JPH0635525B2 - Discoloration resistant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition having excellent thermal stability, heat resistance and discoloration resistance. More specifically, a copolymer containing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride as essential components is first partially imidized with a primary amine having a boiling point of 100 ° C. or higher, and then the boiling point is changed. The present invention relates to a thermoplastic resin composition containing as an essential component an imidized copolymer obtained by performing an imidization reaction with a primary amine and / or ammonia at a temperature of less than 100 ° C.

(Prior art and its problems) An unsaturated dicarboxylic acid imide obtained by first obtaining a copolymer of an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride, and then modifying it into an unsaturated dicarboxylic acid imide copolymer. Since the copolymer has a high heat distortion temperature and excellent thermal stability, it is an important resin as a weak electric component and an automobile interior material. Further, the unsaturated dicarboxylic acid imide copolymer has good compatibility in blending with various other resins, and its application is expanding more and more.

In the unsaturated dicarboxylic acid imide copolymer, the unsaturated dicarboxylic acid anhydride residue is converted to an unsaturated dicarboxylic acid imide residue, that is, an unsaturated dicarboxylic acid imide copolymer obtained when the imidization ratio is low. The thermal stability and hot water resistance tend to decrease. Therefore, as a method of increasing the imidization ratio of the unsaturated dicarboxylic acid anhydride residue, the unsaturated dicarboxylic acid anhydride copolymer and ammonia or primary amine are added in the presence of a tertiary amine in a non-aqueous state to 80%.
Method of reacting at a temperature of ˜350 ° C. (JP-A-57-5)
5901), a method of reacting an unsaturated dicarboxylic acid anhydride copolymer with ammonia or a primary amine in an organic solvent at 0 to 75 ° C., and then removing the organic solvent to carry out a dehydration ring closure reaction (special Unexamined Japanese Patent Publication No. S58-217522) and an unsaturated dicarboxylic acid anhydride copolymer are first melted by heating under a nitrogen gas or an inert gas atmosphere, a primary amine is added, and the state is kept for 5 to 30 minutes. A method has been proposed (KOKAI No. 58-180506) for holding and then removing water and excess primary amine under reduced pressure. In any of the above methods, the imidization reaction of the unsaturated dicarboxylic acid anhydride residue is difficult to proceed 100% quantitatively, and ammonia or primary amine is excessively added to the unsaturated dicarboxylic acid anhydride residue. If not used, it is difficult to obtain a sufficiently high imidization ratio. Therefore, when a primary amine having a high boiling point such as aniline or cyclohexylamine is used, unreacted primary amine tends to remain in the resulting unsaturated dicarboxylic acid imide copolymer, and the molded product is used at high temperature. Then, there is a drawback that the color tends to change. further,
In extrusion molding or injection molding, there is a drawback that the color tone is apt to change due to the change of residence time or molding temperature, and it is difficult to adjust the color.

(Means for Solving the Problems) The present invention aims to provide a resin composition excellent in thermal stability, heat resistance and discoloration resistance. In the blend of the dicarboxylic acid imide copolymer and the polyester resin or the polycarbonate resin, not only the thermal stability as shown in the thermal decomposition behavior of the obtained resin composition (for example, thermogravimetric analysis) but also the retention during molding is observed. They have found that they are also excellent in maintaining their physical properties, and have reached the present invention.

That is, the present invention is: Component A: 40 to 90% by weight of an aromatic vinyl monomer, 5 to 50% by weight of an unsaturated dicarboxylic acid anhydride and 0 to 40 parts by weight of a rubbery polymer, and copolymerizable with these. Monomer mixture 60 to 100 consisting of 0 to 40% by weight of vinyl monomer
First, a primary amine having a boiling point of 100 ° C. or higher at atmospheric pressure is added to a polymer obtained by copolymerizing parts by weight of 0.3 to 0.98 of an acid anhydride group.
After reacting in an equivalent amount, the primary amine and / or ammonia having a boiling point at atmospheric pressure of less than 100 ° C. is converted to 0.02 of the acid anhydride group.
To 0.75 equivalents of 10 to 90% by weight of an imidized copolymer, and component B: 3 to 80% by weight of a rubber-like polymer, 40 to 100% by weight of an aromatic vinyl monomer, preferably 40 to 80% by weight. A graft copolymer 0 to 50 in which 20 to 97% by weight of a monomer composed of 0 to 40% by weight of a vinyl cyanide monomer and 0 to 40% by weight of a vinyl monomer copolymerizable therewith It is a thermoplastic resin composition characterized by containing wt% and C component: 0 to 90 wt% of a thermoplastic polymer.

First, the A-component polymer and its production method will be described. The component A polymer contains 0 to 40% by weight, preferably 0 to 30% by weight of a rubber-like polymer. As the rubber-like polymer, a butadiene polymer, a copolymer of a vinyl monomer copolymerizable with butadiene, an ethylene-propylene copolymer, an ethylene-
A propylene-diene copolymer, a block copolymer of butadiene and aromatic vinyl, an acrylic acid ester polymer, and a copolymer of an acrylic acid ester and a vinyl monomer copolymerizable therewith are used. This is because when the rubber component in the component A polymer exceeds 40% by weight, heat resistance and molding processability are poor. Further, the monomer to be grafted to these is from 40 to 90% by weight of an aromatic vinyl monomer, 5 to 50% by weight of an unsaturated dicarboxylic acid anhydride, and 0 to 40% by weight of a vinyl monomer copolymerizable therewith. When the content of the aromatic vinyl is less than 40% by weight, the characteristics of the aromatic vinyl compound, particularly in the case of styrene, the moldability and the dimensional stability are lost. If the content is less than 5% by weight, the heat resistance is not improved, and if it exceeds 50% by weight, the copolymer becomes brittle and the moldability is significantly deteriorated.

The aromatic vinyl monomer that constitutes the component A is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, or a substituted monomer thereof. And α-methylstyrene are particularly preferred.

Examples of unsaturated dicarboxylic acid anhydrides include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid.
Maleic anhydride is especially preferred. Further, as vinyl monomers copolymerizable with these, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile, acrylic acid such as methyl acrylate, ethyl acrylate and butyl acrylate. Ester monomer, methyl methacrylate,
Methacrylic acid ester monomers such as ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides, methacrylic acid amides, acenaphthylene and N-vinylcarbazole and the like, among them acrylonitrile Monomers such as acrylic acid ester, methacrylic acid ester, acrylic acid and methacrylic acid are preferable.

The process for producing the imidized copolymer of the present invention comprises, as a first step,
After a primary amine having a boiling point of 100 ° C. or higher at atmospheric pressure is subjected to an imidization reaction with 0.3 to 0.98 equivalent of an acid anhydride group, ammonia and / or a boiling point of 100 at atmospheric pressure is used as a second step.
It is characterized in that a primary amine having a temperature lower than 0 ° C. is imidized with 0.02 to 0.75 equivalent of an acid anhydride group. The total amount of amine and ammonia used in the first step and the second step is preferably 1.0 equivalent or more of the acid anhydride group. The total amount of amine and ammonia is 1.
When it is less than 0 equivalent, the thermal stability of the obtained resin composition is lowered.

The primary amine having a boiling point of 100 ° C. or higher at atmospheric pressure is aniline, tolylamine, naphthylamine, 2-aminoanthracene, 2-aminodiphenylmethane, 4-aminodiphenyl, benzylamine, p-aminoethylbenzene, 3,5- Dimethylaniline, p-methoxyaniline, m-ethoxyaniline, p-chloroaniline, p-
Aromatic primary amines such as bromoaniline, 2,4-dichloroaniline and 2,4,6-tribromoaniline, cyclopentylamine, cyclohexylamine, cycloheptylamine, 1-cyclohexenylamine, cyclohexylmethylamine and cyclopentylethylamine Alicyclic primary amines such as alicyclic amines, pentylamines, hexylamines, heptylamines, octylamines, nonylamines, dodecylamines, cetylamines, stearylamines, and other aliphatic primary amines; In order to further improve the heat resistance of the above, aromatic primary amines and alicyclic primary amines are preferable, and aniline, tolylamine and cyclohexylamine are particularly preferable.

Examples of primary amines having a boiling point of less than 100 ° C. at atmospheric pressure include methylamine, ethylamine, propylamine, isopropylamine, tert-butylamine, isobutylamine, sec-butylamine, 2-aminopentane and 3-aminopentane. Among them, ammonia, methylamine, ethylamine and the like are particularly preferable in the second stage.

When the imidization reaction is carried out in a solution state or a suspension state, it is preferable to use an ordinary reaction vessel, for example, an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device may be used.

The temperature of the imidization reaction is about 50 to 350 ° C, preferably 100 to 300 ° C. When the temperature is lower than 50 ° C, the reaction rate is slow and the reaction requires a long time, which is not practical. On the other hand, when the temperature exceeds 350 ° C, the physical properties are deteriorated due to thermal decomposition of the polymer.

When a catalyst is used in the imidization reaction, examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline and the like. As the solvent for imidizing the unsaturated dicarboxylic acid copolymer in a solution state, there are acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, tetrahydrofuran, toluene, xylene, chlorobenzene and the like. The medium for imidization in suspension includes aliphatic carbon such as heptane, hexane, pentane, octane, 2-methylpenta, cyclopentane and cyclohexane.

In the present invention, the time of the first stage imidization reaction is preferably 5 minutes or more, and when it is less than 5 minutes, the reaction rate of the primary amine used in the first step is lowered, and the resulting imide is obtained. The chemical copolymer has a drawback that it is easily discolored at high temperature. The imidization reaction time in the second step is also preferably 5 minutes or more, and when it is less than 5 minutes, the thermal stability and hot water resistance of the resulting imidized copolymer tend to be lowered.

As a method for removing the solvent from the imidization reaction liquid, the reaction liquid is formed into a sheet, dried by air blowing, and then ground and dried again by air blowing,
Method of removing solvent by vacuum drying or extruder with devolatilizer, method of removing solvent by drum dryer or strand devolatilization of reaction liquid, and then drying by blowing, vacuum drying or extruder with devolatilizer, and reaction Examples include a method of directly removing the solvent by using an extruder equipped with a devolatilizing device.

It is also possible to produce a resin composition by solution blending the component B and / or the component C before removing the solvent from the component A and then removing the solvent.

Next, the component B and its manufacturing method will be described. The rubber-like polymer used in the component B is butadiene homopolymer or a polymer composed of vinyl monomer copolymerizable therewith, ethylene-propylene-diene copolymer or acrylic acid ester homopolymer or vinyl monomer copolymerizable therewith. There are polymers that consist of polymers.

The aromatic vinyl monomer of the component B is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene or a substituted monomer thereof, and among these, styrene and α- Monomers such as methylstyrene are particularly preferred.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., and acrylonitrile is particularly preferable. Examples of vinyl monomers copolymerizable with them include acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester and butyl acrylic acid ester, and methacrylic acid ester such as methyl methacrylic acid ester and ethyl methacrylic acid ester. Examples thereof include monomers, vinylcarboxylic acid monomers such as acrylic acid and mectaryl acid, acrylic acid amides, methacrylic acid amides, acenaphthylene and N-vinylcarbazole. Of these, methyl methacrylic acid ester, acrylic acid and methacrylic acid are particularly preferable.

The method for producing the graft copolymer of the component B is rubber-like polymer 3-8.
Aromatic vinyl monomer in the presence of 0% by weight, 40 to 100% by weight, preferably 40 to 80% by weight, vinyl cyanide monomer, 0 to 40% by weight and, if necessary, a vinyl monomer copolymerizable therewith. Monomers 20-97 consisting of 0-40% by weight
Obtained by graft-copolymerizing wt%. For the polymerization, any known polymerization technique can be adopted, for example, suspension polymerization,
There are aqueous heterogeneous polymerization such as emulsion polymerization, bulk polymerization, solution polymerization and precipitation polymerization of the produced polymer in a non-solvent.

Next, the thermoplastic resin that can be used as the C component is a resin that has a good compatibility with the imidized copolymer that is the A component and the graft copolymer that is the B component. Copolymers, polycarbonates, and polybutylenes obtained by copolymerizing a monomer mixture consisting of 1% by weight, 0 to 50% by weight of a vinyl cyanide monomer, and 0 to 50% by weight of a vinyl monomer copolymerizable therewith. Terephthalate, polyethylene terephthalate, polyester elastomer, nylon elastomer, 6,6-nylon, 6-nylon, 12-nylon, polyphenylene oxide, polyphenylene oxide obtained by graft polymerization of styrene, polyetherimide, polyether sulfone, polysulfone , Polyetheretherketone, polyarylate, and polyphenylene oki De, and the like, may be used one or more resins of these resins.

The aromatic vinyl monomer used as the C component is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, or chlorostyrene and a substituted monomer thereof. And α-
Methylstyrene is especially preferred.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., and acrylonitrile is particularly preferable.

Examples of vinyl monomers copolymerizable with them include acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester, and butyl acrylic acid ester, and methacrylic acid ester such as methyl methacrylic acid ester and ethyl methacrylic acid ester. Examples thereof include monomers, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides, methacrylic acid amides, acenaphthylene, N-vinylcarbazole, N-alkyl-substituted maleimides, and N-aromatic-substituted maleimides.

The blending ratio of the resin composition of the present invention is such that the component A polymer is 10 to 90% by weight, particularly 20 to 80% by weight, the component B polymer is 0 to 50% by weight, particularly 10 to 40% by weight, and the component C polymer 0. ˜90 wt%, especially 0 to 80 wt%. If the proportion of the component A polymer is less than 10% by weight, heat resistance is insufficient, and if it exceeds 90% by weight, only a composition having extremely low impact strength can be obtained. Also,
If the proportion of the B component polymer exceeds 50% by weight, the heat resistance and fluidity are deteriorated, and the proportion of the C component polymer is 90% by weight.
When it exceeds the above range, only a composition in which at least one physical property such as fluidity, heat resistance or hot water resistance is deteriorated can be obtained.

The method of blending the resin composition of the present invention is not particularly limited,
Known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a Henschel mixer, a mixing roll, a single-screw or twin-screw extruder, and the like. Examples of the mixing form include ordinary melt mixing, multistage melt kneading using master pellets, solution blending, mixing in a reaction solution, and the like to obtain the composition.

In addition, the composition of the present invention further stabilizer, flame retardant, plasticizer,
It is also possible to add a lubricant, an antistatic agent, an ultraviolet absorber, a colorant and a filler such as talc, silica, clay, mica, crow fiber, calcium carbonate, etc., a conductive material such as carbon fiber, silver powder, etc. .

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. All parts and% in the examples are expressed on a weight basis.

(Examples of Invention) Experimental Example 1 Production of Component A 60 parts of styrene, 100 parts of methyl ethyl ketone, and 10 parts of polybutadiene cut into small pieces were charged into an autoclave equipped with a stirrer, and the mixture was stirred at room temperature for one day to dissolve the rubber. After that, the system was replaced with nitrogen gas and the temperature was raised to 85 ° C. A solution of 40 parts of maleic anhydride and 0.15 parts of benzoyl peroxide dissolved in 250 parts of methyl ethyl ketone was continuously added over 8 hours. The temperature was kept at 85 ° C. for a further 3 hours after the addition. As a result of sampling a part of the viscous reaction liquid and quantifying unreacted monomers by gas chromatography, the polymerization rates were 98% for styrene and 98% for maleic anhydride. As a first step, the copolymer solution thus obtained was treated with maleic anhydride in an amount of 0.3 equivalents of cyclohexylamine and triethylamine shown in Table 1.
Parts were added and reacted at 140 ° C. for 4 hours. Then, in the second step, the equivalent amount of methylamine shown in Table 1 was added to maleic anhydride and the reaction was carried out at 140 ° C. for 3 hours.

The reaction solution was taken out in a bath, vacuum dried at 80 ° C. for 5 hours, pulverized, and vacuum dried at 170 ° C. for 3 hours to obtain imidized copolymers A-1 to A-5. The results of quantitative determination of the residual primary amine in each imidized copolymer by gas chromatography are shown in Table 2.

Experimental Example 2 Preparation of Component A In Experimental Example 1, 0.70 equivalents of cyclohexylamine 28.4 parts, 0.40 equivalents of methylamine 5.1 parts and triethylamine 0.3 parts were simultaneously added to maleic anhydride.
Imidized copolymer A-6 was obtained in the same manner as in Experimental Example 1 except that the reaction was carried out at 40 ° C. for 7 hours.

Experimental Example 3 Production of Component B Polybutadiene latex 65 parts (solid content 50%, average particle size 0.35μ, gel content 90%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.1
Parts, tetrasodium ethylenediaminetetraacetyl citrate 0.03 parts, ferrous sulfate 0.003 parts and water 200 parts to 65 ° C., to which 35 parts of a monomer mixture consisting of 30% acrylonitrile and 70% styrene, t -0.14 parts of dodecyl mercaptan, Kyumen hydroperoxide
Add 0.1 parts continuously over 4 hours and then at 65 ° C after the addition is complete.
Polymerized for 1.5 hours. The polymerization rate reached 96%. After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water and dried to obtain a graft copolymer as a white powder, which was designated as Polymer B-1.

Experimental Example 4 Evaluation of Physical Properties of Resin Composition A- 1 to A-6 imidized copolymer as A component, B-1 graft copolymer as B component, polycarbonate as C component (Panlite manufactured by Teijin Chemicals Ltd.) K-1300W)
Or polyether sulfone (ICI PES200
P) or 6,6-nylon (2020U manufactured by Ube Industries, Ltd.) in various proportions, and the blended product is 30 mmφ
It was extruded into pellets by a devolatilizing screen extruder. Each blend contains 0.2 parts octadecyl 3-
(3,5-ditersialybutyl-4-hydroxyphenyl) -propionate (antioxidant) was included. The physical properties of the composition thus obtained were measured and are shown in Table 1.

The physical properties were measured by the following methods.

(1) Vicat softening point (VSP): According to ASTM D-1525 under a load of 5 kg.

(2) Impact strength (normal molding): according to Izod impact strength with notch ASTM D-256.

Molding was performed at a cylinder temperature of 270 ° C. and a mold clamping time of 45 seconds.

(3) Impact strength during retention molding: Izod impact strength with notch According to ASTM D-256.

Molding is performed at a cylinder temperature of 270 ° C and a mold clamping time of 180
It was done in seconds.

(4) Thermal stability: Nitrogen flow of 50cc / min, heating rate of 10 ℃ / mi
Weight loss of polymer is 1 in thermobalance analysis under n condition
The temperature in% is shown.

(5) Discoloration resistance: The molded product was left standing in a gear oven at 140 ° C. for 5 hours and visually evaluated.

Experimental Example 5 Production of component A 60 parts of styrene was added to an autoclave equipped with a stirrer.
100 parts of methyl ethyl ketone and 10 parts of polybutadiene cut into small pieces were charged, stirred at room temperature for one day to dissolve the rubber, and then the system was replaced with nitrogen gas, and the temperature was raised to 85 ° C. A solution prepared by dissolving 40 parts of maleic anhydride and 0.15 part of benzoyl peroxide in 250 parts of methyl ethyl ketone was continuously added over 8 hours. 3 more after addition
The temperature was kept at 85 ° C for an hour. As a result of sampling a part of the viscous reaction liquid and quantifying the unreacted monomer by gas chromatography, the polymerization rate was styrene 98%,
It was 98% maleic anhydride. As the first step, 0.75 equivalents of aniline (28.5 parts) and triethylamine (0.3 parts) were added to the copolymer solution thus obtained.
The reaction was carried out at 0 ° C for 7 hours. Next, 2.1 parts of 0.30 equivalent of ammonia was added to maleic anhydride, and the mixture was further reacted at 140 ° C. for 3 hours. The reaction solution was taken out in a bath, vacuum dried and pulverized to obtain an imidized copolymer. This is polymer A
It was set to -7. Polymer A-by gas chromatography
As a result of quantitative determination of the residual amine in Example 7, both aniline and ammonia were less than 0.1%.

Experimental Example 6 Production of Component A A maleic anhydride copolymer solution obtained in the same manner as in Experimental Example 5 was added with 0.95 equivalents of aniline 36.1 relative to maleic anhydride.
And triethylamine (0.3 parts) were added, and the mixture was reacted at 140 ° C. for 10 hours. The reaction solution was vacuum dried under the same conditions as in Experimental Example 1 to obtain an imidized copolymer A-8. As a result of quantifying the residual aniline in the polymer A-2 by gas chromatography, the amount of residual aniline was less than 0.1%.

Experimental Example 7 Production of Component C 70 parts of α-methylstyrene in a nitrogen-substituted polymerization vessel,
Acrylonitrile 25 parts, 20% aqueous solution of sodium dodecylbenzene sulfonate 12.5 parts, potassium chloride 0.05
Parts, 0.5 parts of t-dodecyl mercaptan and 213 parts of water were charged, the temperature was raised to 70 ° C., and then 6.7 parts of a 1% potassium persulfate aqueous solution was added to initiate polymerization. Further, after 6 hours, 3.3 parts of a 1% aqueous solution of potassium persulfate was added. One hour after the initiation of polymerization, 10 parts of acrylonitrile was added to the polymerization system over a period of 6 hours using a metering pump. Polymerization 1
After stopping at 0 hour, a latex having a final polymerization rate of 98.5% was obtained. The latex was coagulated with calcium chloride, washed with water, filtered, and dried to obtain a copolymer as a white powder. The copolymer C-
It was set to 1.

Experimental Example 8 Evaluation of physical properties of resin composition As component A, imidized copolymer A-7 or A-8,
Graft copolymer B-1 as component B and C as component C
-1 or polyester elastomer (Toyobo Co., Ltd.
Pelletization and physical properties were measured in the same manner as in Experimental Example 4 except that Perprene P70B) was used, and the results are shown in Table 2.

(Effects of the Invention) An unsaturated dicarboxylic acid anhydride copolymer is used as a first stage to form an aromatic and / or alicyclic primary amine as an acid anhydride group.
After the imidization reaction of 0.3 to 0.98 equivalent, as a second step, imidization of ammonia and / or 0.02 to 0.75 equivalent of an acid anhydride group of a primary amine having a boiling point of less than 150 ° C. under atmospheric pressure is carried out. For the first time in a resin composition containing a copolymer as an essential component, a resin excellent in heat resistance, thermal stability and discoloration resistance was obtained. Further, in the case of blending with polyester or polycarbonate, a resin composition which is excellent not only in thermal stability as shown in thermal decomposition behavior but also in retaining physical properties during residence molding can be obtained.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Reference number in the office FI Technical display location C08L 55/02 LME 7142-4J 101/00 LSZ 7242-4J // (C08L 25/08 55:02 7142-4J 101: 00) (C08L 35/06 51:04 101: 00)

Claims (1)

[Claims] 1. Component A: 40 to 90% by weight of an aromatic vinyl monomer, 5 to 50% by weight of an unsaturated dicarboxylic acid anhydride and 0 to 40 parts by weight of a rubbery polymer and copolymerizable with these. To a polymer obtained by copolymerizing 60 to 100 parts by weight of a monomer mixture consisting of 0 to 40% by weight of a vinyl monomer, a primary amine having a boiling point of 100 ° C. or higher at atmospheric pressure is added to an acid anhydride group.
After reacting 0.3 to 0.98 equivalents, the boiling point at atmospheric pressure is 100.
An imidized copolymer obtained by reacting a primary amine and / or ammonia having a temperature of less than 0 ° C with 0.02 to 0.75 equivalent of an acid anhydride group.
-90 wt%, Component B: 3-80 wt% of rubber-like polymer, 40-100 wt% of aromatic vinyl monomer, 0-40 wt% of vinyl cyanide monomer and copolymerizable with these A graft copolymer 0 to 50% by weight obtained by copolymerizing 20 to 97% by weight of a monomer composed of 0 to 40% by weight of a vinyl monomer, and C component: 0 to 90% by weight of a thermoplastic polymer. A thermoplastic resin composition comprising: