JPH0680134B2 - Heat resistant and impact resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a heat resistant and impact resistant resin composition comprising two or more copolymers and a graft polymer having a specific relationship.

<Prior Art> In recent years, for the purpose of improving the heat resistance of polystyrene, polymethylmethacrylate, acrylonitrile-styrene copolymer, etc., development of resins into which a maleimide monomer component is introduced as a heat resistance-imparting component has been actively conducted. It is being advanced. Further, a composition having excellent heat resistance is proposed by blending a copolymer containing a maleimide-based monomer component with another resin such as an acrylonitrile-styrene copolymer. (For example, JP-A-57-98536, JP-A-58-217537, JP-A-61-91239) <Problems to be solved by the invention> In the composition, a maleimide-based copolymer and another resin are mixed. The content of the maleimide-based monomer in the composition can be varied depending on the blending ratio, and there is a manufacturing advantage that a composition having arbitrary heat resistance can be easily obtained.

However, many of the compositions exhibit incompatibility, and it cannot be said that the composition is superior in physical properties. In particular, in the composition of the maleimide-based copolymer and the acrylonitrile-styrene copolymer, the effect of improving the heat resistance by introducing the maleimide-based monomer is not sufficiently exhibited. In addition, it is inferior in mechanical strength such as impact resistance.

Therefore, since the above problems and the maleimide-based monomer is expensive, the development of a composition excellent in impact resistance as well as excellent in heat resistance was sufficiently improved by the maleimide-based monomer. Was wanted.

<Means for Solving Problems> As a result of intensive investigations by the present inventors in view of the above problems,
A resin composition and a graft polymer comprising two or more copolymers having a specific composition containing a maleimide monomer component and having a specified difference in the maleimide monomer component between the copolymers, or a graft polymer thereof. The present invention has been found to have a heat resistance and impact resistance superior to those of conventional compositions, and has reached the present invention.

That is, the present invention provides a maleimide-based monomer component (A) and an aromatic vinyl-based monomer component (B) or components (A), a component (B) and an unsaturated nitrile-based monomer, and an unsaturated carboxylic monomer. The composition comprises at least two types of copolymers consisting of an acid and one or more types of monomer components (C) selected from ester monomers thereof, and the composition of each copolymer is represented by the formula ( 1) and (2), and the difference in the content of the maleimide monomer component (A) between the copolymers is 3 to 50% by weight. 98
Graft polymer [II] 98 to 90% by weight, a rubber-like polymer and one or more monomer components selected from the above (A), (B) and (C) 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], the graft polymer [II] and the other thermoplastic resin and / or the elastomer [III] is 1 to 50% by weight. %
The present invention provides a heat-resistant and impact-resistant resin composition.

The present invention will be described in detail below.

Maleimide-based monomer component (A) As the maleimide-based monomer component, maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-2,3 or 4-methylphenyl maleimide, N-2,3 or 4-ethylphenyl maleimide, N-2,3 or 4-butylphenyl maleimide , N
-2,6-Dimethylphenylmaleimide, N-2,3 or 4
-Chlorophenylmaleimide, N-2,3 or 4-bromophenylmaleimide, N-2,5-dichlorophenylmaleimide, N-3,4-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-5chlorophenylmaleimide,
N-2-methoxy-5-chlorophenylmaleimide and the like are exemplified, and one or more kinds are contained.
Of these, N-aryl-substituted maleimides are particularly preferable.

Aromatic Vinyl Monomer (B) Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, α-chlorostyrene, pt-butylstyrene, p-methylstyrene, o-chlorostyrene, p. -Chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, p-bromostyrene, o-bromostyrene,
2,5-dibromostyrene, 3,4-dibromostyrene, 2-
Isopropenylnaphthalene and the like can be mentioned, and one kind or two or more kinds can be used. Of these, styrene or α-methylstyrene is usually preferred.

Monomer (C) In the present invention, a monomer (C) capable of forming a copolymer with the above-mentioned maleimide-based monomer (A) component and aromatic vinyl-based monomer (B) component. Is one or more kinds of monomers selected from unsaturated nitrile-based monomers, unsaturated carboxylic acids and their ester-based monomers.

As the unsaturated nitrile-based monomer, acrylonitrile,
Methacrylonitrile, maleonitrile, fumaronitrile, etc. are mentioned, and 1 type (s) or 2 or more types can be used. Of these, acrylonitrile is usually preferred.

Examples of the unsaturated carboxylic acid and its ester monomer include (meth) acrylic acid and its (meth) acrylic acid such as methyl, ethyl, propyl, butyl, lauryl, cyclohexyl, 2-hydroxyethyl, glycidyl and dimethylaminoethyl. Ester monomers, maleic anhydride, itaconic anhydride, citraconic anhydride,
Hymic acid anhydrides and their mono- and dialkyl esters and the like.

These may be used alone or in combination of two or more. Of these, usually methacrylic acid, methyl methacrylate,
Maleic anhydride and the like are preferred.

In addition, in the above-mentioned monomer component (C), the component (C)
It is also possible to replace a part of the above, that is, 50% by weight or less of the component (C) with one or more of the following copolymer components.

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

Copolymer Each of the copolymers constituting the resin composition [I] of the present invention is a maleimide-based monomer component (A) and an aromatic vinyl-based monomer component (B), or a maleimide-based monomer. One or more selected from the body component (A), the aromatic vinyl monomer component (B), the unsaturated nitrile monomer, the unsaturated carboxylic acid and its ester monomer. It is composed of the monomer component (C), and its composition is within the ranges represented by the formulas (1) and (2), respectively.

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

Further, as shown in the formula (2), the ratio of the component (B) in the total of the above-mentioned monomer components (B) and (C) is 10
If the content is less than 10% by weight (the content of the component (C) exceeds 90% by weight), the thermal stability is deteriorated such that coloring or thermal decomposition is likely to occur during molding under high temperature.

The intrinsic viscosity of each copolymer (dimethylformamide solution, value [η] “dl / g” measured at 30 ° C.) is not particularly limited, but is preferably within the range of 0.3 to 1.5.

Resin composition [1] The composition of the present invention is a copolymer 2 having a specific composition as described above.
The composition is composed of at least one species and the difference in the content of the maleimide-based monomer component (A) between the copolymers is 3 to 50% by weight.

When the difference in the content of the maleimide-based monomer component (A) between the copolymers is less than 3% by weight, the heat resistance improving effect of the maleimide-based monomer component is not sufficiently exhibited, while when it exceeds 50% by weight, Since the difference in glass transition temperature of the copolymer is large, for example, when these are blended by the melt kneading method, the difference in melt viscosity between the two becomes large. As a result, not only does it take a long time to uniformly blend the two,
It is difficult to obtain a resin that has the characteristics inherent in these resins.

In the present invention, not only a resin composition composed of two kinds of copolymers having different contents of the maleimide monomer component (A) but also a resin composition composed of three or more kinds are included. When it is composed of three or more kinds of copolymers, the difference in the content of the component (A) between the adjacent copolymers of the maleimide monomer component (A) content must be 3 to 50% by weight. Therefore, the difference in content between the minimum copolymer and the maximum copolymer having the content of component (A) may exceed 50% by weight.

When the copolymer is composed of three or more kinds, the difference in the content of the maleimide-based monomer component (A) between the copolymers is 3
The content difference between the minimum copolymer and the maximum copolymer having the content of the component (A) is preferably 50% by weight or less.

Incidentally, from the aspect of compatibility between the copolymers and the compatibility of the graft polymer and each copolymer, between the high maleimide-based monomer component-containing copolymer and the low maleimide-based monomer component-containing copolymer The composition (weight) ratio is preferably 2/98 to 98/2.

Copolymers containing these maleimide-based monomer components can be produced by known methods. For example, a method of directly copolymerizing a maleimide-based monomer and a copolymer monomer, a copolymer containing maleic anhydride is reacted with ammonia, a primary amine, an isocyanic acid ester, or the like to obtain an imide. There is a method to make it. These copolymers can be produced by bulk polymerization, suspension polymerization, bulk suspension polymerization, emulsion polymerization, solution polymerization and the like.

Graft polymer [II] The graft polymer [II] used as a constituent component of the heat-resistant and impact-resistant resin composition of the present invention is a maleimide-based monomer, an aromatic vinyl-based monomer, or an unsaturated nitrile. It is a graft polymer composed of a rubber-like polymer and one or more kinds of monomer components selected from the group-based monomers, unsaturated carboxylic acids and their ester-based monomers.

The rubber-like polymer has a rubber-like shape at room temperature. As this rubber-like polymer, for example, polybutadiene,
Styrene-butadiene random or block copolymer, 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-methyl (meth) acrylate, ethyl, propyl, butyl, glycidyl or dimethylaminoethyl, etc. (Meth) acrylic acid ester copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, polyvinyl butyral, polyester elastomer, polyamide elastomer and the like. This may be a crosslinked product or an uncrosslinked product, or may be a mixture of two or more kinds.

Maleimide-based monomer graft-polymerized on rubber-like polymer, aromatic vinyl-based monomer, unsaturated nitrile-based monomer,
Examples of the monomer component such as unsaturated carboxylic acid and its ester monomer include the compounds described in the section of the above-mentioned copolymer.

In particular, styrene, d-methylstyrene and p-methylstyrene as the aromatic vinyl-based monomer, acrylonitrile and methacrylonitrile as the unsaturated nitrile-based monomer, and methacrylic acid and glutaric anhydride as the unsaturated carboxylic acid. Further, maleic anhydride, methyl methacrylate as the unsaturated carboxylic acid ester, and N-phenylmaleimide as the maleimide-based monomer are preferable.

Further, as the graft polymer, a graft polymer obtained by graft-polymerizing at least an aromatic vinyl-based monomer, an unsaturated nitrile-based monomer and / or a maleimide-based monomer component into a rubber-like polymer is preferable. .

The graft polymer [II] can be produced by various polymerization methods such as those mentioned above in the section of copolymer. The structure of the graft polymer is not particularly limited, but it is preferable that the weight average particle diameter is 0.05 to 3 μm, the graft ratio is 10 to 150% by weight, and the rubber content is 5 to 80% by weight.

Other thermoplastic resins and elastomers [III] Other thermoplastic resins and elastomers [III] used in the present invention include, for example, polystyrene, maleic anhydride-styrene copolymer, maleic anhydride-acrylonitrile-styrene copolymer. Combined, acrylonitrile-
Styrene copolymer, acrylonitrile-d-methylstyrene copolymer, methacrylonitrile-styrene copolymer, polymethylmethacrylate, methylmethacrylate-styrene copolymer, methylmethacrylate-acrylonitrile-styrene copolymer, methacryl Methyl acid-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-1,
Ethylene-butene-1 copolymer, propylene-butene-
1 copolymer, propylene-ethylene block copolymer,
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, ethyl, propyl, butyl, glycidyl, and dimethylaminoethyl, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl Vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinyl butyral, polyvinyl chloride, butadiene rubber, styrene-butadiene random or block. Copolymer, hydrogenated styrene-butadiene random or block copolymer, acrylonitrile-butadiene rubber, isobutylene rubber, acrylic rubber, silicone resin, polycarbonate, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polyetheretherketone, Examples thereof include polyphenylene sulfide, polysulfone, polyether sulfone, polyphenylene oxide, polyoxymethylene and the like. These 1 type (s) or 2 or more types can be used.

Heat-resistant and impact-resistant resin composition (composition) The composition of the present invention comprises a resin composition [I] of 2 to 98% by weight and a graft polymer [II] of 98-
2% by weight and other thermoplastic resin and / or elastomer [III] 0 to 90% by weight,
And the maleimide-based monomer component (the maleimide-based monomer derived from the resin composition [I] relative to the total of the resin composition [I], the graft polymer [II] and the other thermoplastic resin and / or the elastomer [III]. It is a composition having a ratio of (total body components) of 1 to 50% by weight.

If the resin composition [I] made of a specific copolymer is less than 2% by weight, heat resistance is low, while if it exceeds 98% by weight, it is difficult to obtain a resin composition having high impact strength. If the graft polymer [II] is less than 2% by weight, it is difficult to obtain a polymer having high impact strength.
If it exceeds 98% by weight, the heat resistance is low. In addition, 90% by weight of other thermoplastic resin and / or elastomer [III]
If it exceeds, the properties of the maleimide-based monomer component-containing copolymer and the graft polymer will be lost.

Further, when the proportion of the maleimide-based monomer component is less than 1% by weight, heat resistance is low, while when it exceeds 50% by weight, workability and mechanical strength are deteriorated.

The composition of the present invention can be produced by any method corresponding to the production method of each polymer (resin, elastomer). For example, the composition can be obtained by blending in the state of latex, suspension, solution, powder, beads, pered, block, etc., and finally melt-kneading with a Banbury mixer or an extruder.

For the composition of the present invention, if necessary, an antioxidant, a heat stabilizer, a light stabilizer, a lubricant, a plasticizer, an antistatic agent, a foaming agent,
Inorganic and organic fillers, flame retardants, surface gloss improvers, matting agents and the like can be added. These various additives can be added during the manufacturing process of the composition or in the subsequent processing process.

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, office supplies, etc.,
Glass fiber, metal fiber, carbon fiber or their powders, calcium carbonate, talc, gypsum, alumina, silica, mica, boron nitride, zirconia, silicon carbide, titanium because they have very good affinity with various polar materials. It can be used as a composite material such as potassium acid.

The present invention will be described 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) Pure water was added to a 100 l reactor equipped with a stirring blade and baffles.
Parts, 0.01 parts of potassium persulfate and 0.1 parts of sodium dodecylbenzenesulfonate were charged, the inside of the reactor was replaced with nitrogen gas, and the temperature was raised with stirring. When the internal temperature reached 65 ° C, N-phenylmaleimide 10 Part, acrylonitrile 23
Parts, styrene 67 parts and t-dodecyl mercaptan 0.4
Solution consisting of 10 parts of potassium persulfate, 0.2 parts of potassium persulfate, 0.7 parts of sodium dodecylbenzenesulfonate and 50 parts of pure water are continuously added at a rate of 25 parts / hour and 12.5 parts / hour, respectively, at 75 ° C for 30 minutes. The temperature was raised to. After the continuous addition of these solutions was completed, the temperature was maintained at 75 ° C for 2 hours. As a result, a latex having a polymerization rate of 98.6% and a pH of 2.7 was obtained.

The solid content concentration of this latex was adjusted to 20%, and the mixture was charged into the above reactor and heated to 105 ° C. Add a 15% magnesium sulfate solution to this for 30 parts per 100 parts of latex solids.
After 10 minutes of addition, the latex was coagulated by holding at 110 ° C. for another 10 minutes. After cooling, the polymer was separated from the slurry, washed with water and dried.

Copolymer (2) Maleic anhydride-styrene copolymer (manufactured by ARCO, Dila
Ark 332, maleic anhydride content 14%)
Enter the hopper of the 40mmφ twin-screw extruder with feeder and vent
And supplied at a rate of 10 kg / hour under a nitrogen gas atmosphere.
The resin temperature at the exit of the extruder is set to 230 ° C, and the average residence time is
Was set to 2 minutes. From this side feeder
98 parts of Niline, 50 parts of Ethylbenzene and Trimethylami
The solution consisting of 2 parts was fed at a rate of 2.1 kg / hour. D
Cylbenzene, trimethylamine, unreacted aniline and
And water are removed from the vent by reducing the pressure with a vacuum pump.
It was The strands from the extruder are cut with a cutter and
Let it.

Copolymer (3) 70 parts of pure water, 0.02 part of potassium persulfate and 0.05 part of sodium lauryl sulfate were charged into the reactor used for the copolymer (1), the inside of the reactor was replaced with nitrogen, and the mixture was stirred at 70 ° C. The temperature was raised to. A solution of 30 parts of N-phenylmaleimide, 20 parts of acrylonitrile, 50 parts of styrene and 0.2 part of t-dodecyl mercaptan and an aqueous solution of 0.1 part of potassium persulfate, 0.1 part of sodium lauryl sulfate and 50 parts of pure water were added to each of them. The temperature was raised to 75 ° C. over 30 minutes while continuous addition was performed at a rate of 10 parts / hour and 10 parts / hour. After the continuous addition of these solutions was completed, they were subsequently kept at 75 ° C. for 2 hours.
As a result, a latex having a polymerization rate of 98.8% and a pH of 2.6 was obtained.

The solid content concentration of this latex was adjusted to 15%, and the mixture was charged into the above reactor and heated to 135 ° C. Add 30 parts of 20% calcium chloride aqueous solution to 100 parts of latex solids.
After adding over 0 minutes, the latex was coagulated by holding at 135 ° C. for 10 minutes. After cooling, the polymer was separated from the slurry, washed with water and dried.

Copolymer (4), (5), (6), (7), (8),
(9) and (12) The copolymers shown in Table 1 were obtained according to the method for producing the copolymer (3).

Copolymer (10) Pure water 150 parts and 5% in the reactor used for copolymer (1)
Was charged with 4 parts of an aqueous solution of hydroxypropylmethyl cellulose and the inside of the reactor was replaced with nitrogen gas, and then 28 parts of acrylonitrile, 72 parts of styrene, 0.45 part of t-dodecyl mercaptan and 0.5 part of lauroyl peroxide were charged with stirring. This was heated to 75 ° C and polymerized for 5 hours, then further heated to 80 ° C and held for 1 hour. Then 100 ℃
The temperature was raised to 1, and unreacted monomers were distilled off while blowing steam into the reactor. After cooling, the polymer is separated, washed with water,
Dried.

Copolymer (11) A reactor of 5 liters was charged with 700 parts of dimethylformamide, 6 parts of acrylonitrile, 24 parts of styrene and 0.2 part of t-dodecyl mercaptan, and after replacing the inside with nitrogen gas,
The temperature was raised to 70 ° C with stirring. To this was added a solution consisting of 0.2 part of lauroyl peroxide, 0.05 part of benzoyl peroxide and 5 parts of dimethylformamide, and then N
-A mixed solution of 66 parts of phenylmaleimide, 5 parts of acrylonitrile and 200 parts of dimethylformamide was continuously added over 2 hours. Then, it heated up at 90 degreeC and hold | maintained 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 the copolymer (1), and polybutadiene latex (weight average particle diameter of rubber 0.46 μm, gel content 72%, solid content 41%, emulsifier sodium dehydroabietate 1.5%, pH 12.1 30 parts (as solid content) and butadiene-styrene copolymer latex (weight average particle diameter of rubber 0.12 μm, gel content 82%, Solid content
42%, styrene content 15%, emulsifier sodium oleate 2%, pH 11.7) 30 parts (solid content conversion) was charged. Next, 0.002 part of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate and 0.2 part of dextrose were added, and then the inside of the reactor was replaced with nitrogen gas and heated to 70 ° C. An aqueous solution consisting of 0.01 part of t-butyl hydroperoxide and 2 parts of pure water was charged into this, and then acrylonitrile 15 parts each.
Part, styrene 25 parts and t-dodecyl mercaptan 0.2
A solution of 10 parts by weight and an aqueous solution of 0.2 parts of t-butyl hydroperoxide, 0.6 parts of sodium tetrahydroabietate, 0.2 parts of sodium hydroxide and 20 parts of pure water were continuously added over 3 hours. Then, heat to 75 ° C for 2
Held for hours. As a result, a latex having a polymerization rate of 98.7% and a pH of 11.9 was obtained.

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

Graft polymer (b) The reactor used for the copolymer (1) was charged with an aqueous solution containing 200 parts of pure water and 0.3 part of hydroxyethyl cellulose, and then made into pieces of ethylene (45%)-propylene (52%). 50 parts of) -cyclopentadiene (3%) rubber were charged. To this was added a solution consisting of 18 parts of acrylonitrile, 35 parts of styrene, 0.1 part of dicumyl peroxide and 0.3 part of t-dodecyl mercaptan, and after replacing the inside of the vessel with nitrogen gas, the temperature was raised to 120 ° C. under stirring for 4 hours. Polymerized.
After cooling, the polymer was separated, washed with water and dried.

Graft polymer (c) To the reactor used for the copolymer (1), 30 parts of pure water, 0.003 part of ferrous sulfate heptahydrate, 0.2 part of sodium hydrogen sulfite and 0.2 part of dextrose were added, and then polyacrylic acid was added. Butyl latex (rubber weight average particle size 0.27 μm, gel content
73%, solid content 40%, emulsifier sodium dodecylbenzenesulfonate 1.6% / rubber, pH 5.7 60 parts (as solid content) were charged, and then the inside of the reactor was replaced with nitrogen gas and stirred.
Heated to 75 ° C. In addition to this, a solution consisting of 4 parts of N-phenylmaleimide, 8 parts of acrylonitrile, 28 parts of styrene and 0.2 part of t-dodecyl mercaptan and an aqueous solution consisting of 0.2 part of cumene hydroperoxide, 0.4 part of sodium dodecyl sulfonate and 20 parts of pure water. Was continuously added over 3 hours. Then, raise the temperature to 80 ℃ and
Held for hours. As a result, a latex having a polymerization rate of 98.5% was obtained. Thereafter, the polymer was recovered in the same manner as in the case of the graft polymer (a).

Graft polymer (d) To the reactor used for the copolymer (1), 30 parts of pure water, 0.002 part of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate and 0.2 part of dextrose were added, and then acrylonitrile-
Butadiene copolymer latex (weight average particle size of rubber
0.17 μm, gel content 77%, acrylonitrile content 20%,
Solid content 43%, emulsifier sodium lauryl sulfate 1.6 parts, pH
5.2) After charging 60 parts (solid content conversion), the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 70 ° C. with stirring. to this,
A solution consisting of 7 parts of acrylonitrile, 27 parts of styrene, 6 parts of glycidyl methacrylate and 0.2 part of t-dodecyl mercaptan and an aqueous solution of 0.2 parts of cumene hydroperoxide, 0.5 part of sodium lauryl sulfate and 20 parts of pure water are continuously applied for 3 hours. Was added. After that, it was heated to 80 ° C. and kept for 2 hours. As a result, the polymerization rate
98.5% latex was obtained. Thereafter, the polymer was recovered in the same manner as in the case of the graft polymer (a).

Reference Example 3 Other thermoplastic resin and / or elastomer [III]
As the styrene-acrylonitrile copolymer (copolymer No. 10 in Reference Example 1) "AS", polycarbonate "PC" or acrylonitrile (30%)-butadiene (7
0%) 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 together with the other thermoplastic resin or elastomer shown in Reference Example 3. And the third
Blend in the proportions shown in the table and blend these 100
0.1 part of triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and di (2,4-di-) as stabilizers per part
t-Butylphenyl) pentaerythritol diphosphite (0.2 parts) and ethylenebisstearoamide (0.05 parts) as a lubricant were added, and a vented 40 mmφ twin-screw extruder was used to produce 250-3
The mixture was kneaded at 00 ° C and pelletized. The total amount of residual monomers in these pellets was 0.2% or less in all cases.

The pellets were molded with an injection molding machine at 250 to 320 ° C. to prepare test pieces, and the physical properties were measured. The results are shown in Tables 2 and 3.

The composition is a value determined by CHN and O elemental analysis.

NPMI: N-phenylmaleimide S: Styrene AMS: α-Methylstyrene AN: Acrylonitrile MAN: Methacrylonitrile MMA: Methyl methacrylate MAA: Methacrylic acid Intrinsic viscosity “[η]” is a dimethylformamide solution, 30
Measured value in ° C.

Glass transition temperature "Tg" is a value measured by a differential scanning calorimeter (DSC).

Heat distortion temperature "HDT" is the value measured under the condition of 1/4 inch thickness test piece, 264 psi load and no annealing.

Notched Izod impact strength "N-IS" is a 1/4 inch thickness test piece, measured at 23 ° C.

<Effects of the Invention> The composition of the present invention comprising two or more maleimide-based copolymers and a graft polymer having a specific relationship is remarkably excellent in heat resistance and impact resistance as compared with conventional compositions. It is a thing.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08L 51:04)

Claims (1)

[Claims] 1. A maleimide-based monomer component (A) and an aromatic vinyl-based monomer component (B) or components (A) thereof,
At least two kinds of components (B) and one or more kinds of monomer components (C) selected from unsaturated nitrile-based monomers, unsaturated carboxylic acids and ester-based monomers thereof Of the copolymers, the composition of each copolymer is within the range represented by the formulas (1) and (2), and the difference in the content of the maleimide monomer component (A) between the copolymers is Resin composition [I] 2 to 98 having a content of 3 to 50% by weight
Graft polymer [II] 98 to 90% by weight, a rubber-like polymer and one or more monomer components selected from the above (A), (B) and (C) 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], the graft polymer [II] and the other thermoplastic resin and / or the elastomer [III] is 1 to 50% by weight. %, A heat-resistant and impact-resistant resin composition.