JP3957663B2 - Method for producing heat-resistant thermoplastic resin and heat-imparting material comprising the heat-resistant thermoplastic resin - Google Patents
Method for producing heat-resistant thermoplastic resin and heat-imparting material comprising the heat-resistant thermoplastic resin Download PDFInfo
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本発明はＡＢＳ樹脂に対して耐熱付与効果が極めて高く、色相が良好で、メタノール可溶分の少ない耐熱性熱可塑性樹脂の製造方法とその熱可塑性樹脂とＡＢＳ樹脂を混合することにより得られる、ＡＢＳ樹脂に対して分散性が良好でかつ耐熱付与性能の高い耐熱付与材とそれを用いた樹脂組成物に関するものである。 The present invention has an extremely high heat resistance imparting effect on the ABS resin, has a good hue, and is obtained by mixing the thermoplastic resin and the ABS resin with a method for producing a heat resistant thermoplastic resin having a small amount of methanol soluble matter, The present invention relates to a heat resistance imparting material having good dispersibility with respect to ABS resin and high heat resistance imparting performance, and a resin composition using the same.
従来からＡＢＳ樹脂等の耐熱性を改良する目的で、マレイミド系共重合樹脂を耐熱付与材として用いる事が行われている。マレイミド系共重合樹脂を得る方法の一つとして、先ず中間原料の芳香族ビニル−不飽和ジカルボン酸無水物共重合体を製造し、更に第１級アミンにてイミド化して得る方法、いわゆる後イミド化法による製法が数多く提案されている。マレイミド系共重合樹脂は高価である故、少ない配合量で高耐熱化できるような耐熱付与材が求められている。後イミド化法からなるべく耐熱性の高いマレイミド系共重合樹脂を得る場合、中間体として不飽和ジカルボン酸無水物基含量の多い芳香族ビニル−不飽和ジカルボン酸無水物共重合体を用いることが望まれている。 Conventionally, a maleimide copolymer resin has been used as a heat resistance imparting material for the purpose of improving the heat resistance of an ABS resin or the like. As one method for obtaining a maleimide copolymer resin, a method of first producing an aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer as an intermediate raw material, and further imidizing with a primary amine, so-called post-imide Many production methods using chemical methods have been proposed. Since maleimide copolymer resins are expensive, there is a demand for heat-resistance imparting materials that can increase the heat resistance with a small amount. When obtaining a maleimide copolymer resin having as high heat resistance as possible by post-imidization, it is desirable to use an aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer having a high unsaturated dicarboxylic acid anhydride group content as an intermediate. It is rare.
しかしながら、組成分布が均一な不飽和ジカルボン酸無水物基含量の多い芳香族ビニル−不飽和ジカルボン酸無水物共重合体の工業的かつ生産性の高い製造方法についてはこれまでに殆ど検討されていなかった。また、不飽和ジカルボン酸無水物基含量の多い芳香族ビニル−不飽和ジカルボン酸無水物共重合体を用いて得られたマレイミド系樹脂は耐熱性が高い反面、溶融粘度が高すぎるため流動性が悪くＡＢＳ樹脂との混合が困難であり、単なる高耐熱化だけでは十分ではなかった。 However, there has been little research on an industrial and highly productive method for producing an aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer having a uniform unsaturated dicarboxylic acid anhydride group with a uniform composition distribution. It was. The maleimide resin obtained using an aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer having a high unsaturated dicarboxylic acid anhydride group content has high heat resistance, but its melt viscosity is too high, so it has fluidity. Unfortunately, mixing with ABS resin was difficult, and mere high heat resistance was not sufficient.
本発明者らは、かかる目的を達成すべく鋭意研究を重ねた結果、不飽和ジカルボン酸無水物基含量の多い芳香族ビニル−不飽和ジカルボン酸無水物共重合体を製造する際、用いる芳香族ビニル単量体及び不飽和ジカルボン酸無水物の原料組成を特定の範囲に規定し、不飽和ジカルボン酸無水物を主体とする溶液中に芳香族ビニル単量体を主体とする溶液を分割または連続的に添加しながら溶液重合させることにより初めて、不飽和ジカルボン酸無水物基含量が多く、かつ組成分布が均一な芳香族ビニル−不飽和ジカルボン酸無水物共重合体を工業的に生産性の高い製造方法で得ることができた。そしてその共重合体を第一級アミンまたは／及びアンモニアでイミド化し、その後、例えば脱揮押出機等で、揮発分を除去して得られる（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の製造方法を見出した。
また、この製造方法により得られたマレイミド樹脂は色相が良好で、メタノール可溶分が少なく、更には重量平均分子量を特定範囲に規定した該マレイミド樹脂とＡＢＳ樹脂とを特定の組成範囲で混合した樹脂組成物が、ＡＢＳ樹脂に対して分散性が良好でかつ耐熱付与性能の極めて高い耐熱付与材として使用できる事を見出し本発明に至った。
As a result of intensive studies to achieve such an object, the present inventors have used an aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer having a high unsaturated dicarboxylic acid anhydride group content. The raw material composition of the vinyl monomer and the unsaturated dicarboxylic acid anhydride is defined within a specific range, and the solution mainly composed of the aromatic vinyl monomer is divided or continuously in the solution mainly composed of the unsaturated dicarboxylic acid anhydride. For the first time, by carrying out solution polymerization while adding the aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer having a high unsaturated dicarboxylic acid anhydride group content and a uniform composition distribution, the industrial productivity is high. It could be obtained by the manufacturing method. Then, the copolymer is imidized with a primary amine or / and ammonia, and then (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic acid obtained by removing volatile components with, for example, a devolatilizing extruder or the like. The manufacturing method of the acid anhydride type heat resistant thermoplastic resin was discovered.
In addition, the maleimide resin obtained by this production method has a good hue, a small amount of methanol-soluble matter, and further, the maleimide resin and the ABS resin whose weight average molecular weight is specified in a specific range are mixed in a specific composition range. The present inventors have found that the resin composition can be used as a heat imparting material having good dispersibility with respect to the ABS resin and having extremely high heat imparting performance.
すなわち、本発明は不飽和ジカルボン酸無水物及び芳香族ビニル単量体の合計量が１００質量部であって、（１）不飽和ジカルボン酸無水物４５〜４８質量部を含む溶液が、不飽和ジカルボン酸無水物４５〜４８質量部、連鎖移動剤０.２５〜０.８質量部、及び非重合性溶剤から成る溶液であり、（２）芳香族ビニル単量体５５〜５２質量部を含む溶液が、芳香族ビニル単量体５５〜５２質量部、重合開始剤０.１〜１.５質量部、及び非重合性溶剤から成る溶液であり、（１）の溶液中に（２）の溶液を分割または連続的に添加しながら非重合性溶剤中で溶液重合させることにより得た芳香族ビニル−不飽和ジカルボン酸無水物共重合体に対し、第一級アミンまたは／及びアンモニアでイミド化し、その後揮発分を除去して得られる（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の製造方法、その製造方法から得られる（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂、それを用いた耐熱付与材に関する。 That is, in the present invention, the total amount of unsaturated dicarboxylic acid anhydride and aromatic vinyl monomer is 100 parts by weight, and (1) a solution containing 45 to 48 parts by weight of unsaturated dicarboxylic acid anhydride is unsaturated. dicarboxylic anhydride 45-48 parts by weight, a chain transfer agent 0.25 to 0.8 parts by weight, and a solution consisting of a non-polymerizable solvent comprises (2) an aromatic vinyl monomer 55 to 52 parts by weight The solution is a solution comprising 55 to 52 parts by mass of an aromatic vinyl monomer, 0.1 to 1.5 parts by mass of a polymerization initiator, and a non-polymerizable solvent, and the solution of (2) An aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer obtained by solution polymerization in a non-polymerizable solvent while dividing or continuously adding the solution is imidized with a primary amine or / and ammonia. Then obtained by removing volatiles (N-substituted ) Maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride type heat-resistant thermoplastic resin, (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride type heat-resistant heat obtained from the production method The present invention relates to a plastic resin and a heat resistance imparting material using the same.
本発明の不飽和ジカルボン酸無水物基含量の多い芳香族ビニル−不飽和ジカルボン酸無水物共重合体は、大部分の分子構造が芳香族ビニル単量体と不飽和ジカルボン酸無水物による交互共重合構造を有している。
芳香族ビニル単量体としては、例えばスチレン、α−メチルスチレン、ビニルトルエン、ｔ−ブチルスチレン、クロロスチレン等が挙げられるが、これらの芳香族ビニル単量体は単独で用いてもよいし、２種類以上を併用しても差し支えないが、スチレンを単独で使用する事が特に好ましい。
不飽和ジカルボン酸無水物としては、例えばマレイン酸、イタコン酸、シトラコン酸、アコニット酸等の無水物があり、これらの酸無水物等を使用する事ができるが、これらの中で入手が容易である点、さらに廉価であるという点からマレイン酸無水物が特に好ましい。また、これらの酸無水物は単独で用いてもよいし、２種類以上を併用しても差し支えないが、マレイン酸無水物を単独で使用する事が特に好ましい。
The aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer having a high unsaturated dicarboxylic acid anhydride group content of the present invention is composed of an alternating copolymer of an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride. Has a polymerized structure.
Examples of the aromatic vinyl monomer include styrene, α-methyl styrene, vinyl toluene, t-butyl styrene, chlorostyrene, and the like. These aromatic vinyl monomers may be used alone, Two or more types may be used in combination, but it is particularly preferable to use styrene alone.
Examples of the unsaturated dicarboxylic acid anhydride include maleic acid, itaconic acid, citraconic acid, aconitic acid, and the like, and these acid anhydrides can be used. Maleic anhydride is particularly preferred because it is inexpensive and inexpensive. These acid anhydrides may be used alone or in combination of two or more, but it is particularly preferable to use maleic anhydride alone.
これら単量体群の合計量を１００質量部とすると、不飽和ジカルボン酸無水物基含量の多く、かつ組成分布が均一な芳香族ビニル−不飽和ジカルボン酸無水物共重合体を得るためには、不飽和ジカルボン酸無水物４５〜４８質量部を主体とする溶液中に芳香族ビニル単量体５５〜５２質量部を主体とする溶液を分割または連続的に添加しながら非重合性溶剤中で溶液重合させることが必要であり、本発明の特徴である。好ましくは、ポリマー中の芳香族ビニル−芳香族ビニル−芳香族ビニル三連連鎖の存在割合と芳香族ビニル−芳香族ビニル−不飽和ジカルボン酸無水物三連連鎖の存在割合の和が１０.０モル％以下であり、不飽和ジカルボン酸無水物−芳香族ビニル−不飽和ジカルボン酸無水物三連連鎖の存在割合が９０.０モル％以上であることを満足する芳香族ビニル−不飽和ジカルボン酸無水物共重合体を得るには、不飽和ジカルボン酸無水物４５〜４８質量部を主体とする溶液中に芳香族ビニル単量体５５〜５２質量部を主体とする溶液を分割または連続的に添加しながら非重合性溶剤中で溶液重合させることが必要である。 In order to obtain an aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer having a large unsaturated dicarboxylic acid anhydride group content and a uniform composition distribution, assuming that the total amount of these monomer groups is 100 parts by mass. In a non-polymerizable solvent, a solution mainly composed of 55 to 52 parts by weight of an aromatic vinyl monomer is added to a solution mainly composed of 45 to 48 parts by weight of an unsaturated dicarboxylic acid anhydride while being divided or continuously added. Solution polymerization is required and is a feature of the present invention. Preferably, the sum of the abundance ratio of aromatic vinyl-aromatic vinyl-aromatic vinyl triple chain and aromatic vinyl-aromatic vinyl-unsaturated dicarboxylic anhydride triple chain in the polymer is 10.0. Aromatic vinyl-unsaturated dicarboxylic acid satisfying that the proportion of unsaturated dicarboxylic acid anhydride-aromatic vinyl-unsaturated dicarboxylic anhydride triple chain is 90.0 mol% or more In order to obtain an anhydride copolymer, a solution mainly composed of 55 to 52 parts by weight of an aromatic vinyl monomer is divided or continuously divided into a solution mainly composed of 45 to 48 parts by weight of an unsaturated dicarboxylic acid anhydride. It is necessary to perform solution polymerization in a non-polymerizable solvent while adding.
これら単量体群の合計量を１００質量部とすると、好ましい組成は不飽和ジカルボン酸無水物４６〜４８質量部、芳香族ビニル単量体５４〜５２質量部、さらに好ましい組成は不飽和ジカルボン酸４７〜４８質量部、芳香族ビニル単量体５３〜５２質量部である。
不飽和ジカルボン酸が４５質量部未満であると、重合中に芳香族ビニル単量体含量の多い、組成分布を有する芳香族ビニル−不飽和ジカルボン酸無水物共重合体が生成し、イミド化後に得られる（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の耐熱付与性能が低下する。また４８質量部を超えると重合終了後の不飽和ジカルボン酸無水物の残存量が多くなり、イミド化の工程でイミド化単量体を生成し、イミド化後に得られる（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の色相が著しく悪くなる。
When the total amount of these monomer groups is 100 parts by mass, a preferred composition is 46 to 48 parts by mass of an unsaturated dicarboxylic acid anhydride, 54 to 52 parts by mass of an aromatic vinyl monomer, and a more preferred composition is an unsaturated dicarboxylic acid. 47 to 48 parts by mass and 53 to 52 parts by mass of the aromatic vinyl monomer.
When the unsaturated dicarboxylic acid is less than 45 parts by mass, an aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer having a composition distribution with a large aromatic vinyl monomer content is formed during polymerization, and after imidization The heat resistance imparting performance of the obtained (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride type heat-resistant thermoplastic resin is lowered. On the other hand, when the amount exceeds 48 parts by mass, the amount of unsaturated dicarboxylic acid anhydride remaining after the polymerization is increased, an imidized monomer is produced in the imidization step, and (N-substituted) maleimide- obtained after imidization. The hue of the aromatic vinyl-unsaturated dicarboxylic acid anhydride heat-resistant thermoplastic resin is remarkably deteriorated.
また、本発明の芳香族ビニル−不飽和ジカルボン酸無水物共重合体中の芳香族ビニル三連連鎖と芳香族ビニル−芳香族ビニル−不飽和ジカルボン酸無水物三連連鎖の存在割合の和は１０.０モル％以下が好ましく、さらに好ましくは５.０モル％以下、さらにいっそう好ましくは２.０モル％以下である。
ポリマー中の芳香族ビニル三連連鎖の存在割合と芳香族ビニル−芳香族ビニル−不飽和ジカルボン酸無水物三連連鎖の存在割合の和が１０.０モル％以上となると、イミド化後に得られる目的共重合体の耐熱付与性能が不十分となる場合がある。ポリマー中の芳香族ビニル−芳香族ビニル−芳香族ビニル三連連鎖の存在割合と芳香族ビニル−芳香族ビニル−不飽和ジカルボン酸無水物三連連鎖の存在割合の和は、単量体の仕込み組成、仕込み方法等により制御する事ができる。また、これらの存在割合はＤＥＰＴ法ＮＭＲにより求める事ができる。
Further, the sum of the abundance ratios of the aromatic vinyl triple chain and the aromatic vinyl-aromatic vinyl-unsaturated dicarboxylic anhydride triple chain in the aromatic vinyl-unsaturated dicarboxylic anhydride copolymer of the present invention is 10.0 mol% or less is preferable, more preferably 5.0 mol% or less, and still more preferably 2.0 mol% or less.
When the sum of the abundance ratio of the aromatic vinyl triple chain in the polymer and the abundance ratio of the aromatic vinyl-aromatic vinyl-unsaturated dicarboxylic anhydride triple chain is 10.0 mol% or more, the polymer is obtained after imidization. The target copolymer may have insufficient heat resistance. The sum of the abundance ratio of aromatic vinyl-aromatic vinyl-aromatic vinyl triple chain in the polymer and the abundance ratio of aromatic vinyl-aromatic vinyl-unsaturated dicarboxylic anhydride triple chain is determined by charging the monomer. It can be controlled by composition, preparation method, and the like. These abundance ratios can be determined by DEPT NMR.
本重合で使用される重合開始剤としてはアゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル、アゾビスメチルプロピオニトリル、アゾビスメチルブチロニトリル等の公知のアゾ化合物や、ベンゾイルパーオキサイド、ｔ−ブチルパーオキシベンゾエート、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、ｔ−ブチルパーオキシイソプロピルモノカーボネート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ジ−ｔ−ブチルパーオキサイド、ジクミルパーオキサイド、エチル−３,３−ジ−（ｔ−ブチルパーオキシ）ブチレート等の公知の有機過酸化物を用いることができる。これらの重合開始剤は２種類以上を併用しても差し支えないが、従来のスチレン系樹脂の製造において常用されているもの、例えば１０時間半減期温度が７０〜１２０℃であるアゾ化合物や有機過酸化物を用いるのが好ましい。 As polymerization initiators used in the main polymerization, known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, azobismethylbutyronitrile, benzoyl peroxide, t -Butyl peroxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexanoate, Known organic peroxides such as di-t-butyl peroxide, dicumyl peroxide, ethyl-3,3-di- (t-butylperoxy) butyrate can be used. These polymerization initiators may be used in combination of two or more, but those commonly used in the production of conventional styrene resins, such as azo compounds and organic peroxides having a 10-hour half-life temperature of 70 to 120 ° C. It is preferable to use an oxide.
重合開始剤の使用量は、単量体合計量１００質量部とした場合、芳香族ビニル単量体５５〜５２質量部を主体とする溶液中に０.１〜１.５質量部含ませることが好ましい。さらに好ましくは０.１〜１.０質量部、さらにいっそう好ましくは０.１〜０.５質量部である。０.１質量部未満であると十分な重合速度が得られない場合がある。また、１.５質量部以上であると重合速度が増大し反応制御が困難になったり、目的とする共重合体の分子量が不十分となる場合がある。 The polymerization initiator is used in an amount of 0.1 to 1.5 parts by mass in a solution mainly composed of 55 to 52 parts by mass of the aromatic vinyl monomer when the total amount of monomers is 100 parts by mass. Is preferred. More preferably, it is 0.1-1.0 mass part, More preferably, it is 0.1-0.5 mass part. If the amount is less than 0.1 part by mass, a sufficient polymerization rate may not be obtained. On the other hand, when the amount is 1.5 parts by mass or more, the polymerization rate may increase, making it difficult to control the reaction, or the molecular weight of the target copolymer may be insufficient.
本重合では、連鎖移動剤としてはｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタンや２，４−ジフェニル−４−メチル−１−ペンテン等の公知の連鎖移動剤を用いることができる。 In this polymerization, a known chain transfer agent such as n-dodecyl mercaptan, t-dodecyl mercaptan or 2,4-diphenyl-4-methyl-1-pentene can be used as the chain transfer agent.
連鎖移動剤の使用量は、単量体合計量１００質量部とした場合、不飽和ジカルボン酸無水物４５〜４８質量部を主体とする溶液中には０.２５〜０.８質量部含ませることが好ましい。さらに好ましくは０.３５〜０.６５質量部、さらにいっそう好ましくは０.４５〜０.５５質量部である。０.２５質量部以下であると本発明の（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の分子量が大きくなり、ＡＢＳ樹脂との混合性が悪化する。０.８質量部以上であると本発明の共重合樹脂の十分な分子量が得られない場合がある。 The chain transfer agent is used in an amount of 0.25 to 0.8 parts by mass in a solution mainly composed of 45 to 48 parts by mass of unsaturated dicarboxylic anhydride when the total amount of monomers is 100 parts by mass. It is preferable. More preferably, it is 0.35-0.65 mass part, More preferably, it is 0.45-0.55 mass part. When the amount is 0.25 parts by mass or less, the molecular weight of the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic acid anhydride heat-resistant thermoplastic resin of the present invention is increased, and the miscibility with the ABS resin is deteriorated. . If the amount is 0.8 parts by mass or more, the sufficient molecular weight of the copolymer resin of the present invention may not be obtained.
本発明における共重合方法は溶液重合、塊状重合等公知の方法が採用できるが、溶液重合が好ましい。また、重合プロセスは回分式重合法、連続式重合法のいずれの方式であっても差し支えない。
使用する溶剤は非重合性であることが好ましく、非重合性溶剤の量は、単量体群１００質量部に対し、１００〜４００質量部が好ましく、更に好ましくは１００〜２００質量部である。１００質量部未満であると、重合により得られる重合液が高粘度となり、取り扱いが困難になる場合がある。また４００質量部以上であると重合体混合物は低粘度となり取り扱いが容易にはなるが、生産性の面から十分でない場合がある。
As the copolymerization method in the present invention, known methods such as solution polymerization and bulk polymerization can be adopted, but solution polymerization is preferred. The polymerization process may be either a batch polymerization method or a continuous polymerization method.
The solvent to be used is preferably non-polymerizable, and the amount of the non-polymerizable solvent is preferably 100 to 400 parts by mass, more preferably 100 to 200 parts by mass with respect to 100 parts by mass of the monomer group. If the amount is less than 100 parts by mass, the polymerization solution obtained by the polymerization may have a high viscosity and may be difficult to handle. On the other hand, if it is 400 parts by mass or more, the polymer mixture has a low viscosity and is easy to handle, but it may not be sufficient in terms of productivity.
非重合性溶剤の種類としては、例えばアセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン等のケトン類、テトラヒドロフラン、１、４−ジオキサン等のエーテル類、ベンゼン、トルエン、キシレン、クロロベンゼン等の芳香族炭化水素、Ｎ、Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドン等の溶剤があり、揮発性、共重合体の溶解性等の取り扱い易さ等からメチルエチルケトン、メチルイソブチルケトンが特に好ましい。 Examples of the non-polymerizable solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetophenone, ethers such as tetrahydrofuran and 1,4-dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, There are solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone, and methyl ethyl ketone and methyl isobutyl ketone are particularly preferable from the viewpoint of easiness in handling such as volatility and solubility of the copolymer.
本重合における重合温度は好ましくは６０〜１５０℃であり、さらに好ましくは８０〜１３０℃である。６０℃未満では十分な重合速度が得られず、重合に要する時間が長くなる事から生産性の面から好ましくない場合がある。重合温度が１５０℃を超えると、熱重合の割合が増加するために十分な分子量が得られない場合がある。 The polymerization temperature in the main polymerization is preferably 60 to 150 ° C, more preferably 80 to 130 ° C. If it is less than 60 ° C., a sufficient polymerization rate cannot be obtained, and the time required for the polymerization becomes long, which is not preferable from the viewpoint of productivity. When the polymerization temperature exceeds 150 ° C., a sufficient molecular weight may not be obtained because the rate of thermal polymerization increases.
本重合における、芳香族ビニル単量体の重合率は９７％以上が好ましく、９９％以上がさらに好ましい。本発明における重合率とは、重合に使用した単量体に対して実際に単量体が重合した割合を表しており、ガスクロマトグラフィー等により未反応単量体を定量する事により求める事ができる。９７％未満であると、イミド化の工程で芳香族ビニル単量体の単独重合体が生成し、目的とする共重合樹脂に混在するために物性が悪化する場合があり、さらに目的とする共重合樹脂の収率が低下する場合があり好ましくない。芳香族ビニル単量体の重合率は重合時間、重合温度、重合開始剤量、連鎖移動剤量等により制御する事ができる。 In the main polymerization, the polymerization rate of the aromatic vinyl monomer is preferably 97% or more, and more preferably 99% or more. The polymerization rate in the present invention represents the ratio of actual polymerization of the monomer to the monomer used for the polymerization, and can be obtained by quantifying the unreacted monomer by gas chromatography or the like. it can. If it is less than 97%, a homopolymer of an aromatic vinyl monomer is formed in the imidization step, and the physical properties may deteriorate due to mixing with the target copolymer resin. The yield of the polymerization resin may decrease, which is not preferable. The polymerization rate of the aromatic vinyl monomer can be controlled by the polymerization time, polymerization temperature, amount of polymerization initiator, amount of chain transfer agent and the like.
本重合における不飽和ジカルボン酸無水物の重合率は９９％以上が好ましく、９９.８％以上がさらに好ましい。不飽和ジカルボン酸無水物の重合率とは、重合に使用した不飽和ジカルボン酸無水物に対して実際に単量体が重合した割合を表しており、ガスクロマトグラフィー等により未反応単量体を定量する事により求める事ができる。９９％未満であると、イミド化の工程でイミド化単量体を生成し、目的とする共重合樹脂の外観が著しく悪くなる場合がある。不飽和ジカルボン酸無水物の重合率は重合時間、重合温度、重合開始剤量、連鎖移動剤量等により制御する事ができる。 The polymerization rate of the unsaturated dicarboxylic acid anhydride in the main polymerization is preferably 99% or more, and more preferably 99.8% or more. The polymerization rate of the unsaturated dicarboxylic acid anhydride represents the ratio of the actual monomer polymerization with respect to the unsaturated dicarboxylic acid anhydride used for the polymerization. It can be obtained by quantifying. If it is less than 99%, an imidized monomer is generated in the imidization step, and the appearance of the target copolymer resin may be remarkably deteriorated. The polymerization rate of the unsaturated dicarboxylic acid anhydride can be controlled by the polymerization time, polymerization temperature, amount of polymerization initiator, amount of chain transfer agent and the like.
本重合においては、重合は６時間以内に完結する事が好ましく、５時間以内で完結する事がさらに好ましい。６時間以上であると生産性の面から好ましくない。 In the main polymerization, the polymerization is preferably completed within 6 hours, and more preferably within 5 hours. If it is 6 hours or more, it is not preferable from the viewpoint of productivity.
さらに、重合に際しては必要に応じて公知の可塑剤、熱安定剤、酸化防止剤等の添加剤を添加しても差し支えない。 Furthermore, during polymerization, additives such as known plasticizers, heat stabilizers, antioxidants and the like may be added as necessary.
得られた芳香族ビニル−不飽和ジカルボン酸無水物共重合体を第一級アミンまたは／及びアンモニアによってイミド化反応を行うが、本発明におけるイミド化反応は、非重合性溶剤存在下で芳香族ビニル−不飽和ジカルボン酸無水物共重合体と第一級アミンまたは／及びアンモニアとを溶液状態で反応させることである。
第１級アミンの具体例としてメチルアミン、エチルアミン、ｎ−プロピルアミン、ｉｓｏ−プロピルアミン、ｎ−ブチルアミン、ｎ−ペンチルアミン、ｎ−ヘキシルアミン、ｎ−オクチルアミン、シクロヘキシルアミン、デシルアミン等のアルキルアミン及びクロル又はブロム置換アルキルアミン、アニリン、トルイジン、ナフチルアミン等の芳香族アミンおよびクロル又はブロム置換芳香族アミンが挙げられ、これらの中でアニリン、シクロヘキシルアミンが特に好ましい。また、これらの第１級アミンは単独で用いてもよいし、２種類以上を併用しても差し支えない。
The obtained aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer is subjected to an imidization reaction with a primary amine or / and ammonia, and the imidization reaction in the present invention is carried out in the presence of a non-polymerizable solvent. This is to react a vinyl-unsaturated dicarboxylic acid anhydride copolymer with a primary amine and / or ammonia in a solution state.
Specific examples of primary amines include alkylamines such as methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, cyclohexylamine and decylamine. And aromatic amines such as chloro or bromo-substituted alkylamine, aniline, toluidine, naphthylamine, and the like, and chloro or bromo-substituted aromatic amines, among which aniline and cyclohexylamine are particularly preferable. Moreover, these primary amines may be used alone or in combination of two or more.
アミンの添加量は芳香族ビニル−不飽和ジカルボン酸無水物共重合体の不飽和ジカルボン酸無水物基に対して好ましくは０.９２〜１.１モル当量、さらに好ましくは０.９５〜１.０５モル当量である。０.９モル当量以下であると、目的を達せられない場合がある。また、１.１モル当量以上であると、得られる目的とする共重合樹脂中の残存する第１級アミンが多くなり好ましくない場合がある。また、イミド化に用いる第１級アミン或いはアンモニアは無水である事が好ましい。アミン中に多量に水分が含まれると、イミド化反応の際、芳香族ビニル−不飽和ジカルボン酸無水物共重合体中の不飽和ジカルボン酸無水物基が加水分解しイミド化反応の支障となったり目的とする共重合樹脂の物性が悪化する場合がある。 The amount of amine added is preferably 0.92 to 1.1 molar equivalents, more preferably 0.95 to 1.1, based on the unsaturated dicarboxylic anhydride group of the aromatic vinyl-unsaturated dicarboxylic anhydride copolymer. 05 molar equivalents. If the amount is 0.9 mole equivalent or less, the purpose may not be achieved. On the other hand, if it is 1.1 molar equivalents or more, the remaining primary amine in the intended copolymer resin to be obtained may increase, which may be undesirable. The primary amine or ammonia used for imidization is preferably anhydrous. If a large amount of water is contained in the amine, the unsaturated dicarboxylic acid anhydride group in the aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer is hydrolyzed during the imidation reaction, which hinders the imidization reaction. In some cases, the physical properties of the intended copolymer resin may deteriorate.
イミド化の触媒として第３級アミンを使用する事が好ましい。使用する第３級アミンとしてはトリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、Ｎ、Ｎ−ジメチルアニリン、Ｎ、Ｎ−ジエチルアニリン等が挙げられる。 It is preferable to use a tertiary amine as a catalyst for imidization. The tertiary amine used includes trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline and the like.
第３級アミンの添加量は芳香族ビニル−不飽和ジカルボン酸無水物共重合体中の不飽和ジカルボン酸無水物基に対し、０.０１モル当量以上が好ましい。０.０１モル当量未満であるとイミド化反応の触媒効果が不十分となりイミド化反応に長時間を要しかつイミド化反応を完結させる事が困難となる場合がある。 The addition amount of the tertiary amine is preferably 0.01 molar equivalent or more with respect to the unsaturated dicarboxylic anhydride group in the aromatic vinyl-unsaturated dicarboxylic anhydride copolymer. If it is less than 0.01 molar equivalent, the catalytic effect of the imidization reaction may be insufficient, and it may take a long time for the imidation reaction and it may be difficult to complete the imidation reaction.
本発明におけるイミド化反応の温度は好ましくは８０〜２５０℃であり、さらに好ましくは１００〜２００℃である。８０℃未満の場合には反応速度が遅く反応完結までに長時間を要し生産性の面から好ましくない場合がある。一方、２５０℃を越える場合には芳香族ビニル−不飽和ジカルボン酸無水物共重合樹脂の熱劣化による物性低下をきたし好ましくない場合がある。 The temperature of the imidization reaction in the present invention is preferably 80 to 250 ° C, more preferably 100 to 200 ° C. When the temperature is lower than 80 ° C., the reaction rate is slow, and it takes a long time to complete the reaction, which is not preferable from the viewpoint of productivity. On the other hand, when the temperature exceeds 250 ° C., the physical properties of the aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer resin may deteriorate due to thermal deterioration, which may be undesirable.
本発明における（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂は、脱揮装置付押出機を用いてイミド化反応溶液から揮発分を除去することにより得ることができる。 The (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin in the present invention is obtained by removing volatile components from an imidization reaction solution using an extruder with a devolatilizer. be able to.
本発明の（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の重量平均分子量は７〜１２万であることが好ましい。さらに好ましくは８〜１１万であり、いっそう好ましくは９〜１０万である。１２万を超える場合、（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂とＡＢＳ樹脂等との混合性が悪くなり、混合後に得られる組成物の物性や外観が悪化する場合がある。重量平均分子量が７万未満の場合は、得られる（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の溶融張力が著しく低下するため、脱揮押出後にストランド及びペレットを得る際のハンドリング性が著しく悪化し、更にＡＢＳ樹脂との組成物の機械的特性が悪化する場合がある。重量平均分子量は、連鎖移動剤量、重合開始剤量、重合温度等によって制御できる。 The weight average molecular weight of the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic acid anhydride heat-resistant thermoplastic resin of the present invention is preferably from 7 to 120,000. More preferably, it is 8-1110,000, More preferably, it is 9-100,000. When exceeding 120,000, the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic acid anhydride-based heat-resistant thermoplastic resin and the ABS resin, etc. are poorly mixed, and the physical properties of the composition obtained after mixing Appearance may deteriorate. If the weight average molecular weight is less than 70,000, the melt tension of the resulting (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin is significantly reduced. In addition, handling properties in obtaining pellets may be significantly deteriorated, and mechanical properties of the composition with the ABS resin may be further deteriorated. The weight average molecular weight can be controlled by the amount of chain transfer agent, the amount of polymerization initiator, the polymerization temperature, and the like.
本発明の（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の黄色度は３.０未満であることが好ましい。３.０を超えるとＡＢＳ樹脂との混合後の耐熱付与材の色相が著しく悪化する場合がある。 The yellowness of the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic acid anhydride heat-resistant thermoplastic resin of the present invention is preferably less than 3.0. If it exceeds 3.0, the hue of the heat-resistance-imparting material after mixing with the ABS resin may be significantly deteriorated.
本発明の（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂のメタノール可溶分は１.５質量％未満である事が好ましい。１.５質量％以上であると、ＡＢＳ樹脂と混合する際の耐熱付与効果が低下する場合がある。メタノール可溶分は、重合時の連鎖移動剤量、開始剤量、及びイミド化後脱揮押出時の脱揮条件等により制御する事ができる。 The (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride type heat-resistant thermoplastic resin of the present invention preferably has a methanol soluble content of less than 1.5% by mass. When it is 1.5% by mass or more, the heat resistance imparting effect when mixed with the ABS resin may be lowered. The methanol soluble component can be controlled by the amount of chain transfer agent during polymerization, the amount of initiator, the devolatilization conditions during devolatilization extrusion after imidization, and the like.
本発明の（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の酸価は、１５ｍｇＫＯＨ／ｇ未満である事が好ましく、さらに好ましくは１２ｍｇＫＯＨ／ｇ未満である。
本発明における酸価とは、（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂中の、不飽和ジカルボン酸基、カルボン酸基、およびイミド化反応の中間体のマレアミド酸基を主体とする官能基群に由来する数値を表す。１５ｍｇＫＯＨ／ｇ以上であると、目的とする共重合体をＡＢＳ樹脂等に混合して組成物を得る際、成形後の成形品外観に成形不良が見られる場合がある。本発明における酸価は、イミド化反応において不飽和ジカルボン酸基に対する第１級アミンの添加量等によって制御できる。
The acid value of the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic acid anhydride heat-resistant thermoplastic resin of the present invention is preferably less than 15 mgKOH / g, more preferably less than 12 mgKOH / g. .
The acid value in the present invention is an intermediate between the unsaturated dicarboxylic acid group, the carboxylic acid group, and the imidization reaction in the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic acid anhydride heat-resistant thermoplastic resin. This represents a numerical value derived from a functional group mainly composed of maleamic acid groups of the body. When it is 15 mg KOH / g or more, when the composition is obtained by mixing the target copolymer with ABS resin or the like, molding defects may be observed in the appearance of the molded product after molding. The acid value in the present invention can be controlled by the amount of primary amine added to the unsaturated dicarboxylic acid group in the imidization reaction.
本発明における（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂のイミド化率は好ましくは９０モル％以上、さらに好ましくは９４モル％以上である。
本発明におけるイミド化率とは、芳香族ビニル−不飽和ジカルボン酸無水物共重合体中の不飽和ジカルボン酸無水物基のイミド基への転化率を表しており、ＮＭＲ等から求めることができる。イミド化率９０モル％未満の共重合樹脂は目的を達せられない場合がある。イミド化率は不飽和ジカルボン酸無水物基に対する第１級アミンの添加割合、イミド化反応温度、第３級アミンの添加量等によって制御できる。
The imidation ratio of the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride heat-resistant thermoplastic resin in the present invention is preferably 90 mol% or more, more preferably 94 mol% or more.
The imidization rate in the present invention represents the conversion rate of the unsaturated dicarboxylic anhydride group to the imide group in the aromatic vinyl-unsaturated dicarboxylic anhydride copolymer, and can be determined from NMR or the like. . A copolymer resin having an imidation ratio of less than 90 mol% may not achieve its purpose. The imidization rate can be controlled by the ratio of the primary amine added to the unsaturated dicarboxylic anhydride group, the imidization reaction temperature, the amount of tertiary amine added, and the like.
本発明における耐熱付与材は、（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂５０〜８０質量部とＡＢＳ樹脂５０〜２０質量部とを混合機等を使用して樹脂同士を混合して得られる。混合方法としては単軸押出機や二軸押出機等の公知の混合機を使用する事ができる。また、これらの混合機には脱揮装置が付属しても差し支えない。用いる混合機としては二軸押出機が好ましい。
（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂が５０質量部未満であると、得られる耐熱付与材の耐熱付与効果が十分でなくなる。また８０質量部を超えると、得られる耐熱付与材の耐熱付与効果が高くなるが、その耐熱付与材とＡＢＳ樹脂との溶融粘度差が大きくなるため、混合性が悪化する場合がある。
In the present invention, the heat resistance-imparting material is prepared by mixing 50 to 80 parts by mass of an (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride type heat-resistant thermoplastic resin and 50 to 20 parts by mass of an ABS resin. It is obtained by mixing the resins together. As a mixing method, a known mixer such as a single screw extruder or a twin screw extruder can be used. These mixers may be attached with a devolatilizer. As the mixer to be used, a twin screw extruder is preferable.
When the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin is less than 50 parts by mass, the heat-resistance imparting effect of the resulting heat-resistance imparting material becomes insufficient. On the other hand, when the amount exceeds 80 parts by mass, the heat resistance imparting effect of the obtained heat imparting material is enhanced, but the difference in melt viscosity between the heat imparting material and the ABS resin is increased, so that the mixing property may be deteriorated.
本発明における樹脂組成物は、（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂とＡＢＳ樹脂とを混合して得られた耐熱付与材５〜４０質量部、ＡＢＳ樹脂９５〜６０質量部とを混合機等を利用して樹脂同士を混合して得られる。混合方法としては単軸押出機や二軸押出機等の公知の混合機を使用する事ができる。また、これらの混合機には脱揮装置が付属しても差し支えない。用いる混合機としては、廉価で操作が容易な単軸押出機が好ましい。
（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂とＡＢＳ樹脂を直接混合する場合は、双方の樹脂の溶融粘度差が極めて大きいため、例えば二軸押出機のような操作の煩雑な混合機を用いなければならない。しかし、本発明のように（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂とＡＢＳ樹脂を一旦混合する事で、ＡＢＳ樹脂との溶融粘度差を改善されたＡＢＳ樹脂への分散性の良好な耐熱付与材が得られ、耐熱付与材とＡＢＳ樹脂との混合には廉価で操作が容易な単軸押出機のような混合機を採用する事ができる。
The resin composition in the present invention comprises (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin and ABS resin, obtained by mixing 5 to 40 parts by mass of the heat-resistance imparting material. It is obtained by mixing the resins with 95 to 60 parts by mass of ABS resin using a mixer or the like. As a mixing method, a known mixer such as a single screw extruder or a twin screw extruder can be used. These mixers may be attached with a devolatilizer. As the mixer to be used, a single screw extruder which is inexpensive and easy to operate is preferable.
When (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride type heat-resistant thermoplastic resin and ABS resin are directly mixed, the difference in melt viscosity between the two resins is extremely large. It is necessary to use a complicated mixer such as that described above. However, once the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride heat-resistant thermoplastic resin and ABS resin are mixed as in the present invention, the difference in melt viscosity from the ABS resin can be improved. In addition, a heat imparting material having good dispersibility in the ABS resin can be obtained, and a mixer such as a single screw extruder that is inexpensive and easy to operate can be used for mixing the heat imparting material and the ABS resin.
本発明における耐熱付与材のビカット軟化温度は１５０〜１８５℃である必要がある。１５０℃未満であると、耐熱付与効果が十分でなく本発明の目的を達せられない。また、１８５℃を超える場合は耐熱付与材とＡＢＳ樹脂との混合性が悪化する場合がある。 The Vicat softening temperature of the heat-resistance imparting material in the present invention needs to be 150 to 185 ° C. If it is less than 150 ° C., the effect of imparting heat resistance is not sufficient and the object of the present invention cannot be achieved. Moreover, when it exceeds 185 degreeC, the mixability of a heat-resistant provision material and an ABS resin may deteriorate.
このようにして得られる（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を用いた耐熱付与材はスチレン−アクリロニトリル共重合樹脂（ＳＡＮ樹脂）、アクリロニトリル−ブタジエン−スチレン共重合樹脂（ＡＢＳ樹脂）、アクリロニトリル−ブタジエン−スチレン−α−メチルスチレン共重合樹脂、アクリロニリル−アクリル系ゴム−スチレン共重合樹脂、アクリロニトリル−エチレン・プロピレン系ゴム−スチレン共重合樹脂、スチレン−メチルメタクリレート共重合樹脂、メチルメタクリレート−ブタジエン−スチレン共重合樹脂、芳香族ポリカーボネート、芳香族ポリエステル、ポリフェニレンサルファイド、ポリアミド、ポリウレタン、及びナイロンと混合することもでき、これら樹脂への耐熱付与材として用いる事ができる。 The heat resistance imparting material using the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin thus obtained is styrene-acrylonitrile copolymer resin (SAN resin), acrylonitrile-butadiene. -Styrene copolymer resin (ABS resin), acrylonitrile-butadiene-styrene-α-methylstyrene copolymer resin, acrylonitrile-acrylic rubber-styrene copolymer resin, acrylonitrile-ethylene-propylene rubber-styrene copolymer resin, styrene- Can be mixed with methyl methacrylate copolymer resin, methyl methacrylate-butadiene-styrene copolymer resin, aromatic polycarbonate, aromatic polyester, polyphenylene sulfide, polyamide, polyurethane, and nylon, and these resins It can be used as the heat imparting material.
これらの中でＡＢＳ樹脂とは特に良く相溶する。また、混合時にさらに安定剤、紫外線吸収剤、難燃剤、可塑剤、滑剤、ガラス等の繊維、無機充填剤、着色剤、帯電防止剤等を添加しても差し支えない。 Among these, the ABS resin is particularly well compatible. In addition, stabilizers, ultraviolet absorbers, flame retardants, plasticizers, lubricants, fibers such as glass, inorganic fillers, colorants, antistatic agents and the like may be added during mixing.
以下本発明を参考例及び実施例によって説明する。なお、本発明はこれらの例によって限定されるものではない。 Hereinafter, the present invention will be described by reference examples and examples. Note that the present invention is not limited to these examples.
参考例：芳香族ビニル−不飽和ジカルボン酸無水物共重合体の製造
［参考例１］
攪拌機を備えたオートクレーブ中に無水マレイン酸４５.０質量部、メチルエチルケトン１１.２質量部、２，４−ジフェニル−４−メチル−１−ペンテンを０.３質量部を仕込み、系内を窒素ガスで十分置換した後、温度を９２℃に昇温した。別容器に調製したスチレン５５.０質量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエート０.１５質量部をメチルエチルケトン１２６質量部に溶解した溶液を均一な添加速度で４時間３０分かけて添加した。添加後１１６℃に昇温し、更に３０分反応させて、芳香族ビニル−不飽和ジカルボン酸無水物共重合体を得た。粘調な樹脂液の一部をサンプリングして、ガスクロマトグラフィーにより未反応の単量体の定量を行い、単量体の重合率を算出した。スチレンの重合率は９８.２％であり、無水マレイン酸の重合率は９９.８％以上であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
Reference Example: Production of an aromatic vinyl-unsaturated dicarboxylic anhydride copolymer [Reference Example 1]
An autoclave equipped with a stirrer was charged with 45.0 parts by weight of maleic anhydride, 12.2 parts by weight of methyl ethyl ketone, and 0.3 parts by weight of 2,4-diphenyl-4-methyl-1-pentene, and the system was filled with nitrogen gas. After sufficiently substituting with, the temperature was raised to 92 ° C. A solution prepared by dissolving 55.0 parts by mass of styrene and 0.15 parts by mass of t-butylperoxy-2-ethylhexanoate in 126 parts by mass of methyl ethyl ketone was prepared at a uniform addition rate over 4 hours and 30 minutes. Added. After the addition, the temperature was raised to 116 ° C., and the mixture was further reacted for 30 minutes to obtain an aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer. A part of the viscous resin solution was sampled, the amount of unreacted monomer was determined by gas chromatography, and the polymerization rate of the monomer was calculated. The polymerization rate of styrene was 98.2%, and the polymerization rate of maleic anhydride was 99.8% or more. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例２］
スチレンを５３.５質量部、無水マレイン酸を４６.５質量部に変更した以外は参考例１と同様の方法により、重合、未反応単量体の定量を実施した。スチレンの重合率は９８.６％、無水マレイン酸の重合率は９９.８％以上であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 2]
Polymerization and quantification of unreacted monomers were carried out in the same manner as in Reference Example 1 except that styrene was changed to 53.5 parts by mass and maleic anhydride was changed to 46.5 parts by mass. The polymerization rate of styrene was 98.6%, and the polymerization rate of maleic anhydride was 99.8% or more. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例３］
スチレンを５２.５質量部、無水マレイン酸を４７.５質量部に変更した以外は参考例１と同様の方法により、重合、未反応単量体の定量を実施した。スチレンの重合率は９９.２％、無水マレイン酸の重合率は９９.８％以上であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 3]
Polymerization and quantification of unreacted monomers were carried out in the same manner as in Reference Example 1, except that styrene was changed to 52.5 parts by mass and maleic anhydride was changed to 47.5 parts by mass. The polymerization rate of styrene was 99.2%, and the polymerization rate of maleic anhydride was 99.8% or more. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例４］
スチレンを５２.５質量部、無水マレイン酸を４７.５質量部、２，４−ジフェニル−４−メチル−１−ペンテンを０.４質量部に変更した以外は参考例１と同様の方法により、重合、未反応単量体の定量を実施した。スチレンの重合率は９９.２％、無水マレイン酸の重合率は９９.８％以上であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 4]
By the same method as in Reference Example 1 except that 52.5 parts by mass of styrene, 47.5 parts by mass of maleic anhydride, and 0.4 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were changed. Then, polymerization and quantification of unreacted monomers were carried out. The polymerization rate of styrene was 99.2%, and the polymerization rate of maleic anhydride was 99.8% or more. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例５］
スチレンを５２.５質量部、無水マレイン酸を４７.５質量部、２，４−ジフェニル−４−メチル−１−ペンテンを０.４６質量部に変更した以外は参考例１と同様の方法により、重合、未反応単量体の定量を実施した。スチレンの重合率は９９.２％、無水マレイン酸の重合率は９９.８％以上であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 5]
By the same method as in Reference Example 1 except that 52.5 parts by mass of styrene, 47.5 parts by mass of maleic anhydride, and 0.46 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were changed. Then, polymerization and quantification of unreacted monomers were carried out. The polymerization rate of styrene was 99.2%, and the polymerization rate of maleic anhydride was 99.8% or more. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例６］
スチレンを５２.５質量部、無水マレイン酸を４７.５質量部、２，４−ジフェニル−４−メチル−１−ペンテンを０.２７質量部に変更した以外は参考例１と同様の方法により、重合、未反応単量体の定量を実施した。スチレンの重合率は９９.２％、無水マレイン酸の重合率は９９.８％以上であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 6]
By the same method as in Reference Example 1 except that 52.5 parts by mass of styrene, 47.5 parts by mass of maleic anhydride, and 0.27 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were changed. Then, polymerization and quantification of unreacted monomers were carried out. The polymerization rate of styrene was 99.2%, and the polymerization rate of maleic anhydride was 99.8% or more. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例７］
スチレンを５２.５質量部、無水マレイン酸を４７.５質量部、２，４−ジフェニル−４−メチル−１−ペンテンを０.７８質量部に変更した以外は参考例１と同様の方法により、重合、未反応単量体の定量を実施した。スチレンの重合率は９９.２％、無水マレイン酸の重合率は９９.８％以上であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 7]
By the same method as Reference Example 1 except that 52.5 parts by mass of styrene, 47.5 parts by mass of maleic anhydride, and 0.78 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were changed. Then, polymerization and quantification of unreacted monomers were carried out. The polymerization rate of styrene was 99.2%, and the polymerization rate of maleic anhydride was 99.8% or more. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例８］
攪拌機を備えたオートクレーブ中にスチレン６０質量部、メチルエチルケトン１１.２質量部、２，４−ジフェニル−４−メチル−１−ペンテン０.３質量部を仕込み、系内を窒素ガスで十分置換した後、温度を９２℃に昇温した。別容器に調整した無水マレイン酸４０質量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエート０.１５部をメチルエチルケトン１２６質量部に溶解した溶液を均一な添加速度で５時間かけて添加した。添加後１１６℃に昇温し、更に１時間反応させて、芳香族ビニル−不飽和ジカルボン酸無水物共重合体を得た。粘調な樹脂液の一部をサンプリングして、ガスクロマトグラフィーにより未反応の単量体の定量を行い、単量体の重合率を算出した。スチレンの重合率は９７．４％であり、無水マレイン酸の重合率は９９．８％以上であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 8]
After charging 60 parts by mass of styrene, 12.2 parts by mass of methyl ethyl ketone, and 0.3 parts by mass of 2,4-diphenyl-4-methyl-1-pentene in an autoclave equipped with a stirrer, and sufficiently replacing the system with nitrogen gas The temperature was raised to 92 ° C. A solution prepared by dissolving 40 parts by mass of maleic anhydride and 0.15 part of t-butylperoxy-2-ethylhexanoate in 126 parts by mass of methyl ethyl ketone was added over 5 hours at a uniform addition rate. After the addition, the temperature was raised to 116 ° C., and the mixture was further reacted for 1 hour to obtain an aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer. A part of the viscous resin solution was sampled, the amount of unreacted monomer was determined by gas chromatography, and the polymerization rate of the monomer was calculated. The polymerization rate of styrene was 97.4%, and the polymerization rate of maleic anhydride was 99.8% or more. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例９］
スチレンを５８質量部、無水マレイン酸を４２質量部に変更した以外は参考例１と同様の方法により、重合、未反応単量体の定量を実施した。スチレンの重合率は９５.６％、無水マレイン酸の重合率は９９.８％以上であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 9]
Polymerization and quantification of unreacted monomers were carried out in the same manner as in Reference Example 1 except that styrene was changed to 58 parts by mass and maleic anhydride was changed to 42 parts by mass. The polymerization rate of styrene was 95.6%, and the polymerization rate of maleic anhydride was 99.8% or more. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例１０］
スチレンを５０質量部、無水マレイン酸を５０質量部に変更した以外は参考例１と同様の方法により、重合、未反応単量体の定量を実施した。スチレンの重合率は９９.２％、無水マレイン酸の重合率は９３.０％であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 10]
Polymerization and quantification of unreacted monomers were carried out in the same manner as in Reference Example 1 except that styrene was changed to 50 parts by mass and maleic anhydride was changed to 50 parts by mass. The polymerization rate of styrene was 99.2%, and the polymerization rate of maleic anhydride was 93.0%. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例１１］
スチレンを５２.５質量部、無水マレイン酸を４７.５質量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエート０.０８質量部に変更した以外は参考例１と同様の方法により、重合、未反応単量体の定量を実施した。スチレンの重合率は９６.２％、無水マレイン酸の重合率は９８.３％であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 11]
Polymerization was carried out in the same manner as in Reference Example 1 except that 52.5 parts by mass of styrene, 47.5 parts by mass of maleic anhydride, and 0.08 parts by mass of t-butylperoxy-2-ethylhexanoate were changed. The unreacted monomer was quantified. The polymerization rate of styrene was 96.2%, and the polymerization rate of maleic anhydride was 98.3%. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例１２］
スチレンを５２.５質量部、無水マレイン酸を４７.５質量部、２，４−ジフェニル−４−メチル−１−ペンテン０.２質量部にした以外は参考例１と同様の方法により、重合、未反応単量体の定量を実施した。スチレンの重合率は９９.２％、無水マレイン酸の重合率は９９.８％以上であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 12]
Polymerization was carried out in the same manner as in Reference Example 1, except that 52.5 parts by mass of styrene, 47.5 parts by mass of maleic anhydride, and 0.2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were used. The unreacted monomer was quantified. The polymerization rate of styrene was 99.2%, and the polymerization rate of maleic anhydride was 99.8% or more. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
［参考例１３］
スチレンを５２.５質量部、無水マレイン酸を４７.５質量部、２，４−ジフェニル−４−メチル−１−ペンテン０.８５質量部にした以外は参考例１と同様の方法により、重合、未反応単量体の定量を実施した。スチレンの重合率は９９.２％、無水マレイン酸の重合率は９９.８％以上であった。三連連鎖分布の測定は後記に示す方法により行った。重合方法を表１に、その結果を表２に示した。
[Reference Example 13]
Polymerization was carried out in the same manner as in Reference Example 1 except that 52.5 parts by mass of styrene, 47.5 parts by mass of maleic anhydride, and 0.85 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were used. The unreacted monomer was quantified. The polymerization rate of styrene was 99.2%, and the polymerization rate of maleic anhydride was 99.8% or more. The triple chain distribution was measured by the method described below. The polymerization methods are shown in Table 1, and the results are shown in Table 2.
参考例１で得られた共重合体を用い、無水マレイン酸基に対して０.９７モル当量のアニリン及び無水マレイン酸基に対して０.０１４モル当量のトリエチルアミンを仕込んだ。そして１５５℃で５時間反応を行った。イミド化反応液を脱揮押出機に投入し、揮発分を除去してペレット状の（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表３に示した。 Using the copolymer obtained in Reference Example 1, 0.97 molar equivalents of aniline with respect to maleic anhydride groups and 0.014 molar equivalents of triethylamine with respect to maleic anhydride groups were charged. And reaction was performed at 155 degreeC for 5 hours. The imidization reaction liquid was charged into a devolatilizing extruder, and volatile components were removed to obtain a pellet-like (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin. Mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 3.
参考例２で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表３に示した。 A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 2 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 3.
参考例３で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表３に示した。 A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 3 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 3.
参考例４で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表３に示した。 A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 4 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 3.
参考例５で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表４に示した。 A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 5 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 4.
参考例６で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表４に示した。 A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 6 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 4.
参考例７で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表４に示した。
［比較例１］
A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 7 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 4.
[Comparative Example 1]
参考例８で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表５に示した。
［比較例２］
A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 8 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 5.
[Comparative Example 2]
参考例９で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表５に示した。
［比較例３］
A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 9 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 5.
[Comparative Example 3]
参考例１０で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表５に示した。
［比較例４］
A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 10 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 5.
[Comparative Example 4]
参考例５で得られた共重合体を用い、無水マレイン酸基に対して０.８０モル当量のアニリンを用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表５に示した。
［比較例５］
(N-substituted) maleimide-aromatic vinyl in the same manner as in Example 1 except that the copolymer obtained in Reference Example 5 was used and 0.80 molar equivalent of aniline was used with respect to the maleic anhydride group. -An unsaturated dicarboxylic acid anhydride heat-resistant thermoplastic resin was obtained. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 5.
[Comparative Example 5]
参考例１１で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表６に示した。
［比較例６］
A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 11 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 6.
[Comparative Example 6]
参考例１２で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表６に示した。
［比較例７］
A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 12 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 6.
[Comparative Example 7]
参考例１３で得られた共重合体を用いた以外は実施例１と同様の方法により（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂を得た。また、実施例１と同様に、得られた樹脂とＡＢＳ樹脂との混合および得られた耐熱付与材とＡＢＳ樹脂との混合は後記した方法で実施し、結果を表６に示した。 A (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin was obtained in the same manner as in Example 1 except that the copolymer obtained in Reference Example 13 was used. Further, in the same manner as in Example 1, mixing of the obtained resin and ABS resin and mixing of the obtained heat-imparting material and ABS resin were carried out by the methods described later, and the results are shown in Table 6.
（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂とＡＢＳ樹脂との混合
得られた（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂と一般に市販されているＡＢＳ樹脂（ＧＲ−３０００、電気化学工業製）を表２、表３記載の配合にて２０リットルヘンシェルに投入してブレンド後、二軸押出機を用い、以下に示す条件で混合を実施し、耐熱付与材を得た。
二軸押出機による混合
押出機：ＴＥＭ−３５Ｂ（東芝機械社製二軸押出機、スクリュー径３７ｍｍ、Ｌ/Ｄ＝３２）
シリンダー温度：２６０℃
スクリュー回転数：２００ｒｐｍ（回転方向は二軸同方向）
原料フィード：２０ｋｇ/ｈｒ
耐熱付与材とＡＢＳ樹脂との混合
得られた耐熱付与材と一般に市販されているＡＢＳ樹脂（ＧＲ−３０００、電気化学工業製）を表２、表３記載の配合にて２０リットルヘンシェルに投入してブレンド後、単軸押出機を用い、以下に示す条件で混合を実施し、樹脂組成物をを得た。
単軸押出機による混合
押出機：ＶＳ４０ｍ/ｍ押出機（田辺プラスチック機械製単軸押出機）
シリンダー温度：２６０℃
スクリュー回転数：２００ｒｐｍ
原料フィード：２０ｋｇ/ｈｒ
(N-Substituted) Maleimide-Aromatic Vinyl-Unsaturated Dicarboxylic Anhydride Mixture of Heat Resistant Thermoplastic Resin and ABS Resin Obtained (N-Substituted) Maleimide-Aromatic Vinyl-Unsaturated Dicarboxylic Anhydride System Heat-resistant thermoplastic resin and commercially available ABS resin (GR-3000, manufactured by Denki Kagaku Kogyo Co., Ltd.) are charged into a 20-liter Henschel with the composition shown in Tables 2 and 3, blended, and then a twin screw extruder is used. Then, mixing was performed under the conditions shown below to obtain a heat resistance imparting material.
Mixing with a twin screw extruder Extruder: TEM-35B (Toshiba Machine's twin screw extruder, screw diameter 37 mm, L / D = 32)
Cylinder temperature: 260 ° C
Screw rotation speed: 200 rpm (rotating direction is the same direction of two axes)
Raw material feed: 20 kg / hr
Mixing of heat resistance material and ABS resin The obtained heat resistance material and a commercially available ABS resin (GR-3000, manufactured by Denki Kagaku Kogyo Co., Ltd.) were charged into a 20-liter Henschel with the composition shown in Tables 2 and 3. After blending, mixing was carried out using a single screw extruder under the following conditions to obtain a resin composition.
Mixing with single screw extruder Extruder: VS40m / m extruder (single screw extruder made by Tanabe Plastic Machine)
Cylinder temperature: 260 ° C
Screw rotation speed: 200rpm
Raw material feed: 20 kg / hr
なお参考例、実施例、比較例の評価は以下のように行った。
（１）芳香族ビニル−不飽和ジカルボン酸無水物共重合体の重合率
下記記載の測定条件で未反応の単量体の定量を行い、重合率を算出した。
装置名：Ａｇｉｌｅｎｔ６８９０ｓｅｒｉｅｓ（Ａｇｉｌｅｎｔ社製）
カラム：キャピラリーカラム（ジメチルポリシロキサン、架橋タイプ）
温度：オーブン：５０℃、注入口：２００℃、検出器：２５０℃
検出器：ＦＩＤ
試料重合液０.５０ｇ、ｎ−オクタン０.００１ｇを秤量しメチルエチルケトンに溶解させ全体を２５.０ｇにし、ｎ−オクタンを内部標準として測定した。
In addition, evaluation of the reference example, the example, and the comparative example was performed as follows.
(1) Polymerization rate of aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer Unreacted monomers were quantified under the measurement conditions described below to calculate the polymerization rate.
Device name: Agilent 6890 series (manufactured by Agilent)
Column: Capillary column (dimethylpolysiloxane, cross-linked type)
Temperature: Oven: 50 ° C, inlet: 200 ° C, detector: 250 ° C
Detector: FID
A sample polymerization solution of 0.50 g and n-octane of 0.001 g were weighed and dissolved in methyl ethyl ketone to make 25.0 g of the whole, and n-octane was measured as an internal standard.
（２）芳香族ビニル−不飽和ジカルボン酸無水物共重合体の三連連鎖分布の測定
本発明における芳香族ビニル−不飽和ジカルボン酸無水物共重合体の三連連鎖分布の測定は以下の条件で測定した。なお、共重合体は予め揮発分を除去して精製したものを測定に用いた。
装置名：ＡＶＡＮＣＥ−３００（ＢＲＵＫＥＲ社製）
測定核種：Ｃ１３
測定方法：ＤＥＰＴ４５とＤＥＰＴ１３５の差スペクトル
測定温度：２３℃±２℃
試料濃度：１０質量部
使用溶媒：アセトン−ｄ６
積算回数：
ＤＥＰＴ４５・・・２万回
ＤＥＰＴ１３５・・・２万回
三連連鎖分布の解析方法：
ＤＥＰＴ４５とＤＥＰＴ１３５の差スペクトルよりスチレン−スチレン−無水マレイン酸三連連鎖に由来するメチレンシグナル、スチレン−スチレン−スチレン三連連鎖に由来するメチレンシグナル、及び無水マレイン酸−スチレン−無水マレイン酸三連連鎖に由来するメチレンシグナルをそれぞれ積分して、それらの積分比から三連連鎖分布を算出した。
(2) Measurement of triple chain distribution of aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer The measurement of triple chain distribution of aromatic vinyl-unsaturated dicarboxylic acid anhydride copolymer in the present invention is performed under the following conditions. Measured with In addition, the copolymer used for the measurement what removed the volatile matter beforehand and refine | purified.
Device name: AVANCE-300 (manufactured by BRUKER)
Measurement nuclide: C13
Measuring method: difference spectrum between DEPT45 and DEPT135 Measuring temperature: 23 ° C. ± 2 ° C.
Sample concentration: 10 parts by mass Solvent used: Acetone-d6
Integration count:
DEPT45 ... 20,000 times DEPT135 ... 20,000 times Analysis method of triple chain distribution:
From the difference spectrum of DEPT45 and DEPT135, methylene signal derived from styrene-styrene-maleic anhydride triple chain, methylene signal derived from styrene-styrene-styrene triple chain, and maleic anhydride-styrene-maleic anhydride triple chain The methylene signals derived from were integrated, and the triple chain distribution was calculated from their integration ratio.
（３）（Ｎ−置換）マレイミド−スチレン−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の組成
下記記載の測定条件でＮＭＲを測定し、イミド基のカルボニル炭素の積分値と未反応ジカルボン酸無水物基およびイミド化反応中間体のマレアミド酸中間体のカルボニル炭素の積分値の比等から（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の組成を求めた。
装置名：ＡＶＡＮＣＥ−３００（ＢＲＵＫＥＲ社製）
測定核種：Ｃ１３
測定温度：１１０℃
試料濃度：１０質量部
使用溶媒：ＤＭＳＯ−ｄ６
積算回数：１万回
(3) Composition of (N-substituted) maleimide-styrene-unsaturated dicarboxylic anhydride type heat-resistant thermoplastic resin NMR was measured under the measurement conditions described below, and the integrated value of carbonyl carbon of imide group and unreacted dicarboxylic acid The composition of the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic acid anhydride-based heat-resistant thermoplastic resin from the ratio of the carbonyl carbon integral value of the anhydride group and the imidization reaction intermediate maleamic acid intermediate, etc. Asked.
Device name: AVANCE-300 (manufactured by BRUKER)
Measurement nuclide: C13
Measurement temperature: 110 ° C
Sample concentration: 10 parts by mass Solvent used: DMSO-d6
Integration count: 10,000 times
（４） 重量平均分子量
本発明における（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の重量平均分子量は、下記記載のＧＰＣ測定条件で測定した。
装置名：ＳＹＳＴＥＭ−２１ Ｓｈｏｄｅｘ（昭和電工社製）
カラム：ＰＬ ｇｅｌ ＭＩＸＥＤ−Ｂを３本直列
温度：４０℃
検出：示差屈折率
溶媒：テトラハイドロフラン
濃度：２質量部
検量線：標準ポリスチレン（ＰＳ）（ＰＬ社製）を用いて作製し、重量平均分子量はＰＳ換算値で表した。
(4) Weight average molecular weight The weight average molecular weight of the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride heat-resistant thermoplastic resin in the present invention was measured under the GPC measurement conditions described below.
Device name: SYSTEM-21 Shodex (manufactured by Showa Denko)
Column: 3 series PL gel MIXED-B Temperature: 40 ° C
Detection: Differential refractive index Solvent: Tetrahydrofuran Concentration: 2 parts by mass Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL), and weight average molecular weight was expressed in terms of PS.
（５）黄色度
本発明における（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の黄色度は次に示すような方法により実施した。
装置：ＳＺ−ＩＩシグマ８０ 測色色差計（日本電色社製）
温度：２３℃±２℃
溶媒：テトラヒドロフラン
測定モード：透過法
(5) Yellowness The yellowness of the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic acid anhydride heat-resistant thermoplastic resin in the present invention was determined by the following method.
Apparatus: SZ-II Sigma 80 colorimetric color difference meter (manufactured by Nippon Denshoku)
Temperature: 23 ° C ± 2 ° C
Solvent: Tetrahydrofuran Measurement mode: Permeation method
（６） 酸価
本発明における（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂の酸価測定は、次に示すような滴定法により実施した。
先ず共重合体を溶媒に溶解し、指示薬を加えて試料溶液を作成した。そこへアルカリ溶液を滴下し、良く攪拌させて中和反応を促進させた。試料溶液が淡紫色を呈した点を終点とした。また、溶媒のみを試料としてブランク滴定を実施した。酸価（ｍｇＫＯＨ／ｇ）は下記式１により算出した。
酸価＝{アルカリ濃度（Ｎ）×（滴下量合計−ブランク値）（ｍｌ）×５６.１１（ｇ/ｍｏｌ）}／サンプル秤量値（ｇ） 式１
使用器具：２５ｃｍ3ビュレット、１００ｃｍ３共栓付三角フラスコ
温度：２３℃±２℃
溶媒：メチルエチルケトン
試料溶液濃度：１質量部
アルカリ溶液：０.１Ｎ水酸化カリウムエタノール溶液（和光純薬製）
指示薬：フェノールフタレイン０.５質量部エタノール溶液
(6) Acid value The acid value of the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic acid anhydride heat-resistant thermoplastic resin in the present invention was measured by the titration method as shown below.
First, the copolymer was dissolved in a solvent, and an indicator was added to prepare a sample solution. The alkaline solution was dropped therein and stirred well to promote the neutralization reaction. The point at which the sample solution was light purple was used as the end point. Further, blank titration was performed using only the solvent as a sample. The acid value (mgKOH / g) was calculated by the following formula 1.
Acid value = {alkaline concentration (N) × (total dripping amount−blank value) (ml) × 56.11 (g / mol)} / sample weighing value (g) Formula 1
Equipment used: Erlenmeyer flask with 25 cm3 burette and 100 cm3 stopper Temperature: 23 ° C ± 2 ° C
Solvent: Methyl ethyl ketone Sample solution concentration: 1 part by mass Alkaline solution: 0.1 N potassium hydroxide ethanol solution (manufactured by Wako Pure Chemical Industries)
Indicator: 0.5 parts by mass ethanol solution of phenolphthalein
（７）メタノール可溶分
本発明における（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂のメタノール可溶分は次に示すような方法により行った。
予め重量を測定した樹脂をメチルエチルケトンに溶解し、約５質量部の溶液を作成した。その溶液を大過剰のメタノールに滴下してポリマーを析出させた。析出物を濾過で回収した後、１００℃で６時間乾燥させた。乾燥後の析出物の重量を測定した。重量測定は析出物の乾燥終了直後に行った。メタノール可溶分（質量部）は下記式２により算出した。
メタノール可溶分＝１００−｛乾燥後析出物重量（ｇ）/析出前樹脂重量（ｇ）×１００｝ 式２
(7) Methanol-soluble content The methanol-soluble content of the (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin in the present invention was measured by the following method.
The resin weighed in advance was dissolved in methyl ethyl ketone to prepare a solution of about 5 parts by mass. The solution was dropped into a large excess of methanol to precipitate a polymer. The precipitate was collected by filtration and then dried at 100 ° C. for 6 hours. The weight of the precipitate after drying was measured. The weight measurement was performed immediately after the drying of the precipitate. The methanol soluble part (parts by mass) was calculated by the following formula 2.
Methanol-soluble matter = 100− {precipitate weight after drying (g) / resin weight before precipitation (g) × 100} Formula 2
（８） ビカット軟化温度
ＪＩＳ Ｋ７２０６に従った。荷重５０Ｎ、昇温速度５０℃／ｈｒで測定した。
(8) Vicat softening temperature According to JIS K7206. The measurement was performed at a load of 50 N and a heating rate of 50 ° C./hr.
（９） シャルピー衝撃強さ
ＪＩＳ Ｋ７２１１に従った。なお、シャルピー衝撃強さはノッチタイプＡを有するタイプ１試験片を用い、打撃方向はエッジワイズを採用して測定した。
(9) Charpy impact strength According to JIS K7211. The Charpy impact strength was measured using a type 1 test piece having a notch type A, and the striking direction was measured using edgewise.
（１０）成形品外観
本発明における（Ｎ−置換）マレイミド−芳香族ビニル−不飽和ジカルボン酸無水物系耐熱性熱可塑性樹脂とＡＢＳ樹脂からなる耐熱付与材と、ＡＢＳ樹脂とを混合して得られた樹脂組成物の成形品外観は、以下の条件で成形して外観評価を実施した。
装置：射出成形機（Ｋ−１２５−１、川口鉄工社製）
成形温度：２５０℃
プレート形状：９ｃｍ×５ｃｍ
評価方法：成形品の目視による評価
◎：成形不良が見られない場合。
○：成形不良が見られるが、殆ど目立たない。
△：成形不良が見られ、若干目立つ。
×：成形不良が見られ、著しく目立つ。
(10) Appearance of molded product Obtained by mixing (N-substituted) maleimide-aromatic vinyl-unsaturated dicarboxylic anhydride-based heat-resistant thermoplastic resin and heat-resisting material composed of ABS resin with ABS resin. The appearance of the molded product of the obtained resin composition was evaluated under the following conditions.
Apparatus: Injection molding machine (K-125-1, manufactured by Kawaguchi Tekko)
Molding temperature: 250 ° C
Plate shape: 9cm x 5cm
Evaluation method: Visual evaluation of molded product A: When molding defects are not observed.
○: Molding defects are observed, but are hardly noticeable.
Δ: Molding defects are seen and slightly noticeable.
X: Molding defects are observed and are noticeable.
本発明はＡＢＳ樹脂に対して耐熱付与効果が極めて高く、色相が良好で、メタノール可溶分の少ない耐熱性熱可塑性樹脂の製造方法とその熱可塑性樹脂とＡＢＳ樹脂を混合することにより得られる、ＡＢＳ樹脂に対して分散性が良好でかつ耐熱付与性能の高い耐熱付与材とそれを用いた樹脂組成物に関するものであり、該樹脂組成物は自動車内装部品、車載用音響機器、家電・ＯＡ機器等、広範囲に使用する事ができる。また、本発明のマレイミド系樹脂は耐熱付与性能が極めて高いため、該樹脂組成物を得る際のマレイミド系樹脂の使用量を削減する事ができ、低コスト化を実現する事ができるため、極めて有用である。
The present invention has an extremely high heat resistance imparting effect on the ABS resin, has a good hue, and is obtained by mixing the thermoplastic resin and the ABS resin with a method for producing a heat resistant thermoplastic resin having a small amount of methanol soluble matter, BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat imparting material having good dispersibility with respect to ABS resin and high heat imparting performance and a resin composition using the same, and the resin composition is used for automobile interior parts, in-vehicle acoustic equipment, home appliances and OA equipment. It can be used in a wide range. In addition, since the maleimide resin of the present invention has extremely high heat resistance imparting performance, the amount of maleimide resin used in obtaining the resin composition can be reduced, and the cost can be reduced. Useful.
Claims (6)
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| JP7025834B2 (en) * | 2015-02-25 | 2022-02-25 | 東洋スチレン株式会社 | Styrene-based resin composition and molded article made of the styrene resin composition |
| KR102510711B1 (en) * | 2015-05-19 | 2023-03-16 | 덴카 주식회사 | Heat resistant resin composition and manufacturing method thereof |
| JP7245333B2 (en) * | 2019-07-10 | 2023-03-23 | デンカ株式会社 | Maleimide-based copolymer, method for producing the same, resin composition, and injection-molded article |
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