JPS6218458A - Creep-and heat-resistant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent resistance to creep and heat, consisting of a thermoplastic resin composed of an imide copolymer and a graft copolymer. CONSTITUTION:40-100pts.wt. thermoplastic resin consisting of 10-90% (by weight; the same applies herein below) imide copolymer (A) obtd. by copolymerizing 0-40wt% rubbery polymer (a) and 100-60% monomer mixture of 40-80% arom. vinyl monomer (b), 25-50% unsaturated dicarboxylic acid anhydride (c) and 0-30% copolymerizable monomer (d) in the presence of 0.02-1pt.wt. [per 100pts.wt. of the combined quantity of components (a) and (b)] and reacting NH3 and/or a primary amine with the resulting polymer to imidate 0.8-1.0mol equivalent of the acid anhydride groups, 10-90% graft copolymer (B) obtd. by copolymerizing 5-80% component (a) and 20-95% mixture of 40-80% component (b), 0-40% vinyl cyanide monomer (e) and 0-40% component (d) and 0-80% copolymer (C) composed of 40-80% component (b), 0-40% component (e) and 0-40% component (d) is melt-kneaded together with 60-0pts.wt. other thermoplastic resin.

Description

[Detailed Description of the Invention] [Industrial Application Field] The invention relates to a heat-resistant thermoplastic with excellent creep resistance containing an imidized copolymer whose molecular weight has been increased by polymerization using a polyfunctional radical initiator. The present invention relates to a resin composition. More specifically, the copolymer is produced by polymerizing a monomer mixture containing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride using a polyfunctional radical initiator in the presence or absence of a rubbery polymer. A heat-resistant thermoplastic resin with excellent creep resistance, which contains as an essential component a mixture of an imidized copolymer obtained by reacting ammonia and/or a primary amine with a rubber-modified aromatic vinyl copolymer. Regarding the composition.

The molded article obtained from the resin composition of the present invention can be used particularly in applications requiring creep resistance and anti-corrosion 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 and its problems]

Thermoplastic resin compositions containing copolymers of aromatic vinyl monomers and unsaturated dicarboxylic anhydrides or imide derivatives thereof have been known (USP 3,642,949.U).
SP3651171), has high heat resistance that can withstand heat distortion temperature.

Furthermore, JP-A No. 60-23438 discloses a heat-resistant compound containing an aromatic vinyl monomer and an unsaturated dicarboxylic acid imide derivative;
Examples of thermoplastic resin compositions with excellent impact resistance are disclosed, and this composition is a useful material suitable for fields requiring heat resistance such as automobile parts and electrical and electronic parts. However, these compositions have somewhat insufficient creep resistance at high temperatures for long periods of time, so their applications may naturally be limited. Conventionally, the stiffness of thermoplastic resins, To improve creep resistance,
A method of blending fibrous substances such as glass fibers is often discussed, and U.S. Patent No. 3,632,791 discloses a composition in which glass fibers are blended with a resin containing an aromatic vinyl monomer and maleimide. has been done. However, in this case, since the affinity between the resin and the glass fiber is poor, the effect of improving rigidity is small. Furthermore, even if a sufficient improvement effect can be 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 methods for improving creep resistance without these disadvantages, the present inventors have determined that a monomer mixture containing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride can be added to a rubber-like polymer. Thermoplastic material whose essential component is an imidized copolymer obtained by reacting a copolymer copolymerized with a polyfunctional radical initiator in the presence or absence of a polyfunctional radical initiator with ammonia and/or a primary amine. It was discovered that the resin exhibits excellent creep resistance, and the present invention was completed.

Component A: 0 to 40% by weight of a rubbery polymer, 40 to 80% by weight of an aromatic vinyl monomer, 25 to 50% by weight of an unsaturated dicarboxylic acid anhydride, and a vinyl copolymerizable with these. When copolymerizing 60 to 100 weight % of a monomer mixture consisting of 0 to 30 weight % of monomers, 0.02 to 1 part by weight of polyester is added to 100 parts by weight of these rubbery polymers and monomer mixture. A polymer obtained by copolymerization using a functional radical initiator is reacted with ammonia and/or a primary amine to convert 0.8 to 1.0 molar equivalents of acid anhydride groups into imide groups. imidized copolymer 10-90f
Component B: 5 to 80% by weight of rubbery polymer, 40 to 80% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer, and components that can be combined 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 of a vinyl monomer, and component C: 40 to 80% by weight of an aromatic vinyl monomer. , 40 to 100% by weight of a thermoplastic resin consisting of 0 to 403% by weight of vinyl cyanide monomers and 0 to 801% by weight of vinyl monomers copolymerizable with these. This is a heat-resistant thermoplastic resin composition with excellent creep resistance and impact resistance, comprising 0 to 60 parts by weight of other thermoplastic resins.

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

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

Examples of the aromatic vinyl monomer constituting component A include styrene monomers and substituted monomers thereof such as styrene, α-methylstyrene, vinyltoluene, t-7'' tylstyrene, and chlorostyrene. Styrene is immediately preferred.

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

Vinyl monomers that can be copolymerized with these include vinyl cyanide monomers such as acrylonitrile, tacrylonitrile, α-chloroacrylonitrile, and acrylic ester monomers such as methyl acrylate and ethyl acrylate. Among these, there are methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, vinyl carboxylic acid monomers with acrylic acid and methacrylic acid, acrylic acid amide, methacrylic acid amide, etc. Monomers such as acrylonitrile methacrylate, acrylic acid, and methacrylic acid are preferred.

Examples of rubbery polymers include butadiene polymers, copolymers of butadiene and copolymerizable vinyl monomers, and ethylene-
Propylene copolymers, block copolymers of butadiene and aromatic vinyl, acrylic ester polymers, and copolymers of acrylic esters and vinyl monomers copolymerizable therewith are used. The rubber component in the A component polymer is 4
If the amount exceeds 0, it is unfavorable in terms of heat resistance and moldability.

As a polyfunctional radical initiator, one having a decomposition temperature of 70 to 100°C and 8°C in order to obtain a half-life of 10°C exhibits the greatest molecular weight increasing effect. A preferred multifunctional radical initiator is 2,5-dimethyl-2,5-bis(2-
ethylhexanoylperoxy)hexane, di-t-butylperoxyhexahydroterephthalate, 4-(t
-)f rubberoxycarbonyl)-3-hexyl-6-
(7-(t-butylperoxycarbonyl)hebutyl)
Cyclohexene, C-t-butylperoxyacere-1
-12,5-dimethyl-2,5-di(benzoylperoxy)hexane, Ll-sheet t-7'tilperoxycyclohexane, 1,1-di-t-butylperoxy-3
, 3,5-trimethylcyclohexane, 2,2-di(
t-butylperoxy)butane, etc.

These can be used alone or in combination. In the production of component A, the amount of the polyfunctional radical initiator used is 0.02 to 1 part by weight, preferably 0.02 to 1 part by weight, based on 100 parts by weight of the monomer mixture and rubbery polymer.
．． 05 to 0.8 parts by weight. If it is less than 0.02 parts by weight, the polymerization rate is extremely slow, and if it exceeds 1 part by weight, the amount of oligomers produced increases, increasing the molecular weight and making it impossible to obtain sufficient creep resistance.

In addition to the primary amines used in the imidization reaction, alkylamines such as methylamine, ethylamine, butylamine, and cyclohexylamine, and aromatic amines such as chloro- or bromine-substituted alkylamines, aniline, tolylamine, and naphthylamine, and chloro- or bromine Examples include halogen-substituted aromatic amines such as 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. −
If the temperature exceeds 350°C, the physical properties will deteriorate due to thermal decomposition of the polymer. The amount of ammonia and/or primary amine to be reacted is preferably 0.8 molar equivalent or more based on the unconverted 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 a decrease in thermal stability and hot water resistance, which is not preferable.

Next, component B will be explained. The rubbery polymer used for component B is butadiene alone or a polymer consisting of a vinyl monomer copolymerizable with it, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, or acrylic branched ester alone or this. There are polymers made of vinyl monomers that can be copolymerized with. Aromatic vinyl monomers used for component B include nostyrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and substituted monomers thereof; among these, styrene, α- -Methylstyrene is 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 acrylic ester, ethyl acrylic ester, and 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, acrylic acid amide 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 40-80% by weight of an aromatic vinyl monomer, 0-40% by weight of a vinyl cyanide monomer, and 0-40% 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. The aromatic vinyl monomers used for component C include styrene thread monomers and their substituted products such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, among which styrene and α-methylstyrene is particularly preferred.

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

Vinyl monomers that can be copolymerized with these include acrylic ester monomers such as methyl acrylate ester, ethyl acrylate, butyl acrylate, and methacrylic ester monomers such as methyl methacrylate and handyl methacrylate. 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 uninvented composition is a mixture of the above-mentioned ingredients, component B, component C if necessary, and other thermoplastic resins if necessary, but there are no particular restrictions on the mixing method, and known means can be used. Can be used. For example, as a means of doing so,
Banbury mixer, Henschel mixer, tumbler
Examples include mixers, mixing rolls, single-screw or twin-screw extruders, and the like. As for the mixing form, there are methods of obtaining the composition by ordinary melt mixing, melt kneading in each stage using master pellets, etc., and blending in M-kukuri.

The blending proportions of component A, component B, and component C are 10 to 90% by weight for component A, 10 to 90% by weight for component B, and 0 to 80% by weight for component C, but the preferred range is A.
The component is 20 to 70% by weight, the B component is 30 to 60%, and the C component 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 cold creep properties exhibited by component A, the deterioration of moldability can be prevented by blending with an appropriate blending ratio of components B and C. This is to prevent damage, impart impact resistance, and maintain other physical properties in a well-balanced manner.

In addition, the composition of the present invention may further include stabilizers, flame retardants, plasticizers, lubricants, ultraviolet absorbers, colorants and talc, as required.
Fillers such as silica, clay, calcium carbonate, etc. may be added.

Hereinafter, the present invention will be further explained by examples, but the invention is not limited to the following examples unless the gist thereof is exceeded. Note that all parts and sections in the examples are expressed on a weight basis.

Experimental Example (1) Production of Component A 60 parts of styrene and 70 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, and the system was replaced with gold nitrogen gas.The temperature was then raised to 85°C and 40 parts of maleic anhydride was added.
and 0.2 parts of 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane dissolved in 230 parts of methyl ethyl ketone were added continuously over 7 hours. After the addition, a portion of the viscous reaction solution was kept at 85°C for another 4 hours, and unreacted monomers were quantified by gas chromatography.
Polymerization rate is 98.5% of styrene, 99.0% of maleic anhydride.
%Met. To the copolymer solution obtained here, 36.4 parts of aniline, which is 0.96 equivalent to the maleic anhydride group,
0.3 part of triethalamine was added, and the mixture was reacted at 150°C for 6 hours. Add 200 parts of methyl ethyl ketone to the reaction solution, cool to room temperature, and add 2500 parts of methanol with stirring.
The mixture was poured into a portion, precipitated, separated from p, and dried to obtain an imidized copolymer. According to C-C-13N analysis, almost 100% of aniline was reacted in the reaction of the acid anhydride group to the imide group. Further, as a result of GPC analysis, the Mw (weight average molecular weight) of this imidized copolymer was 220,000. This was designated as Polymer A.

2,5-dimethyl-2,5-bis(2-
The same procedure as in Experimental Example (1) was carried out except that 0.2 g of ethylhexanoyl peroxy)hexane was replaced with 0.2 part of benzoyl peroxide. The polymerization rate was 99.1% for styrene and 98.3% for maleic anhydride. As in Experimental Example (1), almost 100% of the aniline had reacted, and the Mw according to GPC analysis was 115,000. This was designated as Polymer B.

Into the same autoclave as in Experimental Example (1), 57 parts of styrene and 60 parts of methyl ethyl ketone were charged, and after replacing the inside of the system with nitrogen gas, the temperature was raised to 95°C, and 43 parts of maleic anhydride and 1,1-di-t-butyl were added. Peroxy-3,3,5-1-
0.15 parts of remethylcyclohexane was dissolved in 240 parts of methyl ethyl ketone and added continuously for a total of 3.5 hours. After the addition, the temperature was maintained at 95°C for 3 hours, and then the temperature was raised to 105°C.
The procedure was exactly the same as in Experimental Example (1), except that the temperature was raised to 100% and maintained for an additional 3 hours, and 40.0 parts of aniline (0.98 equivalents of maleic anhydride groups) was used. The polymerization rate was 97.2% for styrene and 98.8% for maleic anhydride. C
-C-13 Part analysis reaction rate of aniline is almost 100%
The Mw according to GPC analysis was 20.5 million. This was designated as Polymer C.

The polymerization temperature in Experimental Example (3) was changed from 95°C to 85°C, and 1.1
All experiments were conducted except that 0.15 part of -di-t-butylperoxy-3,3,5-trimethylcyclohexane was replaced with 0.2 part of benzoyl peroxide, and the maleic anhydride solution was added continuously for 7 hours. The same operation as in Example (3) was performed. The total ratio was 98.1% styrene and 97.6% maleic anhydride. Similar to Experimental Example (3), aniline reacted almost 100%, and the MW was 110,000 according to GPC analysis. This was made into a polymer.

Experimental Example (5) Production of Component A 55 parts of styrene and 80 parts of methyl ethyl ketone were charged into the same autoclave as in Experimental Example (1), and after purging the system with nitrogen gas, the temperature was raised to 95°C, and 1 solution of anhydrous maleic was added. 4
5 parts and 0.1 part of di-t-butyl peroxyazelate,
0.03 part of 4-(t-butylperoxycarbonyl)-3-hexyl-6-(7-(t-phthylperoxycarbonyl)hefur)cyclohexene'! A solution dissolved in 220 parts of r-methyl ethyl ketone was added continuously over a period of 4 hours, and the temperature was maintained at 95° C. for an additional 3 hours after the addition.

The temperature was then raised to 105°C and maintained for an additional 3 hours.

Polymerization rate is 99.5% of styrene and 99.0% of maleic anhydride.
%Met. 40.6 parts of Ayu 9F (0.95 equivalent to the maleic anhydride group) and 0.3 parts of triethylamine were added, and the mixture was reacted at 150°C for 7 hours. The following is an experimental example (1)
An imidized copolymer was obtained through exactly the same operation as above. C-
Almost 100% of the C-13N modified aniline reacted, and GPC analysis showed that the MW was 210,000. This was designated as Polymer E.

In Experimental Example (5), di-t-butylperoxyase L/
-0.1 part,! = 0.03 part of 4-(t-butylperoxycarbonyl)-3-hexyl-6-(7-(t-butylperoxycarbonyl)heptyl)cyclohexene was replaced with 0.15 part of benzoyl peroxide, and polymerization The temperature was set to 85°C, and the maleic anhydride solution was added in 7.
All operations were performed in the same manner as in Experimental Example (5) except that the addition was continued for 5 hours. The polymerization rate was 98.0% for styrene and 100% for maleic anhydride. The reaction rate of aniline is approximately 1
00% Ruri, Mw was 120,000. This is polymer F
And so.

Styrene 58 was placed in the same autoclave as in Experimental Example (1).
1 part, 70 parts of methyl ethyl ketone, and 15 parts of polybutadiene cut into small pieces were charged, and after stirring 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 lowered to 85.
The temperature was raised to ℃.

42 parts of maleic anhydride and 0.2 parts of 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane.
A solution of 16 parts dissolved in 230 parts of methyl ethyl ketone was continuously added over 8 hours.

After the addition, the temperature was maintained at 85°C for an additional 3.5 hours, and then the experimental example (
The polymerization rate was determined in the same manner as in 1) and found to be 96.
8%, maleic anhydride [98.0%]. To the copolymer solution obtained here were added 33.9 parts of aniline in an amount of 0.85 equivalent to the maleic anhydride group, 5.8 parts of methylamine (30% aqueous solution) in an amount of 0.13 equivalent, and 0.3 part of triethylamine. The mixture was added and reacted at 140°C for 8 hours. 250 parts of methyl ethyl ketone was added to the reaction solution, and after cooling to room temperature, it was poured into 3,000 parts of vigorously stirred methanol, followed by precipitation, door to door, and drying to obtain an imidized copolymer. As a result of MR analysis of C-13 part, aniline and methylamine were almost 100% reacted. Also, M of the tetrahydrofuran (THF) soluble part
W' was 155,000 as a result of GPC analysis. This imidized copolymer was designated as M-mounted body G.

Experimental example (8) Production of comparative A component 2,5-dimethyl-2,5-bis(2-
The same procedure as in Experimental Example (7) was carried out except that 0.16 parts of benzoyl peroxide was used instead of 0.16 parts of ethylhexanoylperoxy)hexane. The polymerization rate was 97.0% for styrene and 98.0% for maleic anhydride.

Aniline and methylamine reacted almost 100% as in Experimental Example (7). The imidized copolymer is THF
The MW of the soluble portion was 87,000. This was designated as Polymer H.

fruit! v! Example (9) Production of component A In an autoclave similar to Experimental Example (1), 50 parts of styrene, 10 parts of α-methylstyrene, and acrylonitrile (IJ) were added.
After replacing with nitrogen, the temperature was raised to 90°C, and 30 parts of anhydrous maleic acid and 0.15 parts of di-t-butylperoxy-hexahydroterephthalate were added to 260 parts of methyl ethyl ketone. was added continuously over 6 hours. After the addition, the temperature was kept at 90°C for another 3 hours, and then the temperature was raised to 100°C and kept for another 2 hours. The polymerization rate is styrene 96.6%, α-methylstyrene 91.0%, acrylonitrile 94.0%,
Anhydrous maleic [97.3%]. The obtained copolymer solution contains 28.5 aniline equivalents to several maleic anhydride groups.
140°C.
The mixture was allowed to react for 8 hours. Hereinafter, an imidized copolymer was obtained through the same operation as in Experimental Example (1). The reaction rate of aniline is C
-C-13N processing was almost 100%, and the MW measured by GPC was 200,000. This was designated as Polymer I.

0.15 parts of di-t-butylperoxy-hexahydroterephthalate in Experimental Example (9) was replaced with 0.2 parts of benzoyl peroxide, the polymerization temperature was set to 85°C, and the maleic anhydride solution was continuously added for 9 hours. All other examples are experimental examples (9
) was performed. Polymerization rate is styrene 97.9
%, α-methylstyrene: 89.5%, acrylonitrile: 92%, and maleic anhydride: 99.0%. Experimental example (
9) Similarly, aniline is ha! ! , 100% reaction was observed, and Mw was 110,000. This was designated as Polymer J.

Styrene 80 was placed in the same autoclave as in Experimental Example (1).
parts, 10 parts of α-methylstyrene, 7 parts of methyl ethyl ketone
After charging 0 parts and purging the system with gold nitrogen gas, the temperature was raised to 85°C and anhydrous malein! A solution of 10 parts of benzoyl peroxide o and 230 parts of zgk methyl ethyl ketone was added continuously over 9 hours, and the reaction was continued for an additional 5 hours. The polymerization rate was 95% for styrene, 90% for α-methylstyrene, and 96.5% for maleic anhydride. The copolymer solution obtained here contained 0.0% to maleic anhydride groups.
5 equivalents of aniline 4.7°, triethylamine 0.2
150° C. and reacted at 150° C. for 5 hours. Below is an experimental example (
An imidized copolymer was obtained through the same operation as in 1). Almost all of the aniline reacted, and the Mw was 95,000. This was made into a polymer.

Experimental example (12) Production of component B Polybutadiene latex 143 ta (solid content 35
%, weight average particle size 0135μ, gel content 90%), 1 part potassium stearate, 0.1 part sodium formaldehyde sulfoxylate, 0.03 part tetrasodium ethylenediamine tetraacetic acid, 1st sulfuric acid Iron 0
．． 3 parts of OO and 150 parts of ion-exchanged pure water were heated to 5XJ°C, and 65 parts of renystyrene and α-methyls f''
5 parts, 30 parts of acrylonitrile, 0.3 parts of t-dodecylmercaptan, 0.3 parts of cumene hydroperoxide.
18 parts were added continuously over 6 hours, and after further addition, the temperature was increased to 70°C.
The temperature was raised to 1, and polymerization was carried out for 2 hours. The polymerization rate reached 97.0%. After adding an antioxidant to the obtained latex, it was coagulated with cal chloride/rum, washed with water, and dried to obtain a graft copolymer as a white powder. This was made into a polymer.

Experimental Example (13) Production of component C 45 parts of styrene, 25 parts of α-methylstyrene, 30 parts of acrylonitrile, 2.5 parts of potassium stearin, t-
Dodenormel butane 0.4 and ion exchange pure water 2
30 parts was heated to 70°C, and 0.0% of potassium persulfate was added to it.
05 parts were added to start 1 part. 6 from the start of polymerization
After an hour, 0.03 part of potassium perforate was further added, and the temperature was raised to 80° C. and maintained for 3 hours to complete the polymerization. ■
The fraction was 98.0. The obtained latex was coagulated with calcium chloride, washed with water, and dried to obtain a white powder copolymer, which was designated as Polymer M.

Shoshi 8-01-10 A ash, B component, C component, and a commercially available thermoplastic resin were blended in the proportions shown in Table 1, and to this was added 2 parts of trimethialyl phosphite, octadecyl-3-(3,5 -ditertiarybutyl-4-hydroquinphenyl)propionate 0.
After adding 5 parts, it was mixed in a shell/shell mixer.

This chaos! F! The mixture was extruded into pellets using a 30 mmφ screw extruder equipped with a devolatilization device. After molding using this pellet injection molding machine, physical properties were measured, and the results are shown in Part 1.

Ratio 11! ! 2 Examples 1 to 5 Comparative A component, B component, C component and a commercially available thermoplastic resin were combined in the amount ratio shown in Table 1, and after adding the same stabilizer as in Example, pelletized and molded. Physical properties were measured and the results are shown in Table 1.

Commercially available thermoplastic resins include polysulfone manufactured by UCC (grade P-1700, hereinafter abbreviated as PSU), polycarbonate manufactured by Mitsubishi Kasei Corporation (grade 7025, hereinafter abbreviated as PC), and styrene-based resin manufactured by Denki Kagaku Kogyo Co., Ltd. Resin GR-2000 (hereinafter abbreviated as GR) was used.

The physical properties were measured by the following method.

(1) Tensile creep...ASTM D-674-56
Measured according to.

(2) Equilibrium strength: notched isot strength.

6111 standard according to ASTM-D256.

(3) Vikatsu softening point...Load 5 Kg -, AS
Measured according to TM D 1525.

(41GPC... Using GPC column ShodexKF-80M f manufactured by Showa Denko Co., Ltd., THF solvent,
Flow rate 1→-1 detection was performed using TJV (240 nm). In addition, the carrier plane curve was created using standard polystyrene.

〔Effect of the invention〕

As shown in Table 1, the composition of the present invention has significantly improved creep resistance at high temperatures by containing an imidized copolymer whose molecular weight has been increased by monomerization using a polyfunctional radical initiator. A scribble effect on impact resistance is observed. Moreover, the surface appearance of the molded article obtained from the composition of the present invention was good.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedure Supplement iE Book 16W60 August! 3rd Patent Office Commissioner Michibe Uga 1 Case No. 155221 filed in 1985 Title of invention Creep-resistant and heat-resistant thermoplastic resin composition 3 Amendment 1
-Relationship with the person's case Patent applicant address 1-4-1, Arisa-cho, Chiyoda-ku, Tokyo The column in the detailed description of the invention in the specification is corrected to ``Strain resistance J.''

(2) "Acrylonitrile methacrylonitrile" on page 9, line 6 of the specification is corrected to "acrylonitrile, methacrylonitrile."

(3) “Methacrylic acid” on page 9, line 15 of the specification is changed to “
methacrylic acid, etc.”

(4) [Ronitrile, methacrylic acid J] on page 9, line 15 of the specification is corrected to "ronitrile, methacrylic acid."

(5) "Naphthylamine" on page 11, line 15 of the specification has been corrected to "naphthylamine."

(6) [Acrylic acid amide, methacrylic acid amide J] on page 13, line 19 of the specification is corrected to ``acrylic acid amide, methacrylic acid amide.''

(7) "Ethyl methyl acrylate" on page 15, line 4 of the specification is corrected to [methyl acrylate, ethyl].

(8) "Triethylamine" on page 17, lines 19-20 of the specification is corrected to "1 triethylamine/".

(9) "Tristearylphosphite" on page 27, lines 18-19 of the specification is corrected to "tristearylphosphite."

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. When copolymerizing 60 to 100% by weight of a monomer mixture consisting of 0 to 30% by weight of a vinyl monomer, 0.02 to 1 part by weight per 100 parts by weight of the rubbery polymer and monomer mixture. A polymer obtained by copolymerization using a polyfunctional radical initiator is reacted with ammonia and/or a primary amine to convert 0.8 to 1.0 molar equivalents of acid anhydride groups into imide groups. 10 to 90% by weight of an imidized copolymer converted into Component B: 40 to 80% by weight of aromatic vinyl monomer and 0 to 80% of vinyl cyanide monomer based on 5 to 80% by weight of rubbery polymer. 10-90% by weight of a graft copolymer copolymerized with 20-95% by weight of a monomer mixture consisting of 40% by weight and 0-40% by weight of a vinyl monomer copolymerizable with these, component C: aroma. 40 to 80% by weight of group vinyl monomers, 0 to 40% by weight of vinyl cyanide monomers, and 0 to 80% by weight of a copolymer consisting of 0 to 40% by weight of vinyl monomers copolymerizable with these. A heat-resistant thermoplastic resin composition having excellent creep resistance and impact resistance, comprising 40 to 100% by weight of a thermoplastic resin and 0 to 60 parts by weight of another thermoplastic resin.