JPS63161047A - Heat-resistant and impact-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having extremely excellent heat resistance and impact resistance, by blending two or more copolymers having different maleimide monomer component contents with a graft polymer. CONSTITUTION:(A) 2-98% resin consisting of two or more copolymers comprising A1: maleimide monomer component, A2: aromatic vinyl monomer component and optionally further A3: a monomer selected from an unsaturated nitrile monomer, an unsaturated carboxylic acid and an ester monomer thereof, having 1-60% component A based on sum of the monomers and 10-100% component A2 based on sum of the components A2 and A3 (difference in component A1 content is 3-50%) is blended with (B) 98-2% graft copolymer comprising a rubber-like polymer and a monomer component selected from the components A1, A2 and A3 and (C) 0-90% other resin and/or elastomer in such a way that the ratio of maleimide monomer component is 1-50%.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a heat-resistant and impact-resistant resin composition comprising two or more types of copolymers and a graft polymer in a specific relationship.

<Prior art> In recent years, in order to improve the heat resistance of polystyrene, polymethyl methacrylate, acrylonitrile-styrene copolymers, etc., there has been active development of resins that incorporate maleimide monomer components as heat resistance imparting components. It is progressing. Furthermore, a composition having excellent heat resistance has been proposed by blending a copolymer containing a maleimide monomer component with another resin such as an acrylonitrile-styrene copolymer. (For example, JP-A-57-98536, JP-A-58-2
17537, JP-A No. 61-91289) (Problem to be solved by the invention) In the composition, the content of the maleimide monomer in the composition can be controlled by changing the blending ratio of the maleimide copolymer and other resins. There are manufacturing advantages in that it can be varied and compositions with arbitrary heat resistance can be easily obtained.

However, many of these compositions exhibit incompatibility and cannot be said to be superior in terms of physical properties.

In particular, in compositions of maleimide copolymers and acrylonitrile-styrene copolymers, the effect of improving heat resistance by introducing maleimide monomers is not sufficiently exhibited. In addition, it is inferior in mechanical strength such as impact resistance.

Therefore, there has been a desire to develop a composition that overcomes the above-mentioned problems and is superior in maleimin and impact resistance.

<Means for solving the problems> As a result of intensive studies in view of the above problems, the present inventors have found that
A composition consisting of two or more types of copolymers of a specific composition containing a maleimide monomer component, and a specific mer that reduces the difference in the maleimide monomer component between the copolymers, is different from conventional compositions. The present invention was achieved based on the discovery that it has superior heat resistance and impact resistance.

That is, the present invention provides a maleimide monomer component (A) and an aromatic vinyl monomer component (B), or these (A) components, the (B) component, an unsaturated nitrile monomer, and an unsaturated carboxyl monomer component. It consists of at least two types of copolymers consisting of one or more types of monomer components (C) selected from acids and their ester monomers, and each copolymer has a composition of the formula ( Resin compositions [112-
98% by weight, a rubbery polymer, and the above (A), (B) and (C
98 to 2% by weight of a graft polymer [II] consisting of one or more monomer components selected from ), and other thermoplastic resins and/or elastomers (m)
o to 90% by weight, and the ratio of the maleimide monomer component to the total of the resin composition [I], the graft polymer [■], and other thermoplastic resin and/or elastomer [■] is 1 to 50%. % by weight.

The present invention will be explained in detail below.

0 Maleimide monomer component (A) Maleimide monomer components include maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octyl Maleimide, 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 4-chlorophenylmaleimide, N-2,3
or 4-bromophenylmaleimide, N-2,5-dichlorophenylmaleimide, N-1,4-dichlorophenylmaleimide, N-2,5-dibromophenylmaleimide, N-3,4-dibromophenylmaleimide, N-
2,4-6-trichlorophenylmaleimide, N-2,
4,6-tribromophenylmaleimide, 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-5-chlorophenylmaleimide, N-2-methoxy-5-chlorophenylmaleimide, etc.
Contains one dish or two or more dishes. Among these, N-aryl-substituted maleimides are particularly preferred.

0 Aromatic vinyl monomer (B) Examples of the aromatic vinyl monomer include styrene, σ-methylstyrene, d-chlorostyrene, pt-butylstyrene, p-methylstyrene, 0-chlorostyrene, p-chlorostyrene, 2゜5-dichlorostyrene, 3,4-dichlorostyrene, p-bromostyrene, 0-bromostyrene, 2,5-dipromostyrene, 3,4-dipromostyrene, 2-isopromostyrene Examples include lunaphthalene, and one or more of them can be used. Among these, styrene or α-methylstyrene is usually preferred.

0 Monomer (C) In the present invention, a monomer (C) that can constitute a copolymer together with the maleimide monomer (A) component and the aromatic vinyl monomer (B) component. is one or more monomers selected from unsaturated nitrile monomers, unsaturated carboxylic acids, and ester monomers thereof.

Examples of unsaturated nitrile monolayers include acrylonitrile,
Examples include methacrylonitrile, maleonitrile, fumaronitrile, etc., and one or more types can be used. Among these, acrylonitrile is usually preferred.

Examples of unsaturated carboxylic acids and their ester monomers include (meth)acrylic acid and its methyl, ethyl, propyl, butyl, lauryl, cyclohexyl, 2-hydroxyethyl, glycidyl, and dimethylaminoethyl. Examples include ester monomers, maleic anhydride, iconic anhydride, citraconic anhydride, himic anhydride, and mono- and dialkyl esters thereof.

One or more types of these can be used. Among these, methacrylic acid, methyl methacrylate,
Maleic anhydride and the like are preferred.

In addition, in the above-mentioned monomer component (C), component (C)
A part of (C), that is, up to 50% by weight of component (C), can be substituted with one or more of the following copolymer components.

Ethylene, propylene, butene-1, pentyne-1,4
-Methylpentene-1, vinyl chloride, vinylidene chloride,
Tetrafluoroethylene, monochlorotrifluoroethylene, hexafluoropropylene, butadiene, acrylamide, methacrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinyl ether, vinyl ketone, coumaron, indene and acenaphthylene.

0 copolymer Each of the copolymers constituting the resin composition (1) in the present invention comprises the above-mentioned maleimide monomer component (A) and aromatic vinyl monomer component (B), or the maleimide monomer component (B). one or more selected from the polymer component (A), the aromatic vinyl monomer component (B), an unsaturated nitrile monomer, an unsaturated carboxylic acid and its ester monomer; The monomer component (C) has a composition within the range represented by formulas (1) and (2), respectively.

The maleimide monomer component (A) in each copolymer is 1
The reason for limiting the amount to 60% by weight is to obtain a final composition that has excellent compatibility and a good balance of heat resistance, processability, and mechanical strength.

Moreover, as shown in formula (2), the above-mentioned monomer component (
The ratio of component (B) in the total of B) and (C) is 10
-100% by weight, and if it is less than 10% by weight (component (C) exceeds 90% by weight), thermal stability deteriorates, such as coloring and thermal decomposition being likely to occur during molding at high temperatures.

There is no particular limit to the intrinsic viscosity of each copolymer (value measured in dimethylformamide solution at 30°C [η "dt/9"), but those within the range of 0.3 to 1.5 are preferred. preferable.

C resin composition [I] The composition of the present invention comprises a copolymer 2 having a specific composition as described above.
The composition is composed of at least one type of maleimide monomer component (A) and the difference in content of the maleimide monomer component (A) between the copolymers is 3 to 50% by weight.

If the difference in the maleimide monomer component (A) content between the copolymers is less than 3% by weight, the effect of improving heat resistance by the maleimide monomer component will not be sufficiently exhibited;
If it exceeds , the difference in the glass transition temperature of each copolymer will be large, and therefore, for example, when these are blended by the melt mixing method, the difference in melt viscosity between the two will become large. As a result, it not only takes a long time to evenly blend the two, but also
It is difficult to obtain resins that have the characteristics of these resins.

In the present invention, not only resin compositions consisting of two copolymers having different contents of the maleimide monomer component (A) but also resin compositions consisting of three or more types are included. When the copolymer is composed of three or more types of copolymers, the difference in component (A) content between copolymers with close maleimide monomer component (A) contents must be 3 to 50% by weight.

Therefore, the difference in content between the copolymer with the smallest content of component (A) and the copolymer with the largest content may exceed 50% by weight.

In addition, when consisting of three or more types of copolymers, the content difference of maleimide monomer component (A) between each copolymer is 3
50% by weight, and the content difference between the copolymer with the smallest content of component (A) and the copolymer with the largest content is preferably 50% by weight or less.

In addition, in terms of compatibility between the copolymers and the compatibility between the graft polymer and each copolymer, the copolymer containing a high maleimide monomer component and the copolymer containing a low maleimide monomer component are It is preferable that the composition (weight) ratio is 2/98 to 98/2.

Copolymers containing these maleimide monomer components can be produced by known methods. For example, a method in which a maleimide monomer and a copolymerizable monomer are directly copolymerized, or a method in which a copolymer containing maleic anhydride is reacted with ammonia, a primary amine, an isocyanate ester, etc. to form an imide There are ways to make it. These copolymers can be produced by bulk polymerization, suspension polymerization, bulk suspension polymerization, emulsion polymerization, solution polymerization, and the like.

0 Graft polymer [II] Graft polymer (II is one or more monomers selected from precursors) used as the Kusunoki component of the thermal impact resistant resin composition of the present invention It is a graft polymer consisting of a body component and a rubber-like polymer.

A rubbery polymer exhibits a rubbery state at room temperature. Examples of the rubbery polymer include polybutadiene, styrene-butadiene random or block copolymers,
Hydrogenated styrene-butadiene random or block copolymer, acrylonitrile-butadiene copolymer, neoprene rubber, chloroprene rubber, isobutylene rubber, natural rubber, ethylene-propylene rubber, ethylene-propylene-conjugated diene rubber, chlorinated polyethylene, chlorinated Ethylene-propylene-conjugated diene rubber, acrylic rubber,
Ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid ester copolymer such as methyl (meth)acrylate, ethyl, propyl, butyl, glycidyl or dimethylaminoethyl, ethylene-vinyl acetate-glycidyl methacrylate copolymer Examples include ethylene-methyl acrylate-glycidyl methacrylate copolymer, polyvinyl butyral, polyester elastomer, and polyamide elastomer. Both crosslinked and uncrosslinked products can be used, and mixtures of two or more types can also be used.

As monomer components such as maleimide monomers, aromatic vinyl monomers, unsaturated nitrile monomers, unsaturated carboxylic acids and their ester monomers, etc., which are graft-polymerized to rubbery polymers. Examples include the compounds mentioned in the above copolymer section.

In particular, aromatic vinyl monomers include styrene, α-methylstyrene, and p-methylstyrene, and unsaturated nitrile monomers include at least an acrylic monomer and an unsaturated nitrile monomer. A graft polymer obtained by graft polymerization of and/or maleimide monomer components is preferred.

The graft polymer [1) can be produced by various polymerization methods such as those listed in the above section on copolymers. In addition, there is no particular restriction on the structure of the graft polymer, but the weight average particle diameter is 0.05 to 3 μm, and the grafting rate is 10 to 150.
Preferably, the rubber content is 5 to 80% by weight.

0 Other thermoplastic resins and elastomers [I Acrylonitrile-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-σ-methylstyrene copolymer, methacrylonitrile-ru-styrene copolymer,
Polymethyl methacrylate, methyl methacrylate-styrene copolymer, methyl methacrylate-acrylonitrile-
Styrene copolymer, methyl methacrylate-methacrylic acid copolymer, methyl methacrylate-maleic anhydride copolymer, methyl methacrylate-glutaric anhydride copolymer, methyl methacrylate-styrene-glutaric anhydride copolymer, Methyl methacrylate-glutarimide copolymer, styrene-acrylonitrile-methacrylic acid copolymer, polyethylene, polypropylene, polybutene-11 ethylene-butene-1 copolymer, propylene-butene-1 copolymer, propylene-ethylene block copolymer polymer, ethylene-propylene rubber, maleic anhydride 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, dimethylamine ethyl, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene- Perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polybrorotrifluoroethylene, polyvinyl butyral, polyvinyl chloride, butadiene rubber, styrene-butadiene random or block copolymer, hydrogenated styrene- Butadiene random or block copolymers, acrylonitrile-butadiene rubber, isobutylene rubber, acrylic rubber, silicone resins, polycarbonates, polyesters, polyamides, polyimides, polyamideimides, polyetherimides, polyetheretherketones, polyphenylene sulfides.

Examples include polysulfone, polyethersulfone, polyphenylene oxide, polyoxymethylene, and the like. One or more types of these can be used.

0 Heat-resistant impact-resistant resin composition (composition) The composition of the present invention is a resin composition [132-
98% by weight, graft polymer [II] 98 to 2% by weight, and other thermoplastic resin and/or elastomer [■] 0 to 90% by weight, and the resin composition [I], the graft polymer The ratio of the maleimide monomer component (the total of the maleimide monomer components obtained from the resin composition [I]) to the total of the polymer [II] and other thermoplastic resins and/or elastomers (I [)] is 1 to 50% by weight of the composition.

If the resin composition CI) consisting of a specific copolymer is less than 2% by weight, the heat resistance will be low, while if it exceeds 98% by weight, it will be difficult to obtain a product with high impact strength. In addition, graft polymer [11
) is less than 2% by weight, it is difficult to obtain a product with high impact strength;
On the other hand, if it exceeds 98% by weight, heat resistance will be low. Furthermore, other thermoplastic resins and/or elastomers [■]
If the amount exceeds % by weight, the properties of the maleimide monomer component-containing copolymer and graft polymer will be lost.

Furthermore, if the proportion of the maleimide monomer component is less than 1% by weight, heat resistance will be low, while if it exceeds 50% by weight, processability and mechanical strength will decrease.

The composition of the present invention can be produced by any method depending on the production method of each polymer (resin, elastomer). For example, latex, suspension, solution, powder,
They can be blended in the form of beads, pellets, blocks, etc., and finally melt-kneaded in a pan mixer or extruder to form a composition.

For the composition of the present invention, antioxidants, heat stabilizers, light stabilizers, lubricants, plasticizers, antistatic agents, blowing agents,
Inorganic and organic fillers, flame retardants, surface gloss improvers, matting agents, etc. can be added. These various additives can be added during the manufacturing process of the composition or in subsequent processing steps.

It goes without saying that the composition of the present invention can be widely used alone in many fields such as vehicle parts, ship parts, aircraft parts, building materials, electrical parts, furniture, and office supplies.
Because it has a very good affinity with various polar materials, it can be used for glass fibers, metal fibers, carbon a fibers or their powders, calcium carbonate, talc, gypsum, alumina, silica, mica, boron nitride, zirconia, silicon carbide, Can be used as a composite material such as potassium titanate.

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

All parts and percentages given in the examples are by weight.

Reference Example 1 Synthesis of Copolymer Copolymer (1) 70 parts of pure water, 0.01 part of potassium persulfate, and 0.1 part of sodium dodecylbenzenesulfonate were placed in a 100/2 reactor equipped with a stirring blade and baffles. After charging and replacing the inside of the reactor with nitrogen gas, the temperature was raised while stirring until the internal temperature reached 65.
When 6C was reached, a solution consisting of 10 parts of N-phenylmaleimide, 23 parts of acrylonitrile, 67 parts of styrene and 0.4 part of t-dodecylmercaptan, 0.2 part of potassium persulfate, and 0.7 part of sodium dodecylbenzenesulfonate was added. While continuously adding an aqueous solution consisting of 50 parts of pure water and 50 parts of pure water at a rate of 25 parts/hour and 12.5 parts/hour, respectively, the temperature was raised to 75°C over 30 minutes. After the continuous addition of these solutions was completed, the temperature was further maintained at 75° C. for 2 hours. As a result, a latex with a polymerization rate of 98.6% and a pH of 2.7 was obtained.

The solid concentration of this latex was adjusted to 20X, charged into the above reactor, and heated to 105°C. 15% to this
The solid content of latex is 100% by adding an aqueous solution of magnesium sulfate to
Add 30 parts per part over 10 minutes, then add another 10 parts per part.
The latex was coagulated by holding it at 110°C for minutes.

After cooling, the polymer was separated from the slurry, washed with water, and dried.

Copolymer (2) Maleic anhydride-styrene copolymer (manufactured by ARCO, DILARK ■332, maleic anhydride content 14%) was placed in the hopper of a 40 mmφ twin-screw extruder with a side feeder and a vent, and was heated under a nitrogen gas atmosphere. was fed at a rate of Roll/hour. The resin temperature at the exit of the extruder was set to 2306C.
Additionally, the average residence time was set to 2 minutes.

To this, a solution consisting of 98 parts of aniline, 50 parts of ethylbenzene, and 2 parts of trimethylamine was fed from a side feeder at a rate of 2.19/hr. Ethylbenzene, trimethy, reaamine, unreacted aniline, water, etc. The strands coming out of the extruder were cut with a cutter to form pellets.

Copolymer (3) Into the reactor used for copolymer (1), add 70 parts of pure water, 0.02 part of potassium persulfate, and 0.0 part of sodium lauryl sulfate.
After charging 5 parts and purging the inside of the reactor with nitrogen, 7
The temperature was raised to 0°C.

To this was added a solution consisting of 30 parts of N-phenylmaleimide, 20 parts of acrylonitrile, 50 parts of styrene and 0.2 parts of t-dodecylmercaptan, and 0.2 parts of potassium persulfate.
1 part, 1.0 part of sodium lauryl sulfate and 50 parts of pure water
The temperature was raised to 75° C. over 30 minutes while continuously adding 20 parts/hour and 10 parts/hour of an aqueous solution consisting of 20 parts/hour and 10 parts/hour, respectively. After completing the continuous addition of these solutions, 7
It was held at 5°C for 2 hours. As a result, the polymerization rate was 98.8%,
A latex with a pH of 2.6 was obtained.

The solid concentration of this latex was adjusted to 15%, and the latex was charged into the above reactor and heated to 135°C. After adding 30 parts of 20% calcium chloride aqueous solution per 100 parts of latex solid content over 10 minutes,
The latex was coagulated by maintaining it at 5°C. After cooling, the polymer was separated from the slurry, washed with water, and dried.

Copolymer (41, (5), (6), (7),
(8), (9) and (121) respectively copolymer (3
) The copolymers shown in Table 1 were obtained according to the production method of

Copolymer αO) 150 parts of pure water and 5 parts of pure water were added to the reactor used for copolymer (1).
After charging 4 parts of aqueous solution of hydroxypropyl methyl cellulose with a concentration of 4 parts and purging the inside of the reactor with nitrogen gas, 28 parts of acrylonitrile, 72 parts of styrene, 0.43 parts of t-dodecyl mercaptan and 0.5 parts of lauroyl peroxide were added under stirring. I prepared it. Raise the temperature to 75°C and
After polymerization for a period of time, the temperature was further raised to 80°C and held for 1 hour. Next, the temperature was raised to 1OO0C, and unreacted monomers were removed by distillation while blowing steam into the reactor. After cooling, the polymer was separated, washed with water, and dried.

A reactor containing copolymer αυ 5j was charged with 700 parts of dimethylformamide, 6 parts of acrylonitrile, 24 parts of styrene, and 0.2 parts of t-dodecylmercaptan, and after purging the inside of the reactor with nitrogen gas, the temperature was raised to 70°C with stirring. It was warm. Add to this 0.2 parts of lauroyl peroxide and 0 parts of benzoyl peroxide.
．． After adding a solution consisting of 5 parts of N-phenylmaleimide, 5 parts of acrylonitrile, and 5 parts of dimethylformamide, a mixed solution consisting of 66 parts of N-phenylmaleimide, 5 parts of acrylonitrile, and 200 parts of dimethylformamide was continuously added over 2 hours. After that, 9
The temperature was raised to 0°C and held for 1 hour. After cooling, the polymer solution was poured into a large amount of methanol to cause precipitation, and then the polymer was separated, thoroughly washed with methanol, and dried.

Table 1 shows the analytical values of each copolymer obtained in Reference Example 1 above.

Reference Example 2 Synthesis of graft polymer Graft polymer (a) 30 parts of pure water was charged into the reactor used for copolymer (1),
While stirring, add polybutadiene latex (rubber weight average particle size 0.46 μm, gel content 72%, solid content 41%, emulsifier sodium dehydroabietate 1.5%, pH 12).
, 1) 10 parts (solid content equivalent) and butadiene-styrene copolymer latex (rubber weight average particle diameter 0.12
tt m, gel content 82%, solid content 42%, styrene content 15%, emulsifier sodium oleate 2%, pH 1
1,7) 80 parts (in terms of solid content) were charged. Next, ferrous sulfate heptahydrate 0.002 part, sodium pyrophosphate 0.1
After adding 0.2 parts of dextrose and 0.2 parts of dextrose, the inside of the reactor was purged with nitrogen gas and heated to 70°C. t for this
- After charging an aqueous solution consisting of 0.01 part of butyl hydroperoxide and 2 parts of pure water, a solution consisting of 15 parts of acrylonitrile, 25 parts of styrene, and 0.2 parts of t-dodecyl mercaptan, and 0.0 parts of t-butyl hydroperoxide, respectively. .2 parts of sodium tehydroabietate, 0.6 parts of sodium hydroxide, 0.2 parts of sodium hydroxide, and 20 parts of pure water were continuously added over 3 hours. Thereafter, it was heated to 75°C and held for 2 hours. As a result, a latex with a polymerization rate of 98.7% and a pH of 11.9 was obtained.

The solid concentration of this latex was adjusted to 25%, charged into the above reactor, and heated to 90°C. To this was added 20 parts of a 15% aqueous magnesium sulfate solution per 100 parts of solid content of the latex over 10 minutes. After cooling, the polymer was separated from the slurry, washed with water, and dried.

After charging an aqueous solution consisting of 200 parts of pure water and 0.3 parts of hydroxyethyl cellulose into the reactor used for the graft polymer (rostral copolymer (1)), ethylene (45%)-propylene (52%) cut into small pieces was added. %) - cyclopentadiene (3%) rubber 50
I prepared a section. To this were added 18 parts of acrylonitrile, 35 parts of styrene, 0.1 part of dicumyl peroxide and t-
A solution consisting of 0.3 parts of dodecyl mercaptan was added, and after purging the inside of the vessel with nitrogen gas, the temperature was raised to 120° C. with stirring and polymerization was carried out for 4 hours. After cooling, the polymer was separated, washed with water, and dried.

Graft polymer (c) Add 30 parts of pure water and 1st sulfuric acid to the reactor used for copolymer (1).
O, OOA parts of iron heptahydrate, 0.2 parts of sodium bisulfite, and 0.2 parts of dextrose are added, and then polybutyl acrylate latex (rubber weight average particle diameter of 0.0 parts) is added.
27 μm 1 gel content 73%, solid content 40%, emulsifier sodium dodecylbenzenesulfonate 1.6%/rubber, pH
After charging 60 parts (in terms of solid content) of 5,7), the inside of the reactor was purged with nitrogen gas and heated to 75°C with stirring. To this is added a solution consisting of 4 parts of N-phenylmaleimide, 8 parts of acrylonitrile, 28 parts of styrene and 0.2 parts of t-dodecylmercaptan, 0.2 parts of cumene hydroperoxide, 0.4 parts of sodium dodecylsulfonate and pure An aqueous solution consisting of 20 parts of water was added continuously over a period of 3 hours. Thereafter, the temperature was raised to 80°C and held for 2 hours. As a result, latex with a polymerization rate of 98.5% was obtained. Thereafter, the polymer was recovered in the same manner as in the case of graft polymer (a).

Graft polymer (to) Add 30 parts of pure water and 1st sulfuric acid to the reactor used for copolymer (1).
0.002 part of iron heptahydrate, 0.1 part of sodium pyrophosphate and 0.2 part of dextrose were added, and then acrylonitrile-butadiene copolymer latex (rubber weight average particle size 0.17 μm/gel content 77%, acrylonitrile After charging 60 parts (in terms of solid content) of 20% content, 43% solid content, 1.6 parts of emulsifier sodium lauryl sulfate, pH 5.2), the inside of the reactor was replaced with nitrogen gas, and the reactor was heated for 70' while stirring. The temperature was raised to C. To this is added a solution consisting of 7 parts of acrylonitrile, 27 parts of styrene, 6 parts of glycidyl methacrylate and 0.2 parts of t-dodecyl mercaptan, and 0.0 parts of cumene hydroperoxide.
2 parts, 0.5 parts of sodium lauryl sulfate and 20 parts of pure water
of the aqueous solution was added continuously over a period of 3 hours. Thereafter, it was heated to 80°C and held for 2 hours. As a result, the polymerization rate was 9
8.5% latex was obtained. Below, the graft polymer (
The polymer was recovered in the same manner as in case a).

Reference Example 3 Other thermoplastic resin and/or elastomer CI [[
), styrene-acrylonitrile copolymer (copolymer in Reference Example 1 & 10) “AS tri-recarbonate “PC” or acrylonitrile (30%)-
Butadiene (70%) rubber "NBR" was used.

Examples and Comparative Examples Table 2 shows the copolymer obtained in Reference Example 1 and the graft polymer obtained in Reference Example 2, as well as the other thermoplastic resins or elastomers shown in Reference Example 3. and third
Blend in the proportions shown in the table, and make 10 of these blends.
0 parts of triethylene glycol-bis[8-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] and di(2,4
- di-t-butylphenyl) pentaerythritol diphosphite (0.2 part) and 0.05 part of ethylene bisstearamide as a lubricant were added, and 40rIrIn with a vent was added.
250~3o in a φ twin screw extruder.

The mixture was kneaded at ℃ and pelletized. The total amount of residual monomers in these pellets was 0.2% or less in all cases.

This pellet was molded at 250 to 320°C using an injection molding machine to prepare a test piece, and its physical properties were measured. This result is the second
Shown in Table and Table 3.

0 composition is the value determined by CHN and O elemental analysis.

NPMI: N-Phenylmaleimide S: Styrene AMS: σ-Methylstyrene 8N: Acrylonitrile MAN: Methacrylonitrile MMA: Methyl methacrylate MAA: Methacrylic acid 0 Intrinsic viscosity 1 [η]" is dimethylporamide solution, 3
Measured value at 0°C.

0 Glass transition degree "Tg" is measured by differential scanning calorimeter (DSC)
Value measured at.

・Heat distortion temperature "I (DT") is 1 inch thick test piece, 26
Value measured under 4 psi load and no annealing.

The Q-notched Izot impact strength "N-15" is <Effect of the invention> The composition of the present invention, which is composed of two or more maleimide copolymers and a graft polymer in a specific relationship, has a This composition has outstanding heat resistance and impact resistance.

Claims (1)

[Scope of Claims] Maleimide monomer component (A) and aromatic vinyl monomer component (B), or these (A) components, (B) component and unsaturated nitrile monomer, unsaturated carbon It consists of at least two types of copolymers consisting of one or more types of monomer components (C) selected from acids and their ester monomers, and each copolymer has a composition of the formula ( Resin composition [I] 2 which is within the range expressed by 1) and (2) and in which the difference in maleimide monomer component (A) content between each copolymer is 3 to 50% by weight
Graft polymer [II] consisting of ~98% by weight, a rubbery polymer, and one or more monomer components selected from the above (A), (B), and (C). 98-2% by weight, and other thermoplastic resins and/or elastomers [III]
0 to 90% by weight, and the ratio of the maleimide monomer component to the total of the resin composition [I], graft polymer [II], and other thermoplastic resin and/or elastomer [III] is 1 to 50% by weight. % of a heat-resistant and impact-resistant resin composition. [(A)/(A)+(B)+(C)]×100=1 to 6
0% by weight……(1) [(B)/(B)+(C)]×1
00=10-100% by weight……(2)