JPS62179553A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent resistance to heat, hot water and creep and moldability, containing a specified thermoplastic resin. CONSTITUTION:40-100% (by weight; the same applies hereinbelow) thermoplastic resin composed of 10-90% imide copolymer (A) obtd. by imidating 0.8-1.0mol equivalent of acid anhydride groups by reacting a polymer obtd. by copolymerizing 100pts.wt. of the combined amount of 0-40% rubbery polymer and 100-60% monomer mixture of 40-80% arom. vinyl monomer (b), 25-50% unsaturated dicarboxylic acid anhydride and 0-30% vinyl monomer (c) copolymerizable with them in the presence of 0.01-5pts.wt. crosslinking monomer (e) having at least two vinyl groups with NH3 and/or a primary amine, 10-90% graft copolymer (B) obtd. by copolymerizing 5-80% component (a) with 95-20% mixture of 40-80% component (b), 0-40% vinyl cyanide monomer (f) and 0-40% component (d) and 0-80% copolymer (C) composed of 40-80% component (b), 0-40% component (f) and 0-40% component (c), is incorporated.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a resistant copolymer containing an imidized copolymer whose molecular weight has been increased by polymerization in the presence of a crosslinkable monomer having two or more vinyl groups. The present invention relates to a heat-resistant thermoplastic resin composition with excellent creep properties.

More specifically, in the presence or absence of a rubbery polymer, a monomer mixture containing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride is placed in the lower right corner of a crosslinkable monomer having two or more vinyl groups. The essential component is a mixture of an imidized copolymer obtained by reacting a copolymer co-polymerized with ammonia and/or a primary amine, and a rubber-modified aromatic vinyl copolymer.
The present invention relates to a heat-resistant thermoplastic resin composition with excellent creep resistance.

The molded article obtained from the resin composition of the present invention can be used particularly for applications requiring creep resistance and strain resistance at high temperatures. For example, medical instruments that require high heat treatment for a relatively long period of time, automotive parts such as instrument panels and meter hoods, railway vehicle or marine parts such as surface panel materials or coating materials, terminal boards, hair dryer cases, open toasters, etc. It can be preferably used for parts for electrical appliances, nozzles for pots and warmers, parts for heating appliances such as fans for clean heaters, and the like.

[Conventional technology]

Thermoplastic resin compositions containing aromatic vinyl monomers and unsaturated dicarboxylic acid anhydrides or imide derivatives thereof have been known (USP 3642949, USP 365]7),
It has high heat resistance, typified by heat distortion temperature.

Further, JP-A No. 60-23438 discloses an example of a thermoplastic resin composition containing an aromatic vinyl monomer and an unsaturated dicarboxylic acid imide derivative and having excellent heat resistance and impact resistance. This suggests that the composition is a useful material suitable for fields that require heat resistance, such as automobile parts, electrical and electronic parts. However, since these compositions have somewhat insufficient creep resistance at high temperatures for long periods of time, their use may naturally be limited.

Conventionally, methods of blending fibrous materials such as glass fibers have often been proposed to improve the rigidity and creep resistance of thermoplastic resins, and U.S. Pat. and a composition in which glass fiber is blended with a resin containing maleimide is disclosed. However, in this case, since the affinity between the resin and the glass fiber is insufficient, the effect of improving rigidity is small. Further, even if a sufficient improvement effect is obtained, there are disadvantages such as spoiling the appearance of the surface of the molded product and increasing costs.

[Means for solving problems]

Therefore, as a result of repeated studies on a method for improving creep resistance without these disadvantages, the present invention was developed by adding an aromatic vinyl monomer and an unsaturated dicarboxylic anhydride in the presence or absence of a rubbery polymer. A monomer mixture containing 2 vinyl groups
Thermoplastic material whose essential component is an imidized copolymer with increased molecular weight, which is obtained by reacting a copolymer copolymerized with ammonia and/or a primary amine in the presence of a crosslinking monomer having at least It was discovered that the resin exhibits excellent creep resistance, and the present invention was completed.

That is, the present invention uses component A: 0 to 40 weight ratio of rubbery polymer, 40 to 80 weight ratio of aromatic vinyl monomer, 25 to 50 weight ratio of unsaturated dicarboxylic acid anhydride, and copolymerizable with these. 60 to 100 parts by weight of a monomer mixture consisting of 0 to 30 parts by weight of vinyl monomers, and 0.01 to 5 parts by weight of vinyl groups per 100 parts by weight of these rubbery polymers and monomer mixture. 0.8 to 1.0 molar equivalent of acid anhydride groups by reacting ammonia and/or primary amine to the polymer obtained by copolymerizing in the presence of a crosslinkable monomer having two or more of Imidized copolymers 10 to 90 obtained by converting into imide groups
Weight ratio and component B: rubbery polymer 5-80 weight ratio, aromatic vinyl monomer 40-80 weight ratio, cyanide vinyl monomer 0
~4ON amount% and 10 to 90 weight percent of a graft copolymer containing 20 to 95 weight percent of a monomer mixture consisting of 0 to 40 weight percent of a vinyl monomer copolymerizable with these, and C component. : 0-80% by weight of a copolymer consisting of 40-80% by weight of aromatic vinyl monomers, 0-40% by weight of vinyl cyanide monomers, and 0-40% by weight of vinyl monomers copolymerizable with these. This is a heat-resistant thermoplastic resin composition having excellent creep resistance and containing a thermoplastic resin of 40 to 100% by weight.

The thermoplastic resin of the present invention may consist of only components A and B, but even if it is further mixed with component C, an aromatic vinyl copolymer in an amount of 80% by weight or less, the present invention Since the excellent handling properties of the thermoplastic resin are not deteriorated, it has the advantage that a large amount of an inexpensive aromatic vinyl copolymer can be blended. In addition, to the mixture of these A, B%C1 components, 60% by weight or less of other thermoplastic resins, such as aromatic polycarbonate polybutylene terephthalate, polyethylene terephthalate, nylon 6, nylon 6.6, polyphenylene sulfide, polysulfone, etc. It is also possible to mix within a range.

Here, component A will be explained. The monomer mixture used consists of 40-80% by weight of aromatic vinyl monomers, 25-50M unsaturated dicarboxylic acid anhydrides and 0-30% by weight of vinyl monomers copolymerizable therewith. If desired, rubbery polymers can be used in amounts up to 40% by weight, based on the monomer mixture.

If the content of the aromatic vinyl monomer in the monomer mixture is less than 40% by weight, moldability and dimensional stability, which are characteristics of aromatic vinyl compounds, will be impaired. Further, if the unsaturated dicarboxylic anhydride content is less than 25% by weight, the heat resistance will be insufficient, and if it exceeds 50% by weight, the copolymer will become brittle and the moldability will also be significantly impaired.

Aromatic vinyl monomers constituting component A include styrene monomers and their substituted monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene; Styrene is particularly preferred.

Examples of unsaturated dicarboxylic acid anhydrides include anhydrides such as maleic acid, itaconic acid, citraconic acid, and unitic acid.
Among these, maleic anhydride is particularly preferred.

In addition, vinyl monomers that can be copolymerized with these include monovinyl cyanide such as acrylonitrile methacrylonitrile and α-chloroacrylonitrile, acrylic acid ester monomers such as methyl acrylic ester and ethyl acrylic ester, There are methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide, methacrylic acid amide, etc.
Among these, acrylonitrile methacrylate,
Monomers such as acrylic acid and methacrylic acid are preferred.

Rubbery polymers include butadiene polymers, copolymers of butadiene and copolymerizable vinyl monomers, ethylene-propylene copolymers, block copolymers of butadiene and aromatic vinyl, and acrylic acid ester polymers. Also used are copolymers of acrylic esters and vinyl monomers copolymerizable with the acrylic esters. The rubber component in the A component polymer is 40
If it exceeds % by weight, it is unfavorable in terms of heat resistance and moldability.

Diacrylate compounds such as divinylbenzene, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, etc. as crosslinkable monomers having two or more vinyl groups; Triacrylate compounds such as tetramethylolmethane triacrylate, dimethacrylate compounds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diaryl phthalates,
There are diaryl compounds such as diaryl maleate, unsaturated aryl carboxylates such as aryl acrylate, and aryl methacrylate, and these may be used alone or in combination of two or more. In component A, the amount of the crosslinkable monomer having two or more vinyl groups used is 100 in total for the monomer mixture and the rubbery polymer! The amount is 0.01 to 5 parts by weight, preferably 0.02 to 3 parts by weight. If it is less than 0.01 part by weight, the amount of framework formed in the polymer will be small and sufficient creep resistance will not be obtained. On the other hand, if the amount exceeds 5 parts by weight, gelation of the polymer becomes significant, making molding extremely difficult and making it brittle.

The crosslinking monomer is used as follows: I) It is added all at once at the start of polymerization of the monomer mixture. 11) Add continuously or in portions from the start to the end of polymerization. 111) There are methods such as adding all at once just before the end of polymerization, but 1) causes rapid gelation, and 1! Method I) is not preferred because it requires the addition of a larger amount to achieve the same effect. Therefore, we mainly use the it3 method, and use 11 as necessary.
It is best to use 1) together.

Examples of primary amines used in the imidization reaction are methylamine, ethylamine, and butylamine.

Alkylamines such as cyclohexylamine, these chloro- or bromo-substituted alkylamines, aromatic amines such as aniline, tolylamine, naphthylamine, etc.
Examples include halogen-substituted aromatic amines such as aniline or bromo-substituted aniline.

When the imidization reaction is carried out in a solution or suspension state, it is preferable to use a conventional reaction vessel such as an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device may be used. Further, a catalyst may be present during imidization, and for example, a tertiary amine or the like is preferably used.

The temperature of the imidization reaction is about 80°C to 350°C, preferably 100 to 300°C.

If the temperature is lower than 80°C, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand, if the temperature exceeds 350°C, the physical properties will deteriorate due to thermal decomposition of the polymer.

Further, the amount of ammonia and/or primary amine to be reacted is preferably 0.8 molar equivalent or more based on the unsaturated dicarboxylic anhydride group. If it is less than 0.8 molar equivalent, a large amount of acid anhydride groups will be present in the imidized polymer, resulting in decreased thermal stability and hot water resistance, which is not preferable.

Next, component B will be explained.

The rubbery polymer used for component B is a polymer consisting of butadiene alone or a vinyl monomer copolymerizable with it, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, an acrylic ester alone or There are polymers made of vinyl monomers that can be copolymerized with this. Aromatic vinyl monomers used for component B include styrene,
α-methylstyrene Styrene monomers such as vinyltoluene, L-butylstyrene, and chlorostyrene, and substituted monomers thereof, and among these, styrene and α-methylstyrene are particularly preferred.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being particularly preferred. Vinyl monomers that can be copolymerized with these include acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, and methacrylic ester monomers such as methyl methacrylate and ethyl methacrylate. , vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, and methacrylic acid amide. Among these, methyl methacrylate, acrylic acid, and methacrylic acid are particularly preferred.

The method for producing the graft copolymer of component B is to prepare rubber-like polymers 5 to 8.
A monomer consisting of 40 to 80% by weight of an aromatic vinyl monomer, 0 to 40% by weight of a vinyl cyanide monomer, and 0 to 40% by weight of a vinyl monomer copolymerizable with these in the presence of 0% by weight. It is obtained by graft copolymerizing 20 to 95% by weight of the mixture. Any known polymerization method can be used for the polymerization,
Examples include suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, and precipitation polymerization of the produced polymer in a nonsolvent.

Next, the C component will be explained. Aromatic vinyl monomers used for component C include styrene monomers and substituted products thereof, such as styrene, α-methylstyrene, vinyltoluene, t-7" tylstyrene, and chlorostyrene. Among these, styrene and α-methylstyrene are particularly preferred.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, and among these, acrylonitrile is particularly preferred.

Vinyl monomers that can be copolymerized with these include acrylic ester monomers such as methyl acrylic ester, ethyl acrylic ester, butyl acrylic ester, and methacrylic ester monomers such as methyl methacrylic ester and ethyl methacrylic ester. vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide,
Examples include methacrylic acid amide, acenaphthylene, N-vinylcarbazole, N-alkyl substituted maleimide, N-aromatic substituted maleimide, and the like.

The composition of the present invention is a mixture of the above-described components A, B, and if necessary, component C, and other thermoplastic resins if necessary, but there is no particular restriction on the mixing method, and known means can be used. Can be used. For example, Bamba IJ mixer, Henschel mixer, tumbler, etc.
Examples include mixers, mixing rolls, ]-shaft or twin-screw extruders, etc. As for the mixing form, there are methods of obtaining the composition by ordinary melt mixing, step-by-step melt mixing using a master pellet or the like, and blending in a solution.

The ratio of blending each component of component A, component B, and component C is 10 to 90 M% for component A and 10 to 900% for component B.
90% by weight is 0 to 80% by weight, but the preferred range is A
Component B is 20 to 7% by weight, component B is 30 to 60%, and component C is 0 to 50% by weight. The reason for limiting the blend ratio in this way is that while maintaining the excellent heat resistance, hot water resistance, and creep resistance exhibited by component A, blending with an appropriate blending ratio of components B and C reduces the decrease in moldability. This is to prevent this, provide impact resistance that can withstand practical use, and maintain other physical properties in a well-balanced manner.

Furthermore, stabilizers, flame retardants, plasticizers, lubricants, ultraviolet absorbers, colorants, and fillers such as Merck, silica, clay, and calcium carbonate may be added to the composition of the present invention, if necessary.

〔Example〕

Hereinafter, the present invention will be further explained by examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, both parts and parts in the examples are Mi.
Expressed on a t basis.

Experimental Example (1) Production of Component A 60 parts of styrene and 50 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, and after purging the system with nitrogen gas, the temperature was raised to 85°C and 40 parts of maleic anhydride was added.
A solution of 1.5 parts of divinylbenzene, 0.15 parts of divinylbenzene, and 0.15 parts of benzoyl peroxide dissolved in 250 parts of methyl ethyl ketone was added continuously over 7.5 hours. After the addition, the temperature was kept at 85°C for another 3.5 hours, and then a portion of the viscous reaction solution was sampled and the amount of unreacted monomer was determined by gas chromatography.
9.0% Maleic anhydride 98.5%. The copolymer solution obtained here has a concentration of 0.9 to maleic anhydride groups.
37.2 parts of 8 equivalents of aniline, 0.3 parts of triethylamine
150° C. and reacted at 150° C. for 5 hours. 200 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 2000 parts of vigorously stirred methanol, precipitated, separated from P, and dried to obtain an imidized copolymer. C-C-13 moiety analysis revealed that almost 100% of the aniline was reacted in the reaction of the acid anhydride group to the imide group. Furthermore, as a result of GPC analysis, the Mw Cm f & average molecular weight) l″i of this imidized copolymer
It was 220,000. This was designated as Polymer A.

Experimental Example (2) Comparison The same operations as in Experimental Example (1) were carried out except that 5 parts of divinylbenzene O1 in the experiment for producing component A (]) was not added. The polymerization rate was 98.0% for styrene and 98.8% for maleic anhydride. As in Experimental Example (1), almost 100% of the aniline was reacted. Mw by GPC analysis was 130,000.

This was designated as Polymer B.

Experimental Example (3) Production of Component A In an autoclave similar to Experimental Example (]), 55 parts of styrene and 60 parts of methyl ethyl ketone were charged, followed by 45 parts of maleic anhydride, 0.15 parts of benzoyl peroxide, and 0.5 parts of divinylbenzene. Experimental example (except that a solution of 05 parts of diethylene glycol dimethacrylate O and 12 parts of diethylene glycol dimethacrylate O dissolved in 190 parts of methyl ethyl ketone was added continuously over 6 hours, and 40.6 parts of aniline, which is 0.95 equivalents of maleic anhydride group, was used). The same operation as in 1) was performed.

Polymerization rate is styrene 96.5% anhydrous male: /f1197
．． I was in charge 6. Aniline had almost 100 reactions. Mw was 260,000 as a result of GPC analysis.

This was designated as Polymer C.

Experimental Example (4) Manufacture of Comparative Component A The same operation as in Experimental Example (3) was carried out except that divinylbenzene and diethylene glycol were not used. The polymerization rate was 97.0% for styrene and 98.3% for maleic anhydride, and the aniline reaction was approximately 100%. Mw was 120,000 as a result of GPC analysis. This was made into a polymer.

Experimental Example (5) Production of Component A In an autoclave similar to Experimental Example (1), 63 parts of styrene and 45 parts of methyl ethyl ketone were charged, and after purging the inside of the system with nitrogen gas, the temperature was raised to 80°C to prepare anhydrous male 47237.
1 part, 0.1 part of benzoyl peroxide, 0.05 part of azobisisobutyronitrile, 0.3 part of triethylene glycol dimethacrylate, and 205 parts of methyl ethyl ketone.
The solution was added continuously over 8 hours. After keeping the temperature at 80°C for another 2 hours after addition, divinylbenzene 3
1.5% was added, the temperature was raised to 95°C and maintained at that temperature for 1.5 hours. Electricity: styrene 97.2%, maleic anhydride 99%
．． It was 8%. To the obtained copolymer solution were added 24.6 parts of aniline and 0.25 parts of aniline in an amount of 0.7 equivalent to the maleic anhydride group.
Equivalent amounts of 9.8 parts of methylamine (30% aqueous solution) and 0.35 parts of triethylamine were added, and the mixture was reacted at 140°C for 8 hours. An imidized copolymer was obtained in the same manner as in Experimental Example (1). C--C-13 part analysis showed that the reaction rate of aniline and methylamine was approximately 100%. Mw FiG
According to PC analysis, it was 290,000.

This was designated as Polymer E.

Experimental Example (6) Production of 412 parts of components In Experimental Example (5), the same operation as in Experimental Example (5) was performed except that triethylene glycol dimethacrylate and divinylbenzene were not used. The polymerization rate was 96.0% for hastyrene and 98.9% for maleic anhydride. Almost 100% of the aniso/methylamine reacted, and the Mw was 115,000 according to FiG PC analysis. This was designated as Polymer F.

Experimental Example (7) Production of Component A Styrene 60 was placed in the same autoclave as in Experimental Example (]).
1 part, 100 parts of methyl ethyl ketone, and 10 parts of polybutadiene cut into small pieces were charged, stirred overnight at room temperature to dissolve the rubber, then purged the system with nitrogen gas, and lowered the temperature to 85.
The temperature was raised to ℃.

40 parts of maleic anhydride and 0.0 parts of benzoyl peroxide.
A solution of 0.3 parts of ethylene glycol diacrylate (12 parts, ethylene glycol diacrylate) dissolved in 200 parts of methyl ethyl ketone was continuously added over 6 hours. After the addition, the mixture was kept at 85° C. for another 4 hours, and the polymerization rate was determined in the same manner as in Experimental Example (1), and it was found to be 96.0% styrene and 97.1% maleic anhydride. Add 36.1 part of aniline (0.95 equivalent to maleic anhydride group) and 0.3 part of triethylamine,
The reaction was carried out at 40°C for 8 hours. An imidized copolymer was obtained in the same manner as in Experimental Example (]). As a result of the same analysis as in Experimental Example (1), the reaction rate of aniline was approximately 00%, and the Mw of the THF bathable part of the imidized copolymer was 18 from GPC.
It was 10,000. This was designated as Polymer G.

Experimental Example (8) Production of Comparative A Component In Experimental Example (7), the same operation as in Experimental Example (7) was performed except that ethylene glycol diacrylate was not used. The polymerization rate is 98.0% of styrene and 97.0% of maleic anhydride.
It was 81. Aniline reacted almost 100%,
The M bath portion of the 'l'HF soluble portion of the obtained imidized copolymer was 90,000. This was designated as Polymer H.

Experimental Example (9) Production of Component A In an autoclave similar to Experimental Example (1), 57 parts of styrene, 80 parts of methyl ethyl ketone, and 15 parts of polybutadiene cut into small pieces were charged, and the mixture was stirred at room temperature all day and night to dissolve the rubber. , the inside of the system was replaced with nitrogen gas, and the temperature was set to 85°C.
The temperature rose to .

43 parts of maleic anhydride and 0.0 parts of benzoyl peroxide.
A solution of 15 parts of alcohol and 0.2 parts of methacrylic acid dissolved in 220 parts of methyl ethyl ketone was continuously added over 7 hours. After the addition, the temperature was maintained at 85°C for an additional 3 hours, then 2 parts of divinylbenzene was added, the temperature was raised to 95°C, and the temperature was maintained at 95°C for 2 hours. The polymerization rate was 96.9% for styrene and 97.5% for maleic anhydride. To the obtained copolymer solution was added 732.6 parts of anilic acid, which was 0.8 equivalent to the maleic anhydride group, and 0.
．． 6.8 parts of 15 equivalents of methylamine (30% aqueous solution),
0.3 part of triethylamine was added, and the mixture was reacted at 140°C for 8 hours. An imidized copolymer was obtained by performing the same operation as in Experimental Example (1). As a result of the same analysis as in Experimental Example (1), it was found that aniline and methylamine were reacting at a rate of approximately 00, and the Mw of the THF-soluble portion of the imidized copolymer obtained was 9,50,000. . This was designated as Polymer (2).

Experimental Example (10) Comparative Production of Component A The same procedure as in Experimental Example (9) was carried out except that aryl methacrylate and divinylbenzene were not used. The polymerization rate was 95.8% of styrene and 98.8% of maleic anhydride. The reaction rate of aniline methylamine was almost 100%, and the T of the obtained imidized copolymer was
The Mw of the HF soluble portion was 95,000. Polymer J
And so.

Experimental Example (11) Production of Component A Styrene 58 was placed in the same autoclave as in Experimental Example (1).
1 part, 5 parts of acrylonitrile, and 5 parts of methyl ethyl ketone were charged, and after purging with nitrogen, the temperature was raised to 90°C. Benzene 0, 3 parts Azobisisobutyronitrile O, 15
1 part dissolved in 250 parts of methyl ethyl ketone was added continuously over 9 hours. After the addition, the temperature was kept at 90°C for an additional 3 hours. The polymerization rate was 93.4% for styrene/96.0q6 acrylonitrile and 97.5% for maleic anhydride. To the obtained copolymer solution were added 30.4 parts of aniline and 0.3 parts of triethylamine, which were equivalent to the maleic anhydride group.
The reaction was carried out at 150°C for 5 hours. An imidized copolymer was obtained by performing the same operation as in Experimental Example (1).

As a result of C-C-13 part analysis, the reaction rate of AniJn was almost 100%, and as a result of GPC analysis, Mw f'i2
It was 30,000. This was made into a polymer.

In Experimental Example (11), the same operation as in Experimental Example C was carried out except that trimethylolpropane triacrylate and divinylbenzene were not used. The polymerization rate was 95.7% for styrene, 92.6% for acrylonitrile, and 98.0% for maleic anhydride. The reaction rate of aniline was almost 100%, and the Mw was 125,000. This was made into a polymer.

Styrene 90 was added in the same autoclave as in the experimental example (]).
After charging 100 parts of methyl ethyl ketone and replacing the inside of the system with nitrogen gas, the temperature was raised to 85°C, and 10 parts of maleic anhydride and 0.18 parts of azobisisobutyronitrile were dissolved in 150 parts of methyl ethyl ketone. The solution was added continuously over 10 hours and allowed to react for an additional 6 hours. The polymerization rate was 97.0% for styrene and 99.1% for maleic anhydride. To the copolymer solution obtained here, 6.6 parts of aniline, which is 0.7 equivalent to the maleic anhydride group, was added to give 140
The reaction was carried out at ℃ for 7 hours. 250 parts of methyl ethyl ketone was added to the reaction solution, and after cooling to room temperature, it was poured into 2,500 parts of vigorously stirred methanol, precipitated, and dried from door to door to obtain an imidized copolymer. As a result of C-C-13 moiety analysis, aniline was almost 100 times reactive.

As a result of GPC analysis, Mw was 95,000. This was designated as Polymer M.

Experimental example (Production of component 143B) 143 parts of polybutadiene latex (solid content 35%, weight average particle size 0.35μ, gel content 90), 1 part potassium stearate, 11 parts nodium formaldehyde sulfoxylate O, tetrane 0.03 part of dium ethylene diamine tetraacetic azide, 0.003 part of ferrous sulfate
75 parts of styrene, 25 m of acrylonitrile, 0.2 parts of t-dodecyl mercaptaf, and 0.15 parts of cumene hydroperoxide were continuously added to this over 5 hours, After further addition 7
The temperature was raised to 0°C and polymerization was carried out for 3 hours. When a portion of the latex was sampled and the polymerization rate was determined by gas chromatography, the polymerization rate reached 98.4%. 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. This was designated as Polymer N.

Experimental Example (15) Production of component C Styrene 20 parts - α-methylstyrene 52 parts, acrylonitrile 28 parts, potassium stearate z, 5 parts, t
-0.3 parts of dodecyl mercaptan and 25 parts of ion-exchanged water
0 part was heated to 70°C, and 0.0 part of potassium persulfate was added to it.
Polymerization was started by adding 5 parts. After 6 hours from the start of polymerization, 0.02 part of potassium persulfate was added and the temperature was raised to 8
The temperature was raised to 0°C and maintained for 3.5 hours to complete polymerization.

The polymerization rate was 96.6. The obtained latex was coagulated with calcium chloride, washed with water, and dried to obtain a copolymer as a white powder, which was designated as 1-coat 0.

Examples 1 to 13 - Components A, B, C and a commercially available thermoplastic resin were blended in the ratios shown in Table 1, and 0.75 parts of octadecyl-3-(3,5-ditersharif) was added to the mixture. After adding thi-4-hydroxyphenyl) propionate and 1.1 parts of tristearylphosphite, the mixture was mixed using a Henschel mixer. This blended material was extruded using a 30 mφ screw extruder equipped with a devolatilization device and pelletized.

After molding this pellet with an injection molding machine, physical properties were measured and the results are shown in Table 1.

Comparative Examples 1 to 7 Comparative A component, B component, C component, and a commercially available thermoplastic resin were blended in the quantitative ratios shown in Table 1, and after adding a stabilizer in the same manner as in the examples, they were pelletized and molded to determine the physical properties. Measurements were carried out and the results are shown in Table 1.

In addition, as a commercially available thermoplastic resin, polyphenylene sulfide manufactured by Philips Co., Ltd. (grade P-4, P in Table 1) is used.
(abbreviated as PS), East step nylon-6 (Grade CM102
6) Styrenic resin MS-8 manufactured by Denki Kagaku Kogyo Co., Ltd.
00 (hereinafter abbreviated as H8) was used.

The physical properties were measured by the following method.

(1) Tensile creep...ASTM D674-
Measured according to 56.

(2) Impact strength: Notched isot strength.

According to ASTM-D256 Measured.

(3) Vicat softening point...load 5Ky, ASTM
- Measured according to D1525.

(41GPC・・・・・・・・・・・・・・・1 share) Showa Denko GPC Color A 5hodex KF-3Q
M, THF solvent, flow rate I Int/mil. Detection was done with UV (240 parts m2). Further, the calibration curve was created using standard polystyrene.

〔Effect of the invention〕

From Table 1, the composition of the present invention has sufficient impact resistance because it contains an imidized copolymer whose molecular weight has been increased by polymerization in the presence of a crosslinkable monomer having two or more vinyl groups. A significant improvement in creep resistance at high temperatures was observed while maintaining the properties. Furthermore, the surface appearance of the molded product obtained from the composition of the present invention was good.

Claims (1)

[Scope of Claims] Component A: 40 to 80% by weight of aromatic vinyl monomer, 25 to 50% by weight of unsaturated dicarboxylic acid anhydride, and copolymerizable with these, based on 0 to 40% by weight of the rubbery polymer. 60 to 100% by weight of a monomer mixture consisting of 0 to 30% by weight of vinyl monomers, and 0.01 to 5 parts by weight of vinyl groups per 100 parts by weight of these rubbery polymers and monomer mixture. The polymer obtained by copolymerization in the presence of two or more crosslinkable monomers is reacted with ammonia and/or a primary amine to add 0.8 to 1.0 molar equivalents of acid anhydride groups. 10 to 90% by weight of an imidized copolymer converted into an imide group, component B: 5 to 80% by weight of rubbery polymer, and 0 to 40% by weight of vinyl cyanide monomer, and vinyl copolymerizable with these. 10 to 90% by weight of a graft copolymer obtained by copolymerizing 20 to 95% by weight of a monomer mixture consisting of 0 to 40% by weight, component C: 40 to 80% by weight of an aromatic vinyl monomer, Contains 40-100% by weight of a thermoplastic resin consisting of 0-40% by weight of a vinyl cyanide monomer and 0-80% by weight of a copolymer consisting of 0-40% by weight of a vinyl monomer copolymerizable with these. A heat-resistant thermoplastic resin composition with excellent creep resistance.