition is formed from [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 formulas III and IV, and [III] component X. The mixing ratio of components I-III is in the range represented by formulas V and VI.

Description

[Detailed description of the invention] <Industrial application field> This description describes the invention as having excellent heat resistance, weather resistance, chemical resistance, mechanical properties and moldability, and compatibility with various non-polar and polar materials. The present invention also relates to a resin composition having good affinity.

<Prior art> Styrene resin or methyl methacrylate is widely used. 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 ABS resin 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 these Compositions (Japanese Patent Publication No. 58257/1983), etc., have been proposed, which include impact-resistant polystyrene and styrene-butadiene block copolymers.

<The problem that the invention is trying to solve> However,
Resins made by introducing maleimide monomers, etc. as mentioned above have very high polarity, so resins with non-polar or polar This tendency is 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 having the characteristics originally possessed by each resin. In addition, the present inventors have solved the above-mentioned problems, and these sets have excellent heat resistance, weather resistance, chemical resistance, mechanical properties, and moldability, and are compatible with various non-polar and polar materials. As a result of intensive studies to obtain a resin composition with very good compatibility or affinity, we found a copolymer [I] consisting of a specific heat resistance-imparting component and composition, and a copolymer composition [I] having a specific composition distribution. ■] and other thermoplastic resins and/or rubbery polymers (I[[]),
This led to the present invention.

That is, the present invention provides the following methods: in the presence or absence of a thermoplastic resin and/or a rubbery polymer, either the maleimide monomer (A-1) or the unsaturated carboxylic acid monomer (A-2) 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 a monomer (C), and its composition (excluding thermoplastic resin and rubbery polymer).

) is a copolymer [r
) and aromatic vinyl monomer (B-1) and unsaturated carboxylic acid ester monomer (B-3) and these in the presence or absence of a thermoplastic resin and/or rubbery polymer. A composition consisting of a copolymer obtained by polymerizing a monomer (D) copolymerizable with , the average composition (excluding thermoplastic resin and rubbery polymer) of formula (3) and (4), and the content of the unsaturated carboxylic acid ester monomer (B-3) is 10
Copolymer composition [II] consisting of more than 03 to 95% by weight of copolymer and 097 to 5% by weight of copolymer less than 10% by weight, and other thermoplastic resin and/or rubbery polymer (I[[
), the blending ratio of which is within the range expressed by formulas (5) and (6).

○Copolymer (1) (A) + (B) + (C) (1
)(A)+(8)+(C)(
Phantom O copolymer composition [■] (I3-1) + (I3-3) + (D) = 3 to 80% by weight (3) (B-1) + (B-3) + (D) = 0 to 50% by weight (4) 04M fat composition The present invention will be explained in detail below.

O copolymer (1) Examples of the thermoplastic resin and/or rubbery polymer that can constitute the copolymer CI) of the present invention include the following. Boatene-1 copolymer, propylene-ethylene block copolymer, ethylene-propylene rubber, maleic anhydride grafted polyolefin, N-phenylmaleimide grafted polyolefin, chlorinated polyolefin, ethylene-vinyl acetate copolymer% ethylene-vinyl alcohol copolymer Polymers, ethylene-(meth)acrylic acid and its metal salt copolymers, ethylene-(meth)acrylic acid ester copolymers such as methyl (meth)acrylate, ethyl, propyl, butyl, glycidyl, dimethylaminoethyl, Ethylene-(meth)acrylic acid alkyl ester-(meth)acrylic acid copolymer layer, ethylene-(meth)acrylic acid alkyl ester-maleic anhydride copolymer, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer , tetrafluoroethylene-perfluoroalkyl vinyl trifluoroethylene, polyvinyl chloride, polyvinyl chloride, polymethyl methacrylate, polystyrene, rubber-modified polystyrene, ABS resin, AB
S resin, AC3 resin, AAS resin, acrylonitrile-
Styrene copolymer, acrylonitrile-α-methylstyrene copolymer, acrylonitrile-paramethylstyrene copolymer, methacrylonitrile-styrene copolymer, butadiene rubber, styrene-butadiene random or block copolymer, hydrogenated styrene- Butadiene random or block copolymer, aquarylonitrile-butadiene rubber, isoethylene rubber, acrylic rubber, silicone resin, polycarbonate, polyester, polyamide, polyamideimide, polyetherimide, polyetherester, polyetheresteramide, One or more of polyether amide, polyether ether ketone, 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-methylmaleimide, N-ethyl 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-diromophenylmaleimide, N-2,4,6-dolichlorophenylmaleimide, N-2.4゜6-trimophenylmaleimide, 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 F % N 4 > anophenylmaleimide, N-4-phenoxyphenylmaleimide, N
-4-benzylphenylmaleimide, N-2-methyl-
) Turolof-3-nilmaleimide, N-2-methoxy-5-
Examples include chlorophenylmaleimide, and one or m
Ishakotoka ゛teguru.

2 or more types Among these, especially N
-Aryl-substituted maleimides are preferred.

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-mentioned maleimide monomer (A-1) and unsaturated carboxylic acid group monomer (A-2) constitute a copolymer (l) as the monomer (A) .

Aromatic vinyl monomer (B-1> is styrene,
α-methylstyrene, α-chlorostyrene, pt-butylstyrene, p-methylstyrene, 0-chlorostyrene, p-chlorostyrene, 2,5-dichlorostyrene,
3.4-dichlorostyrene, p~dipromostyrene 0-
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, metacyclonitrile, maleonitrile, fumaronitrile, and the like, and one type or two or more types can be used. Among these, acrylonitrile is usually preferred.

Examples of the unsaturated carboxylic acid ester monomer (B-3) include methyl, aethyl, propyl, -thyl, 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 heimincic acid. One or more types of these can be used.

Among these, methyl methacrylate is usually preferred.

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

Furthermore, as is clear from the formula (l+), the above-mentioned monomer (
Monomer (C) is a monomer copolymerizable with A) and (B).
It can be used as As the monomer (C), ethylene, propylene Ly7, Alayer Ten-1. pentene-1,4-methylpentene-1,
Vinyl chloride, vinylidene chloride, tetrafluoroethylene, monochlorotrifluoroethylene, hexafluoropropylene, butadiene, acrylamide, methacrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinyl ether, vinylketone, coumaron, indene and acenaphthylene, etc. Can be mentioned.

The copolymer ([) is composed of a maleimide monomer (A-1) and an unsaturated carboxylic acid monomer (A-2) in the presence or absence of the thermoplastic resin and/or rubbery polymer described above.
) any one or two monomers (A), an aromatic vinyl monomer (B-1), an unsaturated nitrile monomer (
B-2) and unsaturated carboxylic acid ester monomer (B-2)
-3) one or more monomers selected from (
A copolymer obtained by polymerizing B) and a monomer (C) copolymerizable with these, the composition (excluding thermoplastic resin and rubbery polymer) of formulas (1) and (2) It is a copolymer represented by

Here, in formula (1), the amount of monomer (A) is 1% by weight.
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. A more preferable amount of monomer (A) is 3 to 6
A preferable amount of monomer (C) is 0 to 30% by weight, since if it exceeds 0% by weight, the weather resistance will be poor and undesirable.

The compositions shown in formulas (1) and (2) (excluding thermoplastic resin and rubbery polymer) mean the average composition of copolymer el), and the content of monomer (A) Although a mixture of a copolymer with a large amount and a copolymer with a small amount may be used, from the viewpoint of compatibility with the copolymer composition (II), the monopolymer ( It is preferable to widen the composition distribution by changing the addition ratio of A) stepwise or continuously.

In addition, copolymer (1) is a copolymer obtained by polymerizing the above-mentioned 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, if the above monomer is polymerized in the presence of the rubbery polymer, there will be an impact. A graft copolymer with high strength can be obtained. There is no particular restriction on the structure of this grafted carbonate copolymer, but it is preferable that the weight average particle diameter of the grafted copolymer is 0.05 to 10 μm and the graft ratio is 10 to 150% by weight. The intrinsic viscosity of 1) is usually 0.2 to 1.5a
/g is preferred, where the thermoplastic resin and /g are preferred.
Or, when the above-mentioned monomers are graft-polymerized in the presence of a rubbery polymer, generally all the monomers are not graft-polymerized to the thermoplastic resin or rubbery polymer, and some of the monomers remain free. Forms a copolymer. Therefore, the intrinsic viscosity of the copolymer in this case means the intrinsic viscosity of the free copolymer.

In addition, the intrinsic viscosity is dimethylformamide solution, 30℃
This is the measured value at

The copolymer (1) 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 [I], 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.

○Copolymer composition (■) Thermoplastic resin and/or rubbery polymer, aromatic vinyl monomer (B-1) and Examples of the unsaturated carboxylic acid ester monomer (B-3) include those mentioned in the above copolymer (1) section.As a thermoplastic resin and/or rubbery polymer, In particular, those having a glass transition temperature of 0° C. or lower are preferred.In addition, as the copolymerizable monomer CD), monomers (C) exemplified in the section of copolymer (1) above are preferred. and unsaturated nitrile monomer CB-2).

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, i.e., unsaturated carboxylic acid ester monomer (B'-3). A copolymer composition consisting of a copolymer 03 to 95% by weight in which the acid ester monomer (B-3) content exceeds 10% by weight and a copolymer 097 to 5% by weight in which the acid ester monomer (B-3) content is 10% by weight or less. be.

(8-1) + (6-3n + ([)
)=3~841% (3) (I3-1) + (B-3) + (D)-
〇 ~50% by weight (4) The content of monomers (B-3) and CD) shown in formulas (3) and (4) is the average content in the entire copolymer composition (IT) .

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 CD in formula (4)
If the content exceeds 541%, weather resistance will be poor. Especially 0-3
0% by weight is preferred.

In addition, as mentioned above, the copolymer composition [''] is a copolymer containing 03 to 95% by weight and 10% by weight of the unsaturated carboxylic acid ester monomer (B-3). weight%
It consists of 097 to 5% by weight of the following 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 copolymer (1) is preferably 10 to 80% by weight, especially copolymer (05 to 80% by weight) and copolymer (1) 95 -2095-20 weight copolymer compositions are preferred.

Furthermore, the copolymer composition (n) is a composition comprising a copolymer obtained by polymerizing the above monomers in the presence or absence of a thermoplastic resin and/or a rubbery polymer. In this case, the upper limit of the thermoplastic resin and/or rubbery polymer in the copolymer composition (ff) is preferably 80% by weight.

Here, especially when the above-mentioned monomers are polymerized in the presence of a rubbery polymer, a graft copolymer having high impact strength can be obtained.

The structure of this graft copolymer is not particularly limited, but the weight average particle size of the graft copolymer (particle size of the graft copolymer in the molded article) is 0.05 to 10 tt m, and the graft ratio is 10. ~150% by weight is preferred, and
The intrinsic viscosity of the copolymer composition (If) is usually 0.2 to 1.
5d1/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.

Copolymer composition (II) 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.

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, but in particular, in the process of producing the copolymers, each of the above copolymers; A copolymer composition obtained by polymerizing by changing the addition ratio of monomer (B-3) stepwise or continuously so as to satisfy the constituent requirements of the combined composition (II) is preferred; in this case, In particular, a copolymer composition obtained by continuously changing the addition ratio of monomer (B-3) is suitable.
'○ Other thermoplastic resin and/or rubbery polymer (1) The other thermoplastic resin and/or rubbery polymer (III) constituting the resin composition of the present invention is the copolymer (1).
) are the same as those mentioned in the section above. One or more types of these can be used. Especially when the heat distortion temperature ('A'+'55psi, without annealing) is 5
Preferably, the temperature is 0°C or higher.

○Resin composition The resin composition of the present invention comprises the above-mentioned copolymer (1) and copolymer composition [II], as well as other thermoplastic resins and/or
or a rubbery polymer (Ill), and the blending ratio of these is represented by the following formulas (5) and (6).

(1) + CIri(]) + (n) + (II[)
If the amount of 161 copolymer (1) is within the range expressed by formula (5), it will not only have an excellent balance of heat resistance and moldability, but also have good compatibility with other non-polar materials and polar materials. In the formula (5) in which a resin combination acid with good compatibility is obtained, a more preferable amount of the copolymer (1) is 5 to 90% by weight.

As expressed by formula (6), the amount of the other thermoplastic resin and/or rubbery polymer Cl1)) is (1,), (
1 to 99% by weight based on the total of n) and (III). If it exceeds 99% by weight, heat resistance, affinity and compatibility will be poor, and if it is less than 1% by weight, the unique properties of (III) will not be utilized.

The resin composition of the present invention consists of the above-mentioned copolymer CI], copolymer composition [■], and other thermoplastic resin and/or rubbery polymer (III), each of which is manufactured separately. Obtained by mixing.

In the present invention, the following colorants, organic stabilizers, lubricants, fillers or reinforcing agents, plasticizers, flame retardants, blowing agents, and antistatic agents may be used as constituent components of the resin composition, as required. One or more compounding agents selected from among these 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 5ociet
y of Dyers and Co1-7ists (
UK) and fhe A+gerican As5oc
of Textile Chists
and Co1orist (USA)]
A colorant represented by the name or number listed in
Their names are Pigment Red 101, Pigment Red 102, Pigment Red 108, Pigment Trend 122, Pigment Red 149, and Solvent Red 1.
) 1, Solvent Red 151, Solvent Red 17
9. 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 1), Pigment Brown 24, Pigment Green 14, Pigment Green 19, Pigment Green 36, Pigment Blue 15, Pigment White 4, Pigment White 6, Pigment White 7
, Pigment White 21 Pigment Blank 10,
Disvaal Violet 26 and number 77500
etc. are preferably used.

Among these colorants, in particular, when Pigment White 4 and/or Pigment White 7 is 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.

Further, there is no limit to the amount of the colorant added, but it is usually preferably in the range of o,ooot to 20 parts by weight per 100 parts by weight of the resin composition, and various color tones can be obtained by using these. Further, the colorant can be in various forms such as a powder paste, a masterbatch, a dry color, and a moisturizing colorant.

There are no particular limitations on the type of organic stabilizer that can be blended into the resin composition of the present invention, but examples include phenol, sulfur, phosphorus, amine, benzophenone, salicylate, benzotriazole, One or more types selected from hydrazine type and epoxy type are used. Particularly phenolic, sulfur and phosphorus 1
When used in combination with one or more types of amine type, benzophenone type, salicylate type, hydrazine type and benzotriazole type, the effect against heat and light is great. The total amount of these additions varies depending on the composition and components of the resin composition, but
Generally 0.01 to 3 per 100 fifi parts of resin composition
Heavy weight.

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.
divalent metal salts, fatty alcohols having 8 to 30 carbon atoms, naphthenic acids having 8 to 30 carbon atoms and their divalent to tetravalent metal salts,
Examples include polyethylene glycol-based, polyglycerol-based, and silicone-based lubricants.

From the viewpoint of the 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 type or 2 m or more of these lubricants may be used. can.

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, pumice, gypsum, waxite clay, glass alloy, beryllium, molybdenum, aluminum, lead, tin, copper, gold,
Examples include agglomerate powders such as 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, those in powder form generally have a particle diameter of (1,01 to 1) 00I1, and those in fibrous form have a fiber diameter of 0.5 to 30 μm. Furthermore, those surface-treated with an organic titanate, an aminosilane compound, an epoxysilane compound, or a graft of the various monomers mentioned above are preferably used. The upper limit of these addition amounts is generally 200 parts by weight per 100 parts by weight of the resin composition, although it depends on the difference in specific gravity between them.
It is a quantity part.

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.

Idl fuels include phosphate esters, halogen-containing phosphate esters, various halogen-substituted organic compounds, antimony dioxide, barium metaborate, zinc borate, titanium phosphate, tin oxide, calcium phosphite, calcium hypophosphite, and red phosphorus. In addition to these, examples include condensed phosphoric acid amide, fatty monoglyceride boric acid ester, and the like.

Examples of blowing agents include evaporative blowing 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 blowing 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, it can be blended in the form of latex, suspension resin, solution, powder, beads, pellets, etc. These compositions can be directly expanded and molded into powder coatings, foam materials, and other molded products, but generally they are processed using a melt kneader such as a Banbury mixer, a Nigu, or a l-screw or twin-screw extruder. The resin composition can be kneaded to obtain a uniform resin composition.

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 [1)! -fil 70 parts of pure water, 0.02 parts of potassium persulfate, and 0.1 part of sodium dodecylbenzenesulfonate were charged into a 20J reactor equipped with a stirring blade and a plate puffer, and the inside of the reactor was replaced with nitrogen gas. Raise the temperature while stirring until the internal temperature reaches 70℃.
When the temperature reached ℃, a mixed solution consisting of 20 parts of N-phenylmaleimide, 260 parts of Ste 1, 20 parts of cyclonitrile, and 0.2 parts of t-dodecylmercaptan, 0.1 part of potassium persulfate, and 0 parts of sodium dodecylbenzenesulfonate was added. Polymerization was carried out by raising the temperature to 77° C. over 30 minutes while continuously adding an aqueous solution consisting of .5 parts and 50 parts of pure water at a rate of 25 parts/hour and 2.5 parts/hour, respectively. After the continuous addition of these solutions was completed, the temperature 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.

Copolymers 1-+21 to I-+51 having different compositions were obtained according to the method for producing 1-[21 to I-[51 copolymers 1-+1).

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

f −+61 After charging 80 parts of pure water, 1 part of sodium dodecylbenzenesulfonate, and potassium alkenylsuccinate O, SS into the reactor used in the production of copolymer I-(1), potassium dihydrogen phosphate- After adjusting the pH of the aqueous phase to 7.2 with an aqueous solution of disodium hydrogen phosphate and 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, 15 parts of N-phenylmaleimide, 1 part of acrylonitrile
A solution consisting of 0 parts, 18 parts of α-methylstyrene and 0.3 parts of t-dodecylmercaptan, as well as 0.5 parts of sodium dodecylbenzenesulfonate and 0.0 parts of potassium persulfate.
．． An aqueous solution consisting of 3 parts and 50 parts of pure water was continuously added over 5 hours. Then, 4 parts of acrylonitrile was added over 1 hour. Thereafter, it was held at 75°C for 2 hours.

The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymer was recovered. The analysis results of the copolymer are shown in Table 2, and the composition and intrinsic viscosity [η] are shown in Table 1.

I-+71 Maleic anhydride-styrene copolymer (manufactured by ARCO, Dilarc 332, maleic anhydride oxygen pH 4.2%) was used. The composition and intrinsic viscosity [η] of the copolymer are shown in Table 1.

1- +81 70 parts of pure water was added to the reactor used in the production of copolymer r=t+.
0.1 part of potassium persulfate and 0.2 part of sodium lauryl sulfate were charged, and after purging the inside of the reactor with nitrogen gas, the temperature was raised to 70° C. with stirring.

The following monomer solutions (containing t-dodecyl mercaptan) (1) to (3) were successively added to this reactor over a period of 5 hours. Simultaneously with the start of addition of this monomer solution, the following emulsifier and polymerization initiator aqueous solutions were continuously added over 5 hours. After that, the temperature was raised to 80'C and held for 2 hours, and the polymerization rate was 9.
A 9.1% latex was obtained. A calcium chloride aqueous solution was added to the obtained polymer latex to coagulate it, and the copolymer was recovered.

The composition and intrinsic viscosity [η] of the copolymer are shown in Table 1.

O monomer liquid (1) + 21 (31 N-phenylmaleimide (%) 40 20 5 Acrylonitrile (%) 15 20 10 Styrene
(%) 45 60 85 total addition!
(Parts) 30 30 400 Emulsifier-polymerization initiation side solution Pure water 50 parts Sodium lauryl sulfate 1 part Potassium persulfate 0.2 parts 1- +91 Copolymer 1- Based on the manufacturing method of fil, N-phenylmaleimide 20 48 parts of methyl methacrylate and 32 parts of styrene were copolymerized to obtain the copolymers shown in Table 1.

The composition and intrinsic viscosity [η] of the copolymer are shown in Table 1.

Table 1 Table 2 *) Copolymer (composition) at the end of polymerization (■) ■-(1) 70 parts of pure water and potassium persulfate were added to the reactor used in the production of copolymer 1-(1). After charging 0.1 part and 0.3 part of sodium dehydroabietate, and replacing the reactor with nitrogen gas, the following monomer solution (1) was charged with stirring, and 0.3 part of potassium persulfate, Dehydroabietic acid 1.
While continuously adding an aqueous solution consisting of 5 parts and 50 parts of pure water at a rate of 12.5 parts/hour, 25 parts of a zero-order monomer solution +21 WL heated to 70°C was continuously added at a rate of 7 hours. Thereafter, monomer solutions (3) to (5) were successively added at a rate of 25 parts/hour. Note that t-dodecyl mercaptan was used as a chain transfer agent. after that,
It was heated to 75°C 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.

○ Monomer solution +1) +21 (31+41 (517
Styrene ratio (%) Number of parts added 10 20 20 20 30
n -+21 Copolymer 1- Add 70% pure water 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 a methyl methacrylate solution (containing 3% methyl acrylate) was added under stirring. The temperature was raised to 70°C over 1 hour. 50 parts of styrene and 40 parts of methyl methacrylate solution were added, and the ratio of methyl methacrylate solution/styrene was 10010 at the start of addition.
The addition was continued over a period of 6 hours while changing the ratio so that it became 0/100 at the end of one addition and the addition ratio of the methyl methacrylate solution decreased linearly.

Note that t-dodecyl mercaptan 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 analysis results of the obtained latex products are shown in Tables 4 and 6. 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 10% or more content.

II-(31) Into the reactor used in the production of copolymer T-(ll) were added 70 parts of pure water, 0.2 parts of potassium persulfate, 0.3 parts of sodium dodecylbenzenesulfonate, and 0 potassium alkenylsuccinate.
After charging 63 parts, the pH of the aqueous phase was adjusted to 7.2 with an aqueous solution of potassium dihydrogen phosphate and disodium hydrogen phosphate, and 25 parts of styrene was used at the start and end of addition. The addition ratio of methyl methacrylate/styrene is 50%, 150% and 25%/-, respectively.
175%, and methyl methacrylate...
The addition was continued over a period of 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 was continuously added over 1 hour so that the addition ratio decreased linearly. 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, respectively.
．． The addition ratio of methyl methacrylate was added over 2 hours so that the ratio was 5% and 0%/100%, and the addition ratio decreased linearly. Thereafter, the temperature was raised to 75°C and held for 2 hours. Note that turbilcin was used as a chain transfer agent. Simultaneously with the start of monomer addition, 50 parts of pure water, 0.1 part of potassium persulfate, 0.2 part of sodium dodecylbenzenesulfonate and 0° potassium alkenylsuccinate were coagulated, and the product was recovered.

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 10% or more content.

n −+41 II except that polymerization was carried out by continuously adding a mixed solution of 60 parts of methyl methacrylate and 40 parts of styrene over 5 hours.
The product was obtained according to the method of -+31.

The results of this analysis are shown in Table 6.

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

n -(51 I[-
(The product was obtained according to the method of No. 31. The analysis results are shown in Table 6.

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

n −+61 Copolymer 17 Add 30% pure water to the reactor used in the production of (1).
1 part, 0.002 part of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate and 0.3 part of dextrose, and then polybutadiene latex (weight average particle diameter of rubber 0.42 μm, gel content 77%, Solid content 41%) 60 parts (
After charging the reactor (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, the following monomer solutions (1) to (containing -dodecyl mercaptan) are added.
5) The liquids were continuously added one after another 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.

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

II-+71 Ethylene-propylene-cyclopentadiene rubber (propylene content 42%, Mooney viscosity 56, Graft polymerization of a mixture of 50 parts of iodine number 15), 20 parts of styrene and 30 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.

Table 3 Table 5 The abbreviations in Tables 1 to 6 represent the following, and the composition of the copolymer is determined by CH, N, and O elemental analysis and the substances used in the copolymer manufacturing process. Calculated from income and expenditure.

NPMI: N-phenylmaleimide MAH: Maleic anhydride MAA: Methacrylic acid S: Styrene AMS: α-methylstyrene AN: Acrylonitrile MMA: Methyl methacrylate BR: Polybutadiene rubber EPDM: Ethylene-propylene-cyclopentadiene rubber [η Conidium dimethylformamide solution, value measured at 30°C, unit a/g Other thermoplastic composition resin and/or rubbery polymer [1] [
] Other thermoplastic resins and/or rubbery polymers ([[[
), the following were used, respectively.

ml-+1) As (manufactured below) 1[1i21ABS() 1)1-+31AAS() +1l-(41AES() III-+51 Polymethyl methallylate (manufactured by Sumima Kagaku Co., Ltd., Sumipex B-LG) 1[[ -+61 Polystyrene (manufactured by Nippon Polystyrene Co., Ltd., Nisprite 4) III -+71 Impact-resistant polystyrene (manufactured by Nippon Polystyrene Co., Ltd., Nisprite 5003B) fl[-(llll+' Polycarbonate (manufactured by Kijin Kasei Co., Ltd., Pad 1010) ■-〇Φ Ethylene-glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Bond First 2B) m-aυ polyester (manufactured by Toyobo Co., Ltd., Belprene P
40H) +1l-(la PE (0.2% maleic anhydride grafted polyethylene, 210°C, melt index 2.4 under 2.16 kg load) +1)- (1) A S Known suspension polymerization method (Tokuko Showa) 49-37590), 30 parts of acrylonitrile and 70 parts of styrene were copolymerized to produce a product with an acrylonitrile content of 27% and an intrinsic viscosity of 0.
．． A copolymer of 61 dl/H was obtained.

30 parts of pure water, 0.002 parts of ferrous sulfate heptahydrate, 0.1 part of sodium birophosphate, and 0.3 parts of dextrose were added to the reactor used in the production of III-(21A B S copolymer 1-+1). of polybutadiene latex (rubber weight average particle size 0
．． After charging 60 parts (in terms of solid content) of 47 μm (1 gel content: 79%, solid content: 42%), the inside of the reactor was purged with nitrogen gas, and the temperature was raised to 70° C. while stirring. To this, a mixed solution consisting of 15 parts of acrylonitrile, 35 parts of styrene and 0.3 parts of t-dokesylmercabutane, 0.3 parts of potassium alkenylsuccinate 1.2-butyl hydroperoxide and 30 parts of pure water were added. The aqueous solution was continuously added over 3 hours. After that, it was held at 75°C for 2 hours,
A latex with a polymerization rate of 99.1% was obtained. The obtained latex was coagulated with magnesium sulfate, and the graft ratio was 4.
2%, intrinsic viscosity of ungrafted copolymer 0.47 dj/g
copolymer numbers were recovered.

^ III -+31 A $IS Butyl acrylate rubber latex (weight average particle size 0.3
μm, gel content 79%, solid content 42%) was used as the rubber component, and 36 parts of styrene and 14 parts of acrylonitrile were used as the copolymer layer.
Polymerization was carried out according to the production method of (5), and the polymerization rate was 98.9%.
Grafting rate: 47%, intrinsic viscosity of ungrafted copolymer: 0.
A copolymer of 52 d1/g was obtained.

! 1l-(41AES) Ethylene-propylene-cyclopenk diene rubber (propylene content 42%, Mooney viscosity 56, iodine value 15) A mixture of 50 parts of styrene, 34 parts of styrene, and 16 parts of acrylonitrile was graft-polymerized,
A copolymer was obtained with a graft ratio of 50%, an intrinsic viscosity of the ungrafted copolymer of 0.55 dl/g, and a rubber content of 50.4%.

Examples 1 to 3 and Comparative Examples 1 to 4 Each of the copolymers 1 and 2 and other thermoplastic resins were blended in the proportions shown in Table 7, and as a stabilizer per 100 parts of these blends. Triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-
hydroxyphenyl)′i; ropionate] 0.1 part,
Dilauryl-3,3'-thiodipropionate 0.1
1 part and 0.2 parts of (2,4-di-t-butylphenyl)pentaerythritol diphosphite, 0.3 parts of ethylene bisstearamide and 0.1 part of silicone oil as lubricants, and twin-screw extrusion with a vent was added. The mixture was kneaded at 250 to 300°C while being devolatilized in a machine to form pellets. These pele.

The total amount of residual monomers in each sample was 0.2% or less.

The pellets were molded at 250 to 320°C using an injection molding machine to prepare test pieces, and their physical properties were measured.

The results are shown in Table 7.

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

○ Notched Izo impact strength (abbreviated as Nl): A value measured at 23°C using an A-inch thickness test piece.

○Heat distortion temperature (abbreviated as HDT): Value measured on a % inch thick test piece, 264 ps i load, without 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 4 to 1 ■ and Comparative Examples 5 to 9 Each of the copolymers of ■ and ■ and these and other thermoplastic resins or rubbery polymers were blended in the proportions shown in Table 8, and any of the copolymers of The composition was also mixed with the following compounding agents (the amount added is the number of parts per 100 parts of the resin composition) using a Henschel mixer, and then pelletized by the method described in Examples 1 to 3 above, and test pieces were prepared to examine the physical properties. It was measured.

The results are shown in Table 8.

○Compounding agent 1) 2-t-butyl-6-(3°-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylalrylate...0.2 parts2 ) Trisnonylphenyl phosphite...
0.2 parts 3) Dilauryl-3,3゛-thiodipropionate.
...0.1 part 4) Ethylene bisstearamide... 0.2 part 5)
Magnesium stearate 0.3 parts 6) Pigment Red 122 0.1 part 7) Pigment Red 149 0.2 parts 8)
Solvent Red 151 ・・・・・・ 0.2 parts 9
) Solvent Yellow 33..., O, part 1
0) Pigment White 6...0.5 part 1
)) Pigment White 7... 0.2 parts of thermoplastic resin was blended at the layer ratio shown in Table 9, and each composition was prepared using the following compounding agents (the amount added was the same as that of resin composition 1).
00 parts) and mixed with a Henschel mixer, pelletized by the method of Examples 1 to 3 described above, test pieces were prepared, and light resistance was tested.

The light resistance was evaluated by testing for 500 hours using a light resistance tester (manufactured by Suga Test Instruments Co., Ltd., Chew Panel light control weather meter return cycle. These results are shown in Table 9. Yellowness I, which is an indicator of discoloration)
ndex (YI value) is AS'l'MD-19
25, spectrophotometer (Murakami Color Research Institute model, C
This is a value measured using a high-speed spectrophotometer (Model A-35).

○Combination agent 1) Triethylene glycol-bis(3-(3-t-
7'thyl-5-methyl-4-hydroxyphenyl)propionate] ... 0.2 parts 2) 2- (3,5
-di-t-butyl-4-hydroxybenzyl)-2-n
-butylmalonate bis(1,2,2,6-bentamethyl-4-piperidyl) 0.3 parts 3) Di(2,4-di-t-butylphenyl)penta Erythritol diphosphite... 0.2 parts 4) Ethylene bisstearamide... 0.3 parts 5)
Pigment White 7...0.1 Part 9 Table T&r? By blending each of the copolymers of Examples 1 to 15 and Comparative Examples 14 to 15 and 2 with 1 and 2, resin compositions shown in Table 10 were prepared according to the methods of Examples 1 to 3. The adhesive strength with steel plate, aluminum and polyamide was measured using the following method. The results are shown in Table 10.

○Adhesive strength with steel plate: A 0.2-thick steel plate is degreased with trichloroethane,
After treatment with chromium dioxide and an aqueous sulfuric acid solution, a resin composition was interposed between the treated W4 plates, and the plates were bonded together by pressure bonding at 220° C. using a press. A test piece with a low width was prepared from this steel plate, and its peel strength at an angle of 90'' was measured at 23°C.

○ Adhesive strength to aluminum: After degreasing an aluminum plate with a thickness of 0.8 fin with a mixed solvent of acetone and toluene, a test piece was prepared and tested in the same manner as in the case of the steel plate described above.

Adhesive strength with O polyamide: 0.8N thick nylon-6 (Mitsubishi Kasei, Tsubamitsudo 5
A test piece with a width of 25 mm was prepared and tested in the same manner as above using T-220).

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

Claims (1)

[Claims] A maleimide monomer (A-1) and an unsaturated carboxylic acid monomer (A-2) in the presence or absence of a thermoplastic fat and/or a rubbery polymer. Any 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 a monomer (C) whose composition (excluding thermoplastic resin and rubbery polymer) is represented by formulas (1) and (2). Copolymer [
I] and an aromatic vinyl monomer (B-
1) and unsaturated carboxylic acid ester monomer (B-3
) and a copolymer obtained by polymerizing a monomer (D) copolymerizable with these, whose average composition (excluding thermoplastic resin and rubbery polymer) is
A copolymer composition represented by formulas (3) and (4), and an unsaturated carboxylic acid ester monomer (B-3)
Copolymer (1) with a content of more than 10% by weight 3-95
% by weight and 10% by weight or less of copolymer (2) 97-5
% by weight of a copolymer composition [II] and another thermoplastic resin and/or rubbery polymer [III], the blending ratio of which is expressed by formulas (5) and (6). A resin composition characterized by being within the range expressed by: O copolymer [I] (A) / (A) + (B) + (C) × 100 = 1 to 70% by weight (1) (C) / (A) + (B) + (C) × 100 =0 to 50% by weight (2)◯Copolymer composition [II] (B-3)/(B-1)+(B-3)+(D)×100
=3 to 80% by weight (3) (D)/(B-1)+(B-3)+(D)×100=0
~50% by weight (4) ◯Resin composition [I]/[I]+[II]×100=1-95% by weight (
5) [III] / [I] + [II] + [III] x 100 = 1 to 9
9% by weight (6)