JP2005097343A - Maleimide-compound-containing rubber-reinforced styrene resin composition excellent in heat stability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a maleimide-compound-containing rubber-reinforced styrene resin composition excellent in heat resistance and heat stability. <P>SOLUTION: The maleimide-compound-containing rubber-reinforced styrene resin composition comprises 100 pts.wt. resin composition comprising 5 to 95 wt.% (A) maleimide compound copolymer resin and 95 to 5 wt.% (B) rubber-reinforced styrene resin prepared by grafting at least two types of monomer units including aromatic vinyl compound units and vinyl cyanide units onto a rubbery polymer or mixture of rubber-reinforced styrene resin B and (C) a vinyl compound copolymer resin comprising at least two types of monomer units including aromatic vinyl compound units and vinyl cyanide compound units and 0.01 to 20 pts.wt. (D) at least monofunctional compound selected from among compounds having a glycidyl group or a hydroxy group in the molecule. <P>COPYRIGHT: (C)2005,JPO&amp;NCIPI

Description

  The present invention relates to a rubber-reinforced styrene-based resin composition having excellent thermal stability, including a maleimide compound-based copolymer.

  Maleimide-based heat-resistant resins copolymerized with styrene are widely used for imparting heat resistance to styrene-based rubber-reinforced resins. However, the thermal stability of this composition is not always satisfactory, and it occurs during the production of molded products such as sheet extrusion molding and blow molding, even if it does not cause problems for general injection molding. Unnecessary resin parts are reused after being mixed with new molding resin, but when this unnecessary part is repeatedly used at a relatively high rate and the transfer pressure applied to the product during molding is low, There has been known a problem that an appearance defect phenomenon caused by a deteriorated product occurs due to repeated use (see Patent Documents 1 to 3).

Japanese Patent Publication No. 2-41544 Japanese Examined Patent Publication No. 62-8456 JP 2002-161187 A

  An object of the present invention is to provide a maleimide compound-containing rubber-reinforced styrene-based resin composition having excellent thermal stability.

As a result of intensive investigations to solve the above problems, the present inventor has found that the thermal stability of the maleimide compound-containing rubber-reinforced styrene resin composition is further improved by adding a certain compound having a functional group. The headline and the present invention were made.
That is, the present invention

（２）マレイミド化合物共重合体樹脂（Ａ）におけるマレイミド化合物がＮ−フェニルマレイミド、芳香族ビニル化合物がスチレンである前記（１）に記載のマレイミド化合物含有ゴム強化スチレン系樹脂組成物、
（３）ゴム状重合体に芳香族ビニル化合物単位およびシアン化ビニル化合物単位を含む２種以上の単量体単位がグラフト重合しているゴム強化スチレン系樹脂（Ｂ）および芳香族ビニル化合物単位及びシアン化ビニル化合物単位を含む２種以上の単量体単位からなるビニル化合物共重合体樹脂（C）における芳香族ビニル化合物、およびシアン化ビニル化合物が、それぞれ、スチレンおよびアクリロニトリルである前記（１）又は（２）に記載のマレイミド化合物含有ゴム強化スチレン系樹脂組成物に関する。 (1) Maleimide compound copolymer consisting of 5 to 60 mol% of maleimide compound units of the following formula (1), 20 to 95 mol% of aromatic vinyl compound units and 0 to 60 mol% of other copolymerizable vinyl compound units. 5% to 95% by weight of the coalesced resin (A), and a rubber-reinforced styrene resin (B) in which two or more monomer units including an aromatic vinyl compound unit and a vinyl cyanide unit are graft-polymerized on the rubbery polymer. ) Or a mixture 95 of the rubber-reinforced styrene resin (B) and a vinyl compound copolymer resin (C) composed of two or more monomer units including an aromatic vinyl compound unit and a vinyl cyanide compound unit. One or more monofunctional functional compounds selected from compounds having a glycidyl group or a hydroxyl group in the molecule with respect to 100 parts by weight of a resin composition consisting of ˜5% by weight ( ) The comprising 0.01 to 20 parts by weight maleimide compound-containing rubber-reinforced styrene resin composition,

(2) The maleimide compound-containing rubber-reinforced styrene resin composition according to (1), wherein the maleimide compound in the maleimide compound copolymer resin (A) is N-phenylmaleimide and the aromatic vinyl compound is styrene,
(3) A rubber-reinforced styrene resin (B) and an aromatic vinyl compound unit in which two or more kinds of monomer units including an aromatic vinyl compound unit and a vinyl cyanide compound unit are graft-polymerized to a rubber-like polymer; (1) The aromatic vinyl compound and the vinyl cyanide compound in the vinyl compound copolymer resin (C) composed of two or more kinds of monomer units including the vinyl cyanide compound unit are respectively styrene and acrylonitrile. Alternatively, the present invention relates to a maleimide compound-containing rubber-reinforced styrene-based resin composition as described in (2).

  According to the present invention, it is possible to obtain a maleimide compound copolymer-containing rubber-reinforced styrene-based resin composition having very excellent thermal stability.

The present invention will be specifically described below.
The maleimide compound copolymer resin (A) in the present invention is a maleimide compound copolymer resin having a maleimide compound unit represented by the following formula (1), an aromatic vinyl compound unit or a vinyl compound unit copolymerizable therewith.

  Examples of the copolymer (A) include a method of copolymerizing a mixture of an aromatic vinyl compound unit, an unsaturated dicarboxylic imide derivative compound unit, and other copolymerizable vinyl compound units, an aromatic vinyl compound unit and maleic anhydride. Obtained by a method (imidation) in which a maleic anhydride portion of a polymer obtained by copolymerizing other copolymerizable vinyl compound units containing amide is reacted with ammonia and / or a primary amine and substituted with an imide group. Can do.

  Examples of the aromatic vinyl compound used in the maleimide compound copolymer resin (A) used in the present invention include styrene compounds such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and substituted compounds thereof. Styrene is preferred. Examples of unsaturated dicarboxylic acid imide derivative compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, Nphenylmaleimide, N-methylphenylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N- Maleimide compounds such as chlorophenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-cyclohexylmaleimide and N-isopropylmaleimide, itaconic imide derivatives such as N-methylitaconic imide, N-phenylitaconic imide, etc. N-phenylmaleimide is preferred. Examples of primary amines used for imidization include alkylamines such as methylamine, ethylamine and cyclohexylamine, and aromatic amines such as aniline, toluidine and naphthylamine, with aniline being particularly preferred.

  Other copolymerizable vinyl compounds include maleic anhydride, cyan compounds such as acrylonitrile and methacrylonitrile, alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate, acrylic acid and methacrylic acid. Examples include (meth) acrylic acids. Of these, acrylonitrile is preferred. These may be used alone or in combination of two or more. These are 5 to 60 mol% of maleimide compound units, 20 to 95 mol% of aromatic vinyl compound units and 0 to 60 mol% of one or more other copolymerizable vinyl compound units in the copolymer (A).

  The content of the maleimide compound copolymer resin (A) in the composition of the present invention is 5 to 95% by weight of the resin component in the maleimide compound copolymer resin composition. When it is less than 5% by weight, the effect of improving the heat resistance is insufficient, and when it exceeds 95% by weight, the impact strength is insufficient. The content is determined by the content of maleimide and maleic acid in the maleimide compound copolymer resin (A) and the desired heat resistance.

  The rubber-reinforced styrene resin (B) in the present invention is a graft copolymer in which two or more kinds of vinyl compounds containing an aromatic vinyl compound unit and a vinyl cyanide compound unit are graft copolymerized with a rubbery polymer. A rubber-reinforced styrene resin in which the ratio of the vinyl cyanide compound in the vinyl compound is 10 to 50% by weight, preferably 20 to 40% by weight.

  The rubbery polymer in the rubber-reinforced styrene resin (B) can be used as long as it has a glass transition temperature of 0 ° C. or lower. Specifically, dibutadiene rubber such as polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, polyisoprene, polychloroprene, ethylene-propylene rubber, ethylene-propylene- Block copolymers such as diene terpolymer rubber, styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, silicon rubber, and hydrogenated products thereof can be used. Among these polymers, polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, polybutyl acrylate and the like are preferable. The ratio of the rubber-like polymer in the rubber-reinforced styrene resin is used in the range of 1% by weight to 60% by weight, and is determined according to the required mechanical strength, rigidity, and heat resistance. Preferably, it is 5 to 50% by weight, more preferably 10 to 30% by weight.

  The vinyl compound copolymer resin (C) in the present invention is a vinyl copolymer composed of two or more monomers including an aromatic vinyl compound unit and a vinyl cyanide compound unit. Examples of the vinyl compound used for the vinyl compound copolymer resin (C) and the vinyl compound to be graft copolymerized with the rubber-like polymer include aromatic vinyl compounds such as styrene, α-methylstyrene and paramethylstyrene, methyl methacrylate, methyl Alkyl (meth) acrylates such as acrylate, butyl acrylate and ethyl acrylate, (meth) acrylic acids such as acrylic acid and methacrylic acid, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, N-phenylmaleimide, N-methylmaleimide, A maleimide compound such as N-cyclohexylmaleimide and a glycidyl group-containing compound such as glycidyl methacrylate are used, and at least one of them is a vinyl cyanide compound.

  Preferred combinations include vinyl cyanide compounds and aromatic vinyl compounds, alkyl (meth) acrylates, vinyl cyanide compounds, and maleimide compounds, and more preferably, vinyl cyanide compounds other than acrylonitrile and vinyl cyanide compounds. Examples of the vinyl compound include styrene, α-methylstyrene, N-phenylmaleimide, and butyl acrylate. Vinyl compounds other than vinyl cyanide compounds can be used alone or in combination of two or more.

  The ratio of the component grafted to the rubber-like polymer produced in the process of producing the rubber-reinforced styrene resin graft copolymer of the component (B) is determined by dissolving the polymer produced by the polymerization reaction in acetone and centrifuging the insoluble matter. It can be measured by separating and removing with a separator. The component that dissolves in acetone is the component that has not undergone graft reaction (non-grafted component) in the copolymer that has undergone polymerization reaction, and the value obtained by subtracting the amount of rubber-like polymer from the acetone insoluble content is defined as the value of the graft component. The The proportion of the graft component is preferably 10 to 80 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the rubbery polymer. The method for producing the graft copolymer is not particularly limited, and any of emulsion graft polymerization method, continuous method, batch method, and semi-batch method in which a vinyl compound is graft-polymerized to a rubber-like polymer latex produced by emulsion polymerization is possible. It is.

The ratio of the graft polymer in the rubber-reinforced styrene resin (B) is preferably 1 to 60% by weight. When it is less than 1% by weight, the impact resistance is insufficient, and when it exceeds 60% by weight, the rigidity is insufficient. More preferably, it is 5 to 50 weight%, More preferably, it is 10 to 40 weight%.
The ratio of the vinyl cyanide compound in the rubber-reinforced styrene resin (B) is 10% by weight to 50% by weight. When it is less than 10% by weight or more than 50% by weight, the impact strength and the appearance of the molded product are deteriorated. Preferably it is 20 to 40 weight%.

  The rubber-reinforced styrene resin (B) of the present invention may contain a component that is not grafted to the rubber-like polymer produced in the process of producing the graft polymer. Moreover, you may also contain vinyl compound copolymer resin (C) containing the aromatic vinyl compound unit and vinyl cyanide compound unit which were manufactured separately. In this case, the vinyl compound copolymer resin (C) containing an aromatic vinyl compound unit and a vinyl cyanide compound unit is not limited in terms of crystallinity and non-crystallinity, but preferably the above aromatic vinyl compound and cyanide. A copolymer of a vinyl compound, a copolymer of an aromatic vinyl compound, a vinyl cyanide compound, and an acrylate ester, and a copolymer of an aromatic vinyl compound, a vinyl cyanide compound, and a methacrylic acid ester.

  The rubber-reinforced styrenic resin (B) is produced by a usual method, for example, emulsion polymerization, simultaneously producing a graft polymer and a non-grafted vinyl copolymer, and using a coagulant from the rubber-reinforced styrene resin latex. A method of coagulating solids, and a latex of a mixture of a graft polymer and a vinyl copolymer (hereinafter sometimes abbreviated as GRC) having a high ratio of a rubber-like polymer by emulsion polymerization, are produced in the same manner as described above. The solid content is solidified by using a coagulant, and separately blended with a vinyl copolymer produced by bulk polymerization, emulsion polymerization, suspension polymerization or the like to obtain the desired rubber content.

  The content of the rubber-reinforced styrene resin (B) of the present invention is 95 to 5% by weight of the resin component in the maleimide compound-containing rubber-reinforced styrene resin composition. When it is less than 5% by weight, the impact resistance and moldability are insufficient, and when it exceeds 95% by weight, the heat resistance is insufficient. Preferably it is 95-20 weight%.

  The monofunctional compound (D) in the present invention is a compound having only one glycidyl group or hydroxyl group in the molecule. For example, as a compound having only one glycidyl group in the molecule, methyl glycidyl ether, butyl Aliphatic hydrocarbons such as glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl ether of aromatic hydrocarbon, epoxidized fatty acid octyl ester, fatty acid glycidyl ester such as stearyl glycidyl ester, glycidyl acrylate, Glycidyl methacrylate, 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxydecane, 1,2-epoxycyclohexane, 1,2-epoxy-5-hexene, 1,2-epoxy-5,9 -Cyclooctadiene It said epoxy compound of the epoxy compound and the unsaturated hydrocarbons, saturated hydrocarbons, one end epoxidized and mixtures of these polysiloxanes and the like.

  In addition, compounds having only one hydroxyl group in the molecule include alcohols of saturated and unsaturated hydrocarbons such as ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, lauryl alcohol, cetyl alcohol, and stearyl alcohol. Phenyl alcohol and polysiloxy alcohol, such as octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and 3,5-di-t-butyl-4-hydroxybenzyl phosphonate / diethyl Ether, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3, 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydride) Xylphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxy Phenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2-hydroxy-4-n-octyloctibenzophenone, 2,4-di-t-butylphenyl-3,5 -Di-t-butyl-4-hydroxybenzoate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2 -Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, substituted phenyl alcohols, including those commercially available as polymer additives, and mixtures thereof. .

  These may be used alone or in combination of two or more compounds, for example, a compound having a hydroxy group and a compound having a glycidyl group, or a mixture of compounds having two types of glycidyl groups having different substituents. Absent. Alternatively, within the scope of the object of the present invention, a compound having two or more functional groups can be used together with a small amount of a monofunctional compound.

  The content of the monofunctional compound (D) of the present invention is 0.01 to 20 parts by weight with respect to 100 parts by weight of the maleimide compound-containing rubber-reinforced styrene resin composition. When the amount is less than 0.01 parts by weight, the effect of the present invention is insufficient. When the amount exceeds 20 parts by weight, the influence on physical properties such as impact properties and heat resistance is increased, which is not preferable. Preferably it is 0.2-12 weight part.

  In the resin composition of the present invention, for the purpose of modifying the resin, if necessary, usual additives, that is, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a colorant, titanium oxide, a surface It may contain modifiers, dispersants, plasticizers, stabilizers, antibacterial agents, antifungal agents, foaming agents, wood powder, flame retardants, flame retardant aids, matting agents, viscosity modifiers, and the like.

  Furthermore, the resin composition of the present invention can be appropriately blended with other polymers. For example, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyamide, polyester, polysulfone, polyether ketone, polyether sulfone, polyether sulfone, fluororesin, silicone resin, polyethylene, polypropylene, PMMA, polyamide elastomer, AS graft polyethylene, AS Examples include graft polypropylene.

  About the manufacturing method of the resin composition in this invention, it can manufacture by a normal method, for example, the melt blend etc. by extrusion kneading | mixing. As this production method, a maleimide compound copolymer resin (A), a rubber-reinforced styrene resin (B) (which may include a vinyl compound copolymer resin (C)), and one or more monofunctional functional compounds (D ) Or the like may be mixed and kneaded and mixed, and the thermoplastic resin composition (E) is obtained by kneading and mixing the maleimide compound copolymer resin (A) and one or more monofunctional functional compound (D). And kneading and mixing the rubber-reinforced styrene resin (B) with the maleimide compound copolymer resin (A), the vinyl compound copolymer resin (C) and one or more monofunctional functional compounds ( The thermoplastic resin composition (E ′) may be produced in advance by kneading and mixing D), and the rubber-reinforced styrene-based resin (B) may be kneaded and mixed.

  The composition of the present invention can be molded by injection molding, sheet extrusion molding, vacuum molding, pressure forming, profile extrusion molding, blow molding, foam molding, injection press molding, gas injection molding, etc. Particularly effective in molding and sheet extrusion molding. Further, further effects can be expected following the case where unnecessary parts of the molded product are pulverized and blended with the virgin material during processing.

The use of the molded product obtained by using the composition of the present invention is not particularly limited, but is preferably used for sanitary products such as OA equipment housings, bathtubs, vanity panels, and vehicles such as air spoilers, aero parts, bumpers, and the like. It can be used for applications such as wooden interiors, surrounding edges, picture frames, door stops, handrails, and office furniture such as partitions and table curtains.
Next, the present invention will be described with reference to examples and reference examples.

The components used in Examples and Comparative Examples are described below. (Hereinafter, “parts” means “parts by weight”.)
(Maleimide compound copolymer resin (A1))
The contents of styrene, N-phenylmaleimide and maleic anhydride as measured by FT-IR are 48%, 51% and 1% by weight (39 mol%, 60 mol% and 1 mol%), respectively, and the melt volume flow rate (Implemented based on ISO1133 (JIS K7210). Test conditions Temperature 265 ° C., test load 10 kg) is 2.0 and maleimide compound copolymer having a glass transition point of 203 ° C. measured by DSC (DSC220 manufactured by Seiko Denshi). resin.

(Maleimide compound copolymer resin (A2))
The contents of acrylonitrile, styrene, and N-phenylmaleimide measured by FT-IR are 17% by weight, 50% by weight, and 33% by weight (32 mol%, 48 mol%, 19 mol%), respectively, and melt volume flow rate (ISO1133). Conducted based on (JIS K7210) Test conditions A maleimide compound copolymer resin having a temperature of 220 ° C. and a test load of 10 kg) of 1.6 and a glass transition point measured by DSC of 148 ° C.

(Rubber reinforced styrene resin (B))
This is a composition obtained by emulsion polymerization of acrylonitrile and styrene in the presence of polybutadiene rubber, the proportion of acetone insolubles in the composition is 55%, and the contents of acrylonitrile, styrene and butadiene measured by FT-IR are each 20% by weight. %, 47% by weight, 33% by weight, ABS resin having a melt volume flow rate (based on ISO 1133 (JIS K7210), test conditions: temperature 220 ° C., test load 10 kg) of 3.8.
(Vinyl compound copolymer resin (C))
The acrylonitrile and styrene contents measured by FT-IR are 29% by weight and 71% by weight, respectively, and the melt volume flow rate is performed based on ISO1133 (JIS K7210). Test conditions: temperature 220 ° C., test load 10 kg) 27 AS resin.

(Monofunctional group compound (D))
Commercially available products were purchased and used for the compounds shown below.
D1: Stearyl glycidyl ether (Nippon Yushi Co., Ltd. Epiol SK)
D2: p-tert-butylphenylglycidyl ether (Epiol TB manufactured by NOF Corporation)
D3: Epoxidized fatty acid octyl ester (Adekasizer D32 manufactured by Asahi Denka Kogyo Co., Ltd.)
D4: Stearyl alcohol (NAA-45 manufactured by NOF Corporation)
D5:
2- [1- (2-Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate (Sumitomo Chemical Co., Ltd. Sumilizer GS)
D'6: alkylated diphenylamine (Sumilizer 9A manufactured by Sumitomo Chemical Co., Ltd.)

(Comparative Example: Multiple Functional Group Compound (F))
F1: Poly (glycidyl methacrylate)
F2: Calcium stearate (Daiwax C, manufactured by Dainichi Chemical Co., Ltd.)
F3: Glycerol monostearate (Rikenmar S-100, manufactured by Riken Vitamin Co., Ltd.)
[Example 1]

28 parts by weight of maleimide compound copolymer resin (A1), 55 parts by weight of rubber-reinforced styrene resin (B), 17 parts by weight of vinyl compound copolymer resin (C), and monofunctional compound (D) D1 Two parts were kneaded and granulated with a twin-screw extruder set at a cylinder temperature of 270 ° C. to obtain a composition (Y) and used for evaluation. The evaluation results are shown in Table 1. The evaluation method is shown below.
[Examples 2-11, Comparative Examples 1-8]

The maleimide compound copolymer (A1), the rubber-reinforced styrene resin (B), the vinyl compound copolymer resin (C), and the compounds shown in D1 to D5, D′ 6, or F1 to F3 as in Example 1. Each was granulated with a twin-screw extruder set at a cylinder temperature of 270 ° C. at the composition ratio shown in Table 1 or Table 2 to obtain the intended final composition (Y) and used for evaluation. The evaluation results are shown in Tables 1 and 2. The evaluation method is shown below.
[Example 12]

  Biaxial shaft in which 80 parts by weight of maleimide compound copolymer resin (A1), 20 parts by weight of vinyl compound copolymer resin (C), and 5.7 parts by weight of monofunctional compound (D4) were set at a cylinder temperature of 270 ° C. First, an intermediate composition (X) was obtained by kneading and granulating with an extruder. Next, 35 parts by weight of the intermediate composition (X), 55 parts by weight of the rubber-reinforced styrene resin (B), and 10 parts by weight of the vinyl compound copolymer resin (C) were set in a twin-screw extruder set at a cylinder temperature of 270 ° C. The target final composition (Y ′) was obtained by granulation and used for evaluation. The composition ratio of this product was the same as that in Example 6, and only the difference in the manufacturing method was confirmed, but it was confirmed that the effect was not changed. The evaluation results are shown in Table 1.

(Evaluation methods)
・ Evaluation equipment:
Rheometrics RDA II (uses 25mmφ parallel plate)
・ Measurement sample adjustment:
The obtained pellets are compression molded at 250 ° C. to obtain a 1 mm thick flat plate. The obtained flat plate was cut into 30 mm square and used. Two flat plates after drying at 100 ° C. for 2 hours were used in the measuring device in a stack so as not to generate bubbles during the measurement.
·Test conditions:
Gap width: 2 mm to 3 mm, γ: 10%, ω: 0.1 rad / sec,
Measurement temperature: 240 ° C., test time: 24 hours

・ Judgment method:
The viscosity η (Pa · s) before the test and the viscosity η (Pa · s) after the 24 hour test are measured, and the rate of increase R of the viscosity η is calculated. (R = viscosity η value after test / viscosity η value before test)
The increase rate R of the viscosity η is 6 times or less, and the increase rate ratio (R (sample) / R (blank)) with respect to the blank composition was determined as follows.
・ When the rate of increase in viscosity is 70% or less: The effect is very high (◎)
・ When the ratio of viscosity increase rate is 70 to 90% ... Effective (○)
・ When the rate of increase in viscosity is 90% or more: No effect (×)
Judgment of ◎ and ○ was accepted, and x was rejected.

  As shown in Tables 1 and 2, Examples 1 to 12 have an effect of decreasing the rate of increase in viscosity with respect to Comparative Example 1 which is a blank. Moreover, although Comparative Examples 3-5 is a case where a multiple functional group is added, it becomes a reverse effect. Comparative Example 6 is an example of a secondary amine compound that is a monofunctional functional group, but the effect does not appear and the reactivity varies depending on the type of functional group. Moreover, since the comparative example 7 has few addition amounts, an effect is inadequate. Furthermore, as shown in Comparative Example 8, it can be seen that the system containing the rubber-reinforced styrene resin is particularly effective.

  Since the composition of the present invention is excellent in heat resistance and extremely excellent in thermal stability, it is suitable for producing resin products in the chemical industry.

Claims (3)

Maleimide compound copolymer resin comprising 5 to 60 mol% of maleimide compound units of the following formula (1), 20 to 95 mol% of aromatic vinyl compound units and 0 to 60 mol% of other copolymerizable vinyl compound units ( A) A rubber-reinforced styrene-based resin (B) in which 5 to 95% by weight and two or more monomer units containing an aromatic vinyl compound unit and a vinyl cyanide unit are graft-polymerized on a rubber-like polymer, or 95-5 weight of a mixture of the rubber-reinforced styrene resin (B) and a vinyl compound copolymer resin (C) composed of two or more monomer units containing an aromatic vinyl compound unit and a vinyl cyanide compound unit % Of the monofunctional functional compound (D) selected from compounds having a glycidyl group or a hydroxyl group in the molecule with respect to 100 parts by weight of the resin composition comprising: .01～20 comprising parts maleimide compound-containing rubber-reinforced styrene resin composition.

The maleimide compound-containing rubber-reinforced styrene resin composition according to claim 1, wherein the maleimide compound in the maleimide compound copolymer resin (A) is N-phenylmaleimide and the aromatic vinyl compound is styrene. Rubber Reinforced Styrenic Resin (B), Aromatic Vinyl Compound Unit, and Vinyl Cyanide in which Two or More Kinds of Monomer Units Containing Aromatic Vinyl Compound Unit and Vinyl Cyanide Compound Unit are Graft-Polymerized on Rubber Polymer The aromatic vinyl compound and the vinyl cyanide compound in the vinyl compound copolymer resin (C) composed of two or more kinds of monomer units including the compound unit are styrene and acrylonitrile, respectively. The maleimide compound-containing rubber-reinforced styrene-based resin composition described.