JP3141707B2 - High nitrile-containing vinyl copolymer and method for producing the same - Google Patents
High nitrile-containing vinyl copolymer and method for producing the sameInfo
- Publication number
- JP3141707B2 JP3141707B2 JP06264241A JP26424194A JP3141707B2 JP 3141707 B2 JP3141707 B2 JP 3141707B2 JP 06264241 A JP06264241 A JP 06264241A JP 26424194 A JP26424194 A JP 26424194A JP 3141707 B2 JP3141707 B2 JP 3141707B2
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- Prior art keywords
- copolymer
- weight
- polymerization
- monomer
- vinyl
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、溶融時の熱着色安定性
が優れ、かつ耐薬品性の良好な高ニトリル含有ビニル系
共重合体およびその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high nitrile-containing vinyl copolymer having excellent thermal coloring stability upon melting and good chemical resistance, and a method for producing the same.
【０００２】[0002]
【従来の技術】アクリロニトリル−ブタジエン−スチレ
ン共重合体樹脂（ＡＢＳ樹脂）は耐衝撃性、耐薬品性、
成形加工性のバランスに優れ、成形用樹脂として広く使
われている。たとえば電気冷蔵庫用材料の場合、電気冷
蔵庫の断熱層に発砲ポリウレタンを用い、その発砲剤と
してフロンを使用する。そのため断熱層近傍に用いる樹
脂材料には、フロンによって侵されない性質が要求され
ており、ＡＢＳ樹脂がよく用いられる。2. Description of the Related Art Acrylonitrile-butadiene-styrene copolymer resin (ABS resin) has high impact resistance, chemical resistance,
It has an excellent balance of moldability and is widely used as a molding resin. For example, in the case of a material for an electric refrigerator, foamed polyurethane is used for a heat insulating layer of the electric refrigerator, and Freon is used as the foaming agent. Therefore, a resin material used in the vicinity of the heat insulating layer is required to have a property of not being attacked by chlorofluorocarbon, and an ABS resin is often used.
【０００３】ところで近年の環境問題にかかわるフロン
規制にて、前述の発砲剤としてフロン１４１ｂ（代替フ
ロン）が用いられつつある。この代替フロンは従来フロ
ンにくらべ樹脂の侵食力が強いため、従来のＡＢＳ樹脂
では耐久性不足であり、前述の断熱層近傍に用いる樹脂
材料には今まで以上の耐薬品性が要求されている。By the way, in recent years, regulations on chlorofluorocarbons related to environmental problems have been using fluorocarbon 141b (alternative fluorocarbon) as the above-mentioned foaming agent. Since this alternative CFC has a stronger erosion power of the resin than the conventional CFC, the durability of the conventional ABS resin is insufficient, and the resin material used in the vicinity of the heat insulating layer is required to have higher chemical resistance than before. .
【０００４】そこで、ＡＢＳ樹脂の耐薬品性を向上する
手段として、樹脂組成物中のシアン化ビニル系単量体成
分の含有割合を高めることが知られており、特にＡＢＳ
樹脂のマトリックス成分であるアクリロニトリル−スチ
レン共重合体等について、シアン化ビニル系単量体成分
の含有割合を高めた、いわゆる高ニトリル含有ビニル系
共重合体およびその製造方法が幾つか提案されている。Therefore, as a means for improving the chemical resistance of the ABS resin, it is known to increase the content of a vinyl cyanide monomer component in the resin composition.
With respect to acrylonitrile-styrene copolymers and the like that are matrix components of resins, so-called high nitrile-containing vinyl copolymers in which the content ratio of vinyl cyanide-based monomer components is increased, and some methods for producing the same have been proposed. .
【０００５】たとえば単に耐薬品性と機械的特性を向上
させるために、共重合物組成割合を均一に制御する方法
（特公昭４６−２７８０８号公報）、耐薬品性を有し、
かつ軟化点に優れる高ニトリル含有ビニル系共重合体を
得るために、特定の２種の重合開始剤を併用し、計算量
のスチレンを比較的高温（８０〜１００℃）で連続添加
しながら、重合系を段階的に昇温する方法（特公昭５０
−３３９１７号公報）、不飽和ニトリル単量体を主成分
とする未反応モノマをストリッピングして未反応モノマ
分の少ない高ニトリル含有ビニル系共重合体を得る方法
（特開平３−２２７３０６号公報）などがある。For example, in order to simply improve the chemical resistance and mechanical properties, a method of uniformly controlling the composition ratio of a copolymer (Japanese Patent Publication No. 46-27808) is used.
In addition, in order to obtain a high nitrile-containing vinyl copolymer having an excellent softening point, a specific two types of polymerization initiators are used in combination, and a calculated amount of styrene is continuously added at a relatively high temperature (80 to 100 ° C.) A method of gradually raising the temperature of a polymerization system (Japanese Patent Publication No. Sho 50
No. 33917), a method of stripping an unreacted monomer containing an unsaturated nitrile monomer as a main component to obtain a high nitrile-containing vinyl copolymer containing a small amount of unreacted monomer (Japanese Patent Application Laid-Open No. 3-227306). )and so on.
【０００６】しかしながら、上述した従来の処方では、
樹脂組成物中のシアン化ビニル系単量体成分の含有割合
を高めることにより、ある程度耐薬品性に優れた高ニト
リル含有ビニル系共重合体を得ることはできるが、樹脂
成形加工品の初期色調の黄身が強くなり、品質を低下せ
しめるという問題点が新たに生じた。そのため耐薬品性
および溶融時の熱着色安定性の両者に優れた高ニトリル
含有ビニル系共重合体は今だ得られておらず、電気冷蔵
庫用材料として要求される耐衝撃性、耐薬品性、成形加
工性のバランスに優れ、かつ溶融時の熱着色安定性を十
分満足する樹脂材料がいまだ得られていないというのが
現状である。However, in the above-mentioned conventional formulation,
By increasing the content of the vinyl cyanide monomer component in the resin composition, it is possible to obtain a high nitrile-containing vinyl copolymer having a certain degree of chemical resistance. There is a new problem that the yolk becomes stronger and the quality deteriorates. For this reason, a high nitrile-containing vinyl copolymer excellent in both chemical resistance and thermal coloring stability upon melting has not yet been obtained, and the impact resistance, chemical resistance, At present, a resin material which is excellent in molding processability balance and sufficiently satisfies thermal coloring stability at the time of melting has not yet been obtained.
【０００７】[0007]
【発明が解決しようとする課題】従って、本発明はこの
ような耐衝撃性、耐薬品性、成形加工性のバランスに優
れ、かつ溶融時の熱着色安定性を十分満足し、高品質の
ＡＢＳ樹脂が得られる新規な高ニトリル含有ビニル系共
重合体及びその製造方法を提供することを目的とする。
本発明者らは、かかる目的を達成するためにシアン化ビ
ニル系単量体成分の含有割合を高めた、いわゆる高ニト
リル含有ビニル系共重合体について耐薬品性と溶融時の
熱着色安定性の両立について鋭意検討した結果、シアン
化ビニル系単量体の３連シーケンスの割合が一定値以下
の高ニトリル含有ビニル系共重合体が、高い耐薬品性を
保持しつつ溶融時の熱着色安定性が良好である事を見い
だした。またこの新規な高ニトリル含有ビニル系共重合
体は、残存単量体中のシアン化ビニル系単量体成分割合
を制御して重合を行うことにより、製造可能である事を
見いだし、本発明に到達した。SUMMARY OF THE INVENTION Accordingly, the present invention provides an excellent balance of impact resistance, chemical resistance, and moldability, and sufficiently satisfies the thermal coloring stability at the time of melting. An object of the present invention is to provide a novel high nitrile-containing vinyl copolymer from which a resin can be obtained and a method for producing the same.
The present inventors have increased the content of the vinyl cyanide-based monomer component in order to achieve such an object, so-called high nitrile-containing vinyl-based copolymer has high chemical resistance and thermal coloring stability upon melting. As a result of intensive studies on the compatibility, the vinyl nitrate-containing vinyl copolymer in which the ratio of the triple sequence of the vinyl cyanide monomer is a certain value or less can be obtained. Was found to be good. Further, the novel high nitrile-containing vinyl copolymer was found to be producible by controlling the ratio of vinyl cyanide monomer component in the residual monomer and conducting the polymerization. Reached.
【０００８】[0008]
【課題を解決するための手段】すなわち本発明は、 （１）シアン化ビニル系単量体２５〜５５重量％，芳香
族ビニル系単量体７５〜４５重量％およびこれらと共重
合可能な他のビニル系単量体０〜２０重量％を構成単位
とする共重合体であって、シアン化ビニル系単量体の３
連シーケンスの割合が該共重合体中１０重量％以下であ
る高ニトリル含有ビニル系共重合体と、 （２）シアン化ビニル系単量体２５〜５５重量％，芳香
族ビニル系単量体７５〜４５重量％およびこれらと共重
合可能な他のビニル系単量体０〜２０重量％からなる単
量体を重合するに際し、重合開始から重合終了までの残
存単量体中のシアン化ビニル系単量体成分割合を９５重
量％以下にし、かつ重合開始から少なくとも重合率１０
％経過時点までの残存単量体中のシアン化ビニル系単量
体成分割合を７０重量％以上９５重量％以下にして水系
懸濁重合する、上記（１）記載の高ニトリル含有ビニル
系共重合体の製造方法に係るものである。That is, the present invention provides: (1) 25 to 55% by weight of a vinyl cyanide monomer, 75 to 45% by weight of an aromatic vinyl monomer and other copolymerizable with them. A copolymer containing 0 to 20% by weight of a vinyl monomer as a structural unit, wherein 3
(2) 25 to 55% by weight of vinyl cyanide monomer, 75% of aromatic vinyl monomer, When polymerizing a monomer consisting of 0 to 45% by weight and 0 to 20% by weight of another vinyl monomer copolymerizable therewith, vinyl cyanide in the remaining monomer from the start of polymerization to the end of polymerization The monomer component ratio should be 95% by weight or less, and at least 10
% Of the vinyl cyanide monomer component in the residual monomer up to the time point of 70% by weight or more and not more than 95% by weight and subjecting the aqueous suspension polymerization to the aqueous nitrile-containing vinyl copolymer as described in (1) above. The present invention relates to a method for producing a united product.
【０００９】本発明において、高ニトリル含有ビニル系
共重合体の単量体成分の構成単位は、シアン化ビニル系
単量体２５〜５５重量％、芳香族ビニル系単量体７５〜
４５重量％である必要がある。好ましくは、シアン化ビ
ニル系単量体３０〜４５重量％、芳香族ビニル系単量体
７０〜５５重量％の範囲のものがよい。シアン化ビニル
系単量体の共重合量が２５重量％未満であると、得られ
る共重合体を用いた樹脂組成物の耐薬品性が不十分であ
り、また５５重量％を越えると、得られる共重合体を用
いた樹脂組成物の成形加工性および溶融時の熱着色安定
性が共に著しく低下する。また、必要に応じて共重合可
能な他のビニル系単量体を構成成分とすることができ、
好ましくは０〜２０重量％である。２０重量％を越える
と、得られる共重合体を用いた樹脂組成物の耐薬品性を
維持することが困難になる。In the present invention, the constituent units of the monomer component of the high nitrile-containing vinyl copolymer are 25 to 55% by weight of a vinyl cyanide monomer and 75 to 75% of an aromatic vinyl monomer.
It must be 45% by weight. Preferably, the content ranges from 30 to 45% by weight of a vinyl cyanide monomer and from 70 to 55% by weight of an aromatic vinyl monomer. When the copolymerization amount of the vinyl cyanide-based monomer is less than 25% by weight, the chemical resistance of the resin composition using the obtained copolymer is insufficient, and when it exceeds 55% by weight, the obtained resin composition has an insufficient amount. Both the moldability of the resin composition using the resulting copolymer and the thermal coloring stability during melting are significantly reduced. Further, if necessary, other copolymerizable vinyl monomers can be used as a component,
Preferably it is 0 to 20% by weight. If it exceeds 20% by weight, it becomes difficult to maintain the chemical resistance of the resin composition using the obtained copolymer.
【００１０】本発明の高ニトリル含有ビニル系共重合体
に用いられるシアン化ビニル系単量体としては、アクリ
ロニトリルおよびメタクリロニトリルなどが挙げられ、
１種または２種以上用いることができる。アクリロニト
リルが特に好ましい。また芳香族ビニル系単量体として
は、スチレン，α−メチルスチレン，オルソメチルスチ
レン，パラメチルスチレン，パラ−ｔ−ブチルスチレン
およびハロゲン化スチレンなどが挙げられ、１種または
２種以上用いることができる。スチレン，α−メチルス
チレンが特に好ましく、さらに好ましくはスチレンが良
い。他のビニル系単量体としては、アクリル酸，メタク
リル酸などの不飽和カルボン酸；アクリル酸メチル，メ
タクリル酸メチル，アクリル酸ブチルなどの（メタ）ア
クリル酸エステル類；アクリルアミド，メタクリルアミ
ド，Ｎ−メチルアクリルアミドなどの（メタ）アクリル
アミド類およびマレイミド，Ｎ−メチルマレイミド，Ｎ
−フェニルマレイミドなどのマレイミド類；無水マレイ
ン酸、無水シトラコン酸、無水アコニット酸などの不飽
和カルボン酸無水物を挙げることができる。The vinyl cyanide monomer used in the high nitrile-containing vinyl copolymer of the present invention includes acrylonitrile and methacrylonitrile.
One or more kinds can be used. Acrylonitrile is particularly preferred. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, orthomethylstyrene, paramethylstyrene, para-t-butylstyrene, and halogenated styrene, and one or more kinds may be used. it can. Styrene and α-methylstyrene are particularly preferred, and styrene is more preferred. Other vinyl monomers include unsaturated carboxylic acids such as acrylic acid and methacrylic acid; (meth) acrylates such as methyl acrylate, methyl methacrylate and butyl acrylate; acrylamide, methacrylamide, N- (Meth) acrylamides such as methylacrylamide and maleimide, N-methylmaleimide, N
Maleimides such as phenylmaleimide; and unsaturated carboxylic anhydrides such as maleic anhydride, citraconic anhydride and aconitic anhydride.
【００１１】また、本発明の高ニトリル含有ビニル系共
重合体中のシアン化ビニル系単量体の３連シーケンスと
は、次の（式１）に表される当該共重合体中のセグメン
トであり、The triple sequence of a vinyl cyanide monomer in the high nitrile-containing vinyl copolymer of the present invention is defined as a segment in the copolymer represented by the following (formula 1). Yes,
【化１】 ２００℃前後の共重合体が溶融した状態では、次の（式
２）に示す分子内環化反応が進み、着色変化する。Embedded image In a state where the copolymer at about 200 ° C. is melted, an intramolecular cyclization reaction shown in the following (formula 2) proceeds, and the color changes.
【００１２】[0012]
【化２】 本発明の高ニトリル含有ビニル系共重合体は、これらの
熱着色安定性を阻害するシアン化ビニル系単量体の３連
シーケンスの割合が１０重量％以下と少ないため、溶融
時の熱着色安定性に優れている。より好ましくは８重量
％未満である。１０重量％を越えると溶融時の熱着色安
定性が劣るため好ましくない。このような共重合体中の
シアン化ビニル系単量体の３連シーケンスの割合が１０
重量％以下に制御された新規な高ニトリル含有ビニル系
共重合体は、残存単量体中のシアン化ビニル系単量体成
分割合を制御して重合を行うことにより製造することが
できる。Embedded image In the high nitrile-containing vinyl copolymer of the present invention, the ratio of the triple sequence of the vinyl cyanide monomer which inhibits the thermal coloring stability is as low as 10% by weight or less. Excellent in nature. More preferably Ru der less than 8 wt%. If it exceeds 10% by weight, the thermal coloring stability at the time of melting is inferior. When the ratio of the triple sequence of the vinyl cyanide monomer in such a copolymer is 10
The novel high nitrile-containing vinyl copolymer controlled to not more than% by weight can be produced by controlling the ratio of the vinyl cyanide monomer component in the remaining monomer to carry out the polymerization.
【００１３】また、本発明の高ニトリル含有ビニル系共
重合体の還元粘度（ηsp/c）は、得られる共重合体を用
いた樹脂組成物の耐薬品性をより向上させるために、
０．２０以上であることが好ましく、より好ましくは
０．４０以上である。また得られる共重合体を用いた樹
脂組成物の成形加工性をより向上させるために、０．８
０ｄｌ／ｇ以下、より好ましくは０．７０ｄｌ／ｇ以下
である。なお還元粘度は、連鎖移動剤量、開始剤量、重
合温度で制御可能である。The reduced viscosity (ηsp / c) of the high nitrile-containing vinyl copolymer of the present invention is determined in order to further improve the chemical resistance of the resin composition using the obtained copolymer.
It is preferably at least 0.20, more preferably at least 0.40. Further, in order to further improve the moldability of the resin composition using the obtained copolymer, 0.8
0 dl / g or less, more preferably 0.70 dl / g or less. The reduced viscosity can be controlled by the amount of the chain transfer agent, the amount of the initiator, and the polymerization temperature.
【００１４】ここで、還元粘度（ηsp/c）は、高ニトリ
ル含有ビニル系共重合体をメチルエチルケトン５０ｍｌ
に０．２０ｇを溶解し、粘度管を用いて３０℃で流下時
間を測定したのち、次式（３）により算出した値であ
る。Here, the reduced viscosity (ηsp / c) is such that a high nitrile-containing vinyl copolymer is obtained by adding 50 ml of methyl ethyl ketone.
Was dissolved in the solution and the flow time was measured at 30 ° C. using a viscosity tube, and the value was calculated by the following equation (3).
【００１５】 還元粘度（ηsp/c）＝〔（ｔ１／ｔ０）−１〕／Ｃ （式３） 式中、ｔ１；試料溶液中の流下時間（秒） ｔ０；ブランク溶液の流下時間（秒） Ｃ ；測定用試料の樹脂濃度（ｇ／１００ｍｌ） また、本発明の高ニトリル含有ビニル系共重合体中のオ
リゴマー量は、成形時の金型汚れを低減させるために
０．６重量％以下であることが好ましい。これは製造方
法に水系懸濁重合法を用いることにより実現するもので
ある。Reduced viscosity (ηsp / c) = [(t1 / t0) -1] / C (Equation 3) where t1: Flow time in sample solution (second) t0: Flow time of blank solution (second) C: Resin concentration of sample for measurement (g / 100 ml) The amount of oligomer in the high nitrile-containing vinyl copolymer of the present invention is 0.6% by weight or less in order to reduce mold contamination during molding. Preferably, there is. This is realized by using an aqueous suspension polymerization method as a production method.
【００１６】以下、本発明の高ニトリル含有ビニル系共
重合体の製造方法について述べる。本発明の高ニトリル
含有ビニル系共重合体を得る重合方法としては水系懸濁
重合である必要がある。水系懸濁重合以外の重合方法で
は、残存単量体中のシアン化ビニル系単量体成分割合の
制御が難しく、またオリゴマー割合を０．６重量％以下
にすることができない。さらに乳化剤、溶媒などの副原
料が溶融時の熱着色安定性を著しく悪化させてしまう。Hereinafter, a method for producing the high nitrile-containing vinyl copolymer of the present invention will be described. The polymerization method for obtaining the high nitrile-containing vinyl copolymer of the present invention needs to be aqueous suspension polymerization. In a polymerization method other than the aqueous suspension polymerization, it is difficult to control the ratio of the vinyl cyanide-based monomer component in the residual monomer, and the oligomer ratio cannot be reduced to 0.6% by weight or less. Further, auxiliary materials such as an emulsifier and a solvent significantly deteriorate the thermal coloring stability at the time of melting.
【００１７】前記重合に用いられる懸濁安定剤として
は、粘土、硫酸バリウム、水酸化マグネシウム等の無機
系懸濁安定剤、ポリビニルアルコール、カルボキシメチ
ルセルロース、ポリアクリルアミド、メタクリル酸メチ
ル／アクリルアミド共重合体等の有機系懸濁安定剤など
が挙げられ、中でも有機系懸濁安定剤が共重合体の溶融
時の熱着色安定性の面で好ましく、より好ましくはメタ
クリル酸メチル／アクリルアミド共重合体がよい。Examples of the suspension stabilizer used in the above polymerization include inorganic suspension stabilizers such as clay, barium sulfate and magnesium hydroxide, polyvinyl alcohol, carboxymethyl cellulose, polyacrylamide, methyl methacrylate / acrylamide copolymer and the like. And organic suspension stabilizers. Among them, organic suspension stabilizers are preferable in view of thermal coloring stability at the time of melting of the copolymer, and more preferable is methyl methacrylate / acrylamide copolymer.
【００１８】前記重合に用いられる、仕込みモノマー総
量１００重量部に対する分散媒体としての水の仕込み総
量は、モノマの良好な水中分散性の維持および水中への
シアン化ビニル系単量体の多量の溶解移行防止といった
観点から８０〜３５０重量部の範囲から選ぶのが好まし
い。残存単量体中のシアン化ビニル系単量体成分割合の
制御上より好ましくは１００〜２００重量部がよい。The total amount of water used as a dispersion medium per 100 parts by weight of the total amount of charged monomers used in the polymerization is to maintain good dispersibility of the monomer in water and to dissolve a large amount of the vinyl cyanide monomer in water. It is preferable to select from the range of 80 to 350 parts by weight from the viewpoint of preventing migration. From the viewpoint of controlling the ratio of the vinyl cyanide monomer component in the residual monomer, the amount is more preferably 100 to 200 parts by weight.
【００１９】本発明の高ニトリル含有ビニル系共重合体
を得る重合温度は、モノマ種、開始剤種、連鎖移動剤種
に応じて、３０〜１６０℃、好ましくは５０〜１２０℃
の範囲から選べば良い。The polymerization temperature for obtaining the high nitrile-containing vinyl copolymer of the present invention is from 30 to 160 ° C., preferably from 50 to 120 ° C., depending on the type of monomer, type of initiator and type of chain transfer agent.
You can choose from the range.
【００２０】前記重合に使用される重合開始剤としては
２，２’−アゾビス（２，４−ジメチルバレロニトリ
ル），２，２’−アゾビス（２，４，４−トリメチルバ
レロニトリル）などのアゾニトリル化合物およびｔ−ブ
チルパーオキサイド，ｔ−ブチルパーオキシネオデカネ
ート，ｔ−ブチルパーオキシネオセキサノエート，ｔ−
ブチルパ−オキシピバレートなどの有機過酸化物が挙げ
られ、これらは１種または２種以上併用して用いること
ができるが、中でもアゾニトリル化合物が特に好まし
い。Examples of the polymerization initiator used in the polymerization include azonitriles such as 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2,4,4-trimethylvaleronitrile). Compound and t-butyl peroxide, t-butyl peroxy neodecanoate, t-butyl peroxy neosexanoate, t-butyl peroxide
Organic peroxides such as butyl peroxypivalate and the like can be mentioned, and these can be used alone or in combination of two or more. Among them, azonitrile compounds are particularly preferable.
【００２１】ここで用いられる連鎖移動剤についてはｎ
−オクチルメルカプタン，ｔ−ドデシルメルカプタン，
ｎ−ドデシルメルカプタンなどのアルキルメルカプタン
類などが挙げられる。これらの連鎖移動剤は１種または
２種以上併用して用いることができる。使用方法として
は一括添加、分割添加、または連続添加のいずれの方法
でも差支えない。The chain transfer agent used here is n
-Octyl mercaptan, t-dodecyl mercaptan,
and alkyl mercaptans such as n-dodecyl mercaptan. These chain transfer agents can be used alone or in combination of two or more. The method of use may be any of batch addition, divisional addition, and continuous addition.
【００２２】本発明の高ニトリル含有ビニル系共重合体
を得るためには、重合開始〜重合終了までの重合系内の
残存単量体中のシアン化ビニル系単量体成分割合を９５
％以下に制御し、かつ重合開始から少なくとも重合率１
０％経過時点までの残存単量体中のシアン化ビニル系単
量体成分割合を７０重量％以上９５重量％以下にする必
要がある。９５％を越えると共重合体中のシアン化ビニ
ル系単量体の３連シーケンスの割合を１０重量％以下に
することができない。In order to obtain the high nitrile-containing vinyl copolymer of the present invention, the ratio of the vinyl cyanide monomer component to the remaining monomer in the polymerization system from the start of polymerization to the end of polymerization is 95%.
% And a polymerization rate of at least 1 from the start of polymerization.
It is necessary that the proportion of the vinyl cyanide-based monomer component in the residual monomer up to the point of 0% is 70% by weight or more and 95% by weight or less. If it exceeds 95%, the ratio of the triple sequence of the vinyl cyanide monomer in the copolymer cannot be reduced to 10% by weight or less.
【００２３】また重合開始から少なくとも重合率１０％
経過時点までの残存単量体中のシアン化ビニル系単量体
成分割合が７０重量％未満であると、得られる共重合体
を用いた樹脂組成物の耐薬品性を維持することが困難に
なる。なぜなら、本発明の高ニトリル含有ビニル系共重
合体の長所である耐薬品性は、重合開始から重合率１０
％経過時点までの残存単量体中のシアン化ビニル系単量
体成分割合を７０重量％以上に保つことによって生成す
る、シアン化ビニル系単量体含有割合の高い、高ニトリ
ル共重合体成分により発現しているためである。つま
り、重合開始から重合率１０％経過時点までの残存単量
体中のシアン化ビニル系単量体成分割合が７０重量％以
下である場合、シアン化ビニル系単量体含有割合の低い
共重合体成分しか生成しないため、耐薬品性に寄与しな
いからである。At least 10% of the polymerization rate from the start of polymerization
If the ratio of the vinyl cyanide-based monomer component in the residual monomer up to the elapse of time is less than 70% by weight, it is difficult to maintain the chemical resistance of the resin composition using the obtained copolymer. Become. This is because the chemical resistance, which is an advantage of the high nitrile-containing vinyl copolymer of the present invention, is that the polymerization rate is 10% from the start of polymerization.
%, A high nitrile copolymer component having a high vinyl cyanide monomer content, which is produced by maintaining the vinyl cyanide monomer component ratio in the residual monomer to 70% by weight or more. It is because it is expressed by. That is, when the ratio of the vinyl cyanide-based monomer component in the residual monomer from the start of polymerization to the point when the polymerization rate has passed 10% is 70% by weight or less, the copolymer having a low vinyl cyanide-based monomer content ratio This is because only a coalesced component is generated and does not contribute to chemical resistance.
【００２４】ここで述べた高ニトリル共重合体成分は、
本発明の高ニトリル含有ビニル系共重合体をメチルエチ
ルケトンに溶解後、シクロヘキサン滴下により再析出し
た成分のことであり、析出物のシアン化ビニル系単量体
成分割合は、ＦＴ−ＩＲ分析により定量できる。The high nitrile copolymer component described here is
It is a component obtained by dissolving the high nitrile-containing vinyl copolymer of the present invention in methyl ethyl ketone and then reprecipitating it by dropwise addition of cyclohexane.The ratio of the vinyl cyanide monomer component of the precipitate can be quantified by FT-IR analysis. .
【００２５】残存単量体中のシアン化ビニル系単量体成
分割合は、重合開始剤の量、重合禁止剤の添加、ストリ
ッピングによるシアン化ビニル系単量体の重合系内から
の除去もしくはシアン化ビニル系単量体成分以外の単量
体の重合中の重合系内への添加にて、制御することがで
きる。The proportion of the vinyl cyanide monomer component in the residual monomer is determined by the amount of the polymerization initiator, the addition of a polymerization inhibitor, the removal of the vinyl cyanide monomer from the polymerization system by stripping or It can be controlled by adding a monomer other than the vinyl cyanide monomer component into the polymerization system during polymerization.
【００２６】[0026]
【実施例】本発明をさらに具体的に説明するために、以
下に実施例および比較例を挙げて説明するが、これら実
施例は本発明を限定するものではない。表１〜３、図
１、実施例および比較例中の部、％はそれぞれ重量部、
重量％を表す。EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but these examples do not limit the present invention. Parts in Tables 1 to 3, FIG. 1, Examples and Comparative Examples,% are parts by weight, respectively.
It represents% by weight.
【００２７】黄変度（ＹＩ）は、高ニトリル系共重合体
５ｇを直径５０ｍｍのアルミ皿に厚みがほぼ均一になる
ように敷きつめ、１８０℃ギアーオーブン内に６０分間
放置した後、２３℃、５０％相対湿度雰囲気下で１時間
静置し、日本電色工業（株）製、測色色差計（ＮＤ−１
００型）を用いて３刺激値Ｘ，Ｙ，Ｚを測定し、下記式
４により算出した。The degree of yellowing (YI) was determined by laying 5 g of a high nitrile copolymer on an aluminum plate having a diameter of 50 mm so that the thickness became almost uniform, and leaving it in a gear oven at 180 ° C. for 60 minutes. After standing for 1 hour in an atmosphere of 50% relative humidity, a colorimeter (ND-1) manufactured by Nippon Denshoku Industries Co., Ltd.
(00 type), the tristimulus values X, Y, and Z were measured and calculated by the following equation (4).
【００２８】 黄変度（ＹＩ）＝１００（１．２８Ｘ−１．０６Ｚ）Ｙ （式４） 還元粘度（ηｓｐ/c）はウベローデ粘度計を使用し、水
槽の温度（測定温度）を３０±０．１℃に調整して測定
した測定用試料の流下時間から、下記式５により算出し
た。ただし、式５中、ｔｓは測定用試料の流下時間であ
り、ｔ0 は測定用溶媒の流下時間であり、Ｃは測定用試
料の樹脂濃度（ｇ／１００ｍｌ）である。また、測定用
試料としては、精秤した約０．２ｇの樹脂を、５０ｍｌ
・メスフラスコを使用して測定溶媒であるメチルエチル
ケトンに溶解したものを使用した。 還元粘度（ηsp/c）＝〔（ｔｓ／ｔ0 ）−１〕／Ｃ （式５） 重合系内の未反応モノマの成分割合および共重合体中の
オリゴマー量は、島津製作所（株）製、ガスクロマトグ
ラフ（ＧＣ−１４Ａ型）を用いて測定した。未反応モノ
マ中のシアン化ビニル系単量体成分割合は次の式６によ
り、また、重合率は次の式７により算出した。Yellowing degree (YI) = 100 (1.28X-1.06Z) Y (Equation 4) The reduced viscosity (ηsp / c) was measured using an Ubbelohde viscometer, and the temperature of the water tank (measured temperature) was 30 ±. It was calculated by the following equation 5 from the falling time of the measurement sample measured at 0.1 ° C. In Equation 5, ts is the flow time of the measurement sample, t0 is the flow time of the measurement solvent, and C is the resin concentration (g / 100 ml) of the measurement sample. In addition, as a measurement sample, approximately 0.2 g of resin that was precisely weighed was placed in 50 ml.
A solution dissolved in methyl ethyl ketone, which is a measuring solvent, using a volumetric flask was used. The reduced viscosity (ηsp / c) = [(ts / t0) -1] / C (Equation 5) <br/> oligomer of the component parts and the copolymer unreacted mono Ma in the polymerization system is Shimadzu The measurement was performed using a gas chromatograph (GC-14A type) manufactured by Co., Ltd. Unreacted goods
The ratio of the vinyl cyanide monomer component in the polymer is given by the following formula 6.
Further, the polymerization rate was calculated by the following equation 7.
【００２９】 未反応モノマ中のシアン化ビニル系単量体成分割合（重量％）＝ ［（未反応 シアン化ビニル系単量体量) ／（未反応モノマ量）］ ×１００ （式６） 重合率（％）＝［（仕込みモノマ量−未反応モノマ量）／全モノマ量］×１０ ０ （式７） シアン化ビニル系単量体の３連シーケンスの割合は、13
Ｃ−ＮＭＲに現れるシアン化ビニル系単量体のα−炭素
のシグナルシフトが隣接モノマ種の違いで若干異なる事
を利用し、３連シーケンスの割合をそのシグナル積分値
から定量した。測定条件は以下の通りである。 Ratio of vinyl cyanide monomer component in unreacted monomer (% by weight) = [(unreacted vinyl cyanide monomer amount) / (unreacted monomer amount)] × 100 (formula 6) Rate (%) = [( amount of charged monomer−amount of unreacted monomer) / amount of all monomers ] × 100 (formula 7) The ratio of the triple sequence of the vinyl cyanide monomer is 13
Taking advantage of the fact that the signal shift of the α-carbon of the vinyl cyanide monomer appearing in C-NMR is slightly different depending on the type of adjacent monomer, the ratio of the triple sequence was quantified from the signal integrated value. The measurement conditions are as follows.
【００３０】 装置 ：ＪＥＯＬ ＪＮＭ−ＧＳＸ４００型 観測周波数 ：１００．５ＭＨｚ 溶媒 ：ＤＭＳＯ−ｄ6 濃度 ：４４５ｍｇ／２．５ｍＬ 化学シフト基準：Ｍｅ4 Ｓｉ 温度 ：１１０℃ 観測幅 ：２００００Ｈｚ データ点 ：３２Ｋ flip angle ：９０°（２１μｓ） pulsedelaytime：５．０ｓ 積算回数 ：７４００または８４００ デカップリング：gated decoupling(without NOE) 共重合体中の高ニトリル共重合体成分含有割合は、以下
に示す方法にて定量した。共重合体１ｇをメチルエチル
ケトン４０ｇに溶解し、これにシクロヘキサン２０ｇを
少しずつ滴下する。５０℃でよく撹拌したのち、室温下
一夜放置し、さらに恒温槽で３０℃とした後、析出して
いる共重合体成分を遠心分離し、この乾燥重量より含有
割合を定量した。Apparatus: JEOL JNM-GSX400 type Observation frequency: 100.5 MHz Solvent: DMSO-d 6 concentration: 445 mg / 2.5 mL Chemical shift standard: Me 4 Si Temperature: 110 ° C. Observation width: 20000 Hz Data point: 32K flip angle : 90 ° (21 μs) pulsedelaytime: 5.0 s Cumulative times: 7400 or 8400 Decoupling: gated decoupling (without NOE) The content ratio of the high nitrile copolymer component in the copolymer was determined by the following method. 1 g of the copolymer is dissolved in 40 g of methyl ethyl ketone, and 20 g of cyclohexane is added dropwise to the solution. After well stirring at 50 ° C., the mixture was allowed to stand at room temperature overnight, and then set at 30 ° C. in a constant temperature bath. The precipitated copolymer component was centrifuged, and the content ratio was determined from the dry weight.
【００３１】高ニトリル共重合体成分中のシアン化ビニ
ル系単量体成分割合は、以下に示す方法にて定量した。
前述の処理を施した共重合体成分を、加熱プレス成形し
て３０μｍ程度のフィルム状とし、これをＦＴ−ＩＲ分
析し２２６０ｃｍ-1と１６００ｃｍ-1に生じる吸光度ピ
ークのベースライン高さの比から式８に示す検量線を用
いてシアン化ビニル系単量体成分割合を定量した。The proportion of the vinyl cyanide monomer component in the high nitrile copolymer component was determined by the following method.
The copolymer component which has been subjected to the processing described above, the heating press molding in a 30μm about a film-like, which from the ratio of the baseline level of absorbance peak occurring FT-IR analysis was 2260 cm -1 and 1600 cm -1 The ratio of the vinyl cyanide-based monomer component was quantified using the calibration curve shown in Equation 8.
【００３２】 Ｘ＝（Ｒ＋０．５８７４４８２３）／０．０７３９６４２２ （式８） Ｘ：シアン化ビニル系単量体成分割合（重量％） Ｒ：吸光度ピ−ク高さ比｛＝Ｈ（２２６０）／Ｈ（１６
００）｝ 耐薬品性試験およびメルトフローレートは、以下に示す
熱可塑性樹脂組成物のそれぞれ成形試験片およびペレッ
トで測定を行った。X = (R + 0.5874482) /0.07396422 (Formula 8) X: Ratio of vinyl cyanide monomer component (% by weight) R: Absorbance peak height ratio ｛= H (2260) / H (16
00)｝ The chemical resistance test and the melt flow rate were measured on molded test pieces and pellets of the thermoplastic resin compositions shown below, respectively.
【００３３】参考例 （グラフト共重合体の製造）窒素置換した反応器に純水
１２０部、ブドウ糖０．５部、ピロリン酸ナトリウム
０．５部、硫酸第一鉄０．００５部およびポリブタジエ
ンラテックス（ゴム粒子径０．３μｍ，ゲル含有率８５
％）５０部（固形分換算）を仕込み、撹拌しながら反応
器内の温度を６５℃に昇温した。内温が６５℃に達した
時点を重合開始としてモノマ（スチレン３５部，アクリ
ロニトリル１５部）およびｔ−ドデシルメルカプタン
０．３部からなる混合物を５時間かけて連続滴下した。
同時に並行してクメンハイドロパーオキサイド０．２５
部，オレイン酸カリウム２．５部および純水２５部から
なる水溶液を７時間かけて連続滴下し、反応を完結させ
た。得られたグラフト共重合体ラテックスを硫酸で凝固
し、苛性ソ−ダで中和後、洗浄、濾過、乾燥してパウダ
−状のグラフト共重合体を得た。このグラフト共重合体
のグラフト率は４５％、樹脂質成分のηsp/cは０．６８
dl/gであった。 Reference Example (Production of Graft Copolymer) In a reactor purged with nitrogen, 120 parts of pure water, 0.5 part of glucose, 0.5 part of sodium pyrophosphate, 0.005 part of ferrous sulfate and polybutadiene latex ( Rubber particle diameter 0.3 μm, gel content 85
%) (Solid content), and the temperature in the reactor was raised to 65 ° C. while stirring. When the internal temperature reached 65 ° C., polymerization was started, and a mixture consisting of a monomer (35 parts of styrene and 15 parts of acrylonitrile) and 0.3 part of t-dodecylmercaptan was continuously added dropwise over 5 hours.
At the same time, cumene hydroperoxide 0.25
, 2.5 parts of potassium oleate and 25 parts of pure water were continuously added dropwise over 7 hours to complete the reaction. The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain a powdery graft copolymer. The graft ratio of this graft copolymer is 45%, and the ηsp / c of the resin component is 0.68.
dl / g.
【００３４】（熱可塑性樹脂組成物の製造）以下の実施
例１〜１０および比較例１〜６にて製造された共重合体
７３重量部とグラフト共重合体２７重量部およびエチレ
ンビスステアリルアミド０．８重量部をヘンシェルミキ
サーで混練後、４０ｍｍφ押出機により押出温度２３０
℃でガット状に押出しペレット化した。得られたペレッ
トは成形温度２３０℃、金型温度４０℃で射出成形し、
評価用の試験片を作成した。耐薬品性試験方法は射出成
形して得られたＵＬ試験片（米国燃焼性規格評価専用試
験片、幅約１３ｍｍ，長さ約１２６ｍｍ，厚さ約１．５
ｍｍ）を３０℃ＤＯＰ（フタル酸ジオクチル）中に２４
ｈｒ浸漬した後、取り出し、試験片の変質状況に応じ、
◎：変化無し，○：わずかに吸収，△：フクレあり，
×：著しいフクレありのように目視判定した。(Production of thermoplastic resin composition) 73 parts by weight of the copolymer prepared in Examples 1 to 10 and Comparative Examples 1 to 6, 27 parts by weight of the graft copolymer, and ethylene bisstearylamide 0 After kneading 0.8 parts by weight with a Henschel mixer, the extruder was heated at an extrusion temperature of 230 using a 40 mmφ extruder.
The mixture was extruded in the form of a gut at ℃ and pelletized. The obtained pellets were injection molded at a molding temperature of 230 ° C and a mold temperature of 40 ° C,
Test pieces for evaluation were prepared. The test method for chemical resistance is a UL test piece obtained by injection molding (a test piece for evaluating the US flammability standard, a width of about 13 mm, a length of about 126 mm, and a thickness of about 1.5.
mm) in 30 ° C. DOP (dioctyl phthalate).
After immersion for hrs, take out, and according to the deterioration condition of the test piece,
◎: No change, ○: Slight absorption, △: Swelling,
X: Visual determination was made as if there were significant blisters.
【００３５】メルトフローレート（以下ＭＦＲと略）
は、ＪＩＳ Ｋ ７２１０（日本工業規格：熱可塑性プ
ラスチックの流れ試験方法，Ｂ法）に準じ、温度２２０
℃、荷重１０ｋｇｆで行った。Melt flow rate (hereinafter abbreviated as MFR)
Is a temperature of 220 according to JIS K 7210 (Japanese Industrial Standard: Flow test method for thermoplastics, method B).
C. and a load of 10 kgf.
【００３６】以下、実施例および比較例を示す。なお、
表１、表２は実施例及び比較例の重合開始〜重合完了ま
での残存単量体中のシアン化ビニル系単量体成分割合の
経時変化（重合率換算）であり、図１はこれらをグラフ
化したものである。また、得られた共重合体および熱可
塑性樹脂組成物の諸物性値は表３にそれぞれ、総括記載
する。Hereinafter, examples and comparative examples will be described. In addition,
Tables 1 and 2 show the change over time (in terms of polymerization rate) of the ratio of the vinyl cyanide-based monomer component in the residual monomer from the start of polymerization to the completion of polymerization in Examples and Comparative Examples, and FIG. It is a graph. Table 3 summarizes various physical property values of the obtained copolymer and thermoplastic resin composition.
【００３７】実施例１ 容量が２０ｌで、バッフルおよびファウドラ型攪拌翼を
備えたステンレス製オートクレーブに、０．０５部のメ
タクリル酸メチル／アクリルアミド共重合体（特公昭４
５−２４１５１号公報記載）を１６５部のイオン交換水
に溶解した溶液を４００ｒｐｍで攪拌し、系内を窒素ガ
スで置換した。次に４２部のアクリロニトリル、４．Ｏ
部のスチレン、０．４６部のｔ−ドデシルメルカプタ
ン、０．３９部の２，２’−アゾビス（２，４−ジメチ
ルバレロニトリル），０．０５部の２，２’−アゾビス
イソブチルニトリルの混合溶液を反応系を攪拌しながら
添加し、５８℃にて共重合反応を開始した。重合開始か
ら１５分が経過した後オートクレーブ上部に備え付けた
供給ポンプから５４部のスチレンを１１０分かけて断続
添加した。この間、反応温度は重合開始時点の５８℃〜
６５℃まで昇温した。スチレンの反応系への断続添加が
終了した後、５０分かけて１００℃に昇温した。重合途
中の残存単量体中シアン化ビニル系単量体成分割合は図
１の通りである。以降は、通常の方法に従って、反応系
の冷却、ポリマーの分離、洗浄、乾燥を行って、ビーズ
状共重合体を得た。最終重合率は９５％、重合終了時の
残存単量体中シアン化ビニル系単量体成分割合は９０％
であった。 Example 1 In a stainless steel autoclave having a capacity of 20 l and equipped with a baffle and a Faudler type stirring blade, 0.05 part of a methyl methacrylate / acrylamide copolymer (Japanese Patent Publication No.
No. 5-24151) was dissolved in 165 parts of ion-exchanged water, stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, 42 parts of acrylonitrile; O
Parts of styrene, 0.46 parts of t-dodecyl mercaptan, 0.39 parts of 2,2'-azobis (2,4-dimethylvaleronitrile), 0.05 parts of 2,2'-azobisisobutylnitrile. The mixed solution was added while stirring the reaction system, and a copolymerization reaction was started at 58 ° C. After a lapse of 15 minutes from the start of the polymerization, 54 parts of styrene were intermittently added over 110 minutes from a feed pump provided at the top of the autoclave. During this period, the reaction temperature was 58 ° C.
The temperature was raised to 65 ° C. After the intermittent addition of styrene to the reaction system was completed, the temperature was raised to 100 ° C. over 50 minutes. The proportion of the vinyl cyanide monomer component in the remaining monomer during the polymerization is as shown in FIG. Thereafter, the reaction system was cooled, the polymer was separated, washed, and dried according to a conventional method to obtain a bead copolymer. The final polymerization rate is 95%, and the ratio of the vinyl cyanide monomer component in the residual monomer at the end of the polymerization is 90%.
Met.
【００３８】実施例２ 実施例１の条件のうち、 混合溶液：アクリロニトリル ２８部 スチレン １２部 ｔ−ドデシルメルカプタン ０．３３部 ２，２’−アゾビス（２，４−ジメチルバレロニトリル） ０部 ２，２’−アゾビスイソブチルニトリル ０．３２部 スチレンの追添加： ６０部 重合開始から追添加終了までの反応温度： ６５℃〜７３℃ とし、あとは実施例１と同様の方法で重合を行い、ビー
ズ状共重合体を得た。 Example 2 Among the conditions of Example 1, a mixed solution: acrylonitrile 28 parts styrene 12 parts t-dodecylmercaptan 0.33 parts 2,2'-azobis (2,4-dimethylvaleronitrile) 0 parts 2, 2′-azobisisobutylnitrile 0.32 parts Additional addition of styrene: 60 parts Reaction temperature from the start of polymerization to the end of additional addition: 65 ° C. to 73 ° C. After that, polymerization was carried out in the same manner as in Example 1, A beaded copolymer was obtained.
【００３９】実施例３ 実施例１の条件のうち、 混合溶液：アクリロニトリル ５０部 スチレン ４部 スチレンの追添加： ４６部 とし、あとは実施例１と同様の方法で重合を行い、ビー
ズ状共重合体を得た。 Example 3 Among the conditions of Example 1, the mixed solution was 50 parts of acrylonitrile, 4 parts of styrene, and the additional amount of styrene was 46 parts. After that, polymerization was carried out in the same manner as in Example 1 to obtain a beaded copolymer. A coalescence was obtained.
【００４０】実施例４ 実施例１の条件のうち、 混合溶液：アクリロニトリル ４２部 スチレン ４部 Ｎ−フェニルマレイミド ５部 スチレンの追添加： ４９部 とし、あとは実施例１と同様の方法で重合を行い、ビー
ズ状共重合体を得た。 Example 4 Among the conditions of Example 1, the mixed solution was 42 parts of acrylonitrile, 4 parts of styrene, 5 parts of N-phenylmaleimide, 5 parts of styrene was added, and the polymerization was carried out in the same manner as in Example 1. Then, a beaded copolymer was obtained.
【００４１】実施例５ 実施例１の条件のうち、 混合溶液：メタクリロニトリル ４２部 スチレン ４部 スチレンの追添加： ５４部 とし、あとは実施例１と同様の方法で重合を行い、ビー
ズ状共重合体を得た。 Example 5 Among the conditions of Example 1, the mixed solution was 42 parts of methacrylonitrile, 4 parts of styrene, and the additional amount of styrene was 54 parts. After that, polymerization was carried out in the same manner as in Example 1 to obtain beads. A copolymer was obtained.
【００４２】実施例６ 実施例２の条件のうち、 混合溶液：アクリロニトリル ３４部 α−メチルスチレン ９部 スチレンの追添加 ３９部 α−メチルスチレンの追添加： １８部 とし、あとは実施例２と同様の方法で重合を行い、ビー
ズ状共重合体を得た。 Example 6 Among the conditions of Example 2, mixed solution: acrylonitrile 34 parts α-methylstyrene 9 parts Styrene addition 39 parts α-methylstyrene addition: 18 parts Polymerization was carried out in the same manner to obtain a bead copolymer.
【００４３】実施例７ 実施例１の条件のうち、ｔ−ドデシルメルカプタンを
１．５部とし、あとは実施例１と同様の方法で重合を行
い、ビーズ状共重合体を得た。 Example 7 From the conditions of Example 1, 1.5 parts of t-dodecyl mercaptan was used, and the remainder was polymerized in the same manner as in Example 1 to obtain a bead copolymer.
【００４４】実施例８ 実施例１の条件のうち、ｔ−ドデシルメルカプタンを
０．３部とし、あとは実施例１と同様の方法で重合を行
い、ビーズ状共重合体を得た。 Example 8 Polymerization was carried out in the same manner as in Example 1 except that the amount of t-dodecyl mercaptan was changed to 0.3 part from the conditions of Example 1, and a bead-like copolymer was obtained.
【００４５】実施例９ 実施例１の条件のうち、 ２，２´−アゾビス（２，４−ジメチルバレロニトリル） ０．３９部 ２，２´−アゾビスイソブチロニトリル ０．０５部 を ｔ−ブチルパ−オキシピバレ−ト ０．４５部 とし、あとは実施例１と同様の方法で重合を行い、ビー
ズ状共重合体を得た。 Example 9 Of the conditions of Example 1, 0.39 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) 0.05 part of 2,2'-azobisisobutyronitrile was replaced by t -Butyl peroxypivalate was adjusted to 0.45 parts, and polymerization was carried out in the same manner as in Example 1 to obtain a bead copolymer.
【００４６】実施例１０ 実施例１の条件のうち、 メタクリル酸メチル／アクリルアミド共重合体 ０．０５部 を 硫酸バリウム １．００部 とし、あとは実施例１と同様の方法で重合を行い、ビー
ズ状共重合体を得た。 Example 10 Among the conditions of Example 1, 0.05 parts of methyl methacrylate / acrylamide copolymer was changed to 1.00 part of barium sulfate, and polymerization was carried out in the same manner as in Example 1 to obtain beads. A copolymer was obtained.
【００４７】比較例１ 実施例２の条件のうち、 混合溶液：アクリロニトリル ２４部 スチレン ７６部 スチレンの追添加： ０部 とし、あとは実施例２と同様の方法で重合を行い、ビー
ズ状共重合体を得た。 Comparative Example 1 Among the conditions of Example 2, mixed solution: acrylonitrile 24 parts Styrene 76 parts Styrene additional addition: 0 parts, polymerization was carried out in the same manner as in Example 2, and bead-shaped copolymerization was carried out. A coalescence was obtained.
【００４８】比較例２ 実施例１の条件のうち、 混合溶液：アクリロニトリル ４２部 スチレン ３部 スチレンの追添加： ５５部 とし、あとは実施例１と同様の方法で重合を行い、ビー
ズ状共重合体を得た。 Comparative Example 2 Among the conditions of Example 1, the mixed solution was 42 parts of acrylonitrile, 3 parts of styrene, and the addition of styrene was 55 parts. Thereafter, polymerization was carried out in the same manner as in Example 1 to obtain a bead-like copolymer. A coalescence was obtained.
【００４９】比較例３ 公知の塊状重合装置を用いてスチレン６２部、アクリロ
ニトリル３８部、トルエン１０部、Ｎ−オクチルメルカ
プタン０．２部、ｔ−ブチルパーオキサイド０．０１部
からなる混合物を重合槽に連続的に供給し重合率７５％
で脱モノマし、見掛上の重合率を９９％以上にして重合
を完結させ、共重合体を得た。 Comparative Example 3 A mixture comprising 62 parts of styrene, 38 parts of acrylonitrile, 10 parts of toluene, 0.2 part of N-octyl mercaptan and 0.01 part of t-butyl peroxide was prepared using a known bulk polymerization apparatus. 75% polymerization rate
And the polymerization was completed by setting the apparent polymerization rate to 99% or more to obtain a copolymer.
【００５０】比較例４ 特公昭４６−２７８０８公報中の実施例１に基づいて重
合を行った。重合率は９０％、重合終了時の残存単量体
中シアン化ビニル系単量体成分割合は５０重量％であっ
た。重合開始から重合完了までの残存単量体中シアン化
ビニル系単量体成分割合は図１の通りである。比粘度は
０．３５４（ηsp/c＝０．８９dl/g，メチルエチルケト
ン０．４重量％溶液，３０℃）、共重合体中のシアン化
ビニル系単量体成分割合は２９重量％であった。 Comparative Example 4 Polymerization was carried out according to Example 1 in JP-B-46-27808. The polymerization rate was 90%, and the ratio of the vinyl cyanide-based monomer component in the residual monomer at the end of the polymerization was 50% by weight. The ratio of the vinyl cyanide monomer component in the remaining monomer from the start of the polymerization to the completion of the polymerization is as shown in FIG. The specific viscosity was 0.354 (ηsp / c = 0.89 dl / g, 0.4% by weight solution of methyl ethyl ketone, 30 ° C.), and the ratio of the vinyl cyanide monomer component in the copolymer was 29% by weight. .
【００５１】比較例５ 特開昭５０−３３９１７公報中の実施例４に基づいて重
合を行った。懸濁重合終了時重合率は９９％、重合終了
時の残存単量体中シアン化ビニル系単量体成分割合は６
７重量％であった。重合開始から重合完了までの残存単
量体中シアン化ビニル系単量体成分割合は図１の通りで
ある。ηsp/cは０．７８dl/g，メチルエチルケトン０．
４重量％溶液，３０℃）、共重合体中のシアン化ビニル
系単量体成分割合は２９重量％であった。 Comparative Example 5 Polymerization was carried out based on Example 4 in JP-A-50-33917. At the end of the suspension polymerization, the polymerization rate is 99%, and at the end of the polymerization, the ratio of the vinyl cyanide monomer component to the remaining monomer is 6%.
7% by weight. The ratio of the vinyl cyanide monomer component in the remaining monomer from the start of the polymerization to the completion of the polymerization is as shown in FIG. ηsp / c is 0.78 dl / g, methyl ethyl ketone 0.
(4% by weight solution, 30 ° C.), and the ratio of the vinyl cyanide monomer component in the copolymer was 29% by weight.
【００５２】比較例６ 特開平３−２２７３０６中の実施例１に基づいて重合を
行った。懸濁重合終了時重合率は７３％、重合終了時の
残存単量体中シアン化ビニル系単量体成分割合は９７重
量％であった。重合開始から重合完了までの残存単量体
中シアン化ビニル系単量体成分割合は図１の通りであ
る。ηsp/cは０．５０dl/g，メチルエチルケトン０．４
重量％溶液，３０℃）、共重合体中のシアン化ビニル系
単量体成分割合は７０重量％であった。 Comparative Example 6 Polymerization was carried out based on Example 1 in JP-A-3-227306. At the end of the suspension polymerization, the polymerization rate was 73%, and the ratio of the vinyl cyanide-based monomer component to the remaining monomers at the end of the polymerization was 97% by weight. The ratio of the vinyl cyanide monomer component in the remaining monomer from the start of the polymerization to the completion of the polymerization is as shown in FIG. ηsp / c is 0.50 dl / g, methyl ethyl ketone 0.4
Wt% solution, 30 ° C.), and the ratio of the vinyl cyanide monomer component in the copolymer was 70% by weight.
【００５３】まず、本発明の高ニトリル含有ビニル系共
重合体について、実施例と比較例との差異について説明
する。実施例１〜３から、本発明の請求項記載の共重合
体組成範囲内にある共重合体が、樹脂溶解時の熱着色安
定性および耐薬品性に優れていることが判る。実施例４
から共重合可能な他のビニル系単量体を構成成分とした
場合にも同様の効果が得られることが判る。実施例５、
６からアクリロニトリルおよびスチレン以外のシアン化
ビニル系単量体および芳香族ビニル系単量体を１種また
は２種以上構成単位とした場合にも同様の効果が得られ
ることが判る。しかし、比較例１および６の共重合体
は、本発明の請求項記載の共重合体組成範囲外であるた
めに、比較例１は耐薬品性に劣り、比較例６は、樹脂溶
融時の熱着色安定性に劣る。実施例１、７および８から
は、本発明の請求項記載のηsp/c範囲内にある共重合体
が、樹脂溶融時の熱着色安定性および耐薬品性に優れて
いることが判る。比較例３は、共重合体中のオリゴマー
割合が０．６重量％を越えている。故に実施例に比べ、
比較例３の共重合体を用いた樹脂組成物の成形時、金型
の汚れが著しく、成形加工上実用的ではない。First, the difference between the Examples and Comparative Examples of the high nitrile-containing vinyl copolymer of the present invention will be described. From Examples 1 to 3, it can be seen that the copolymer within the copolymer composition range described in the claims of the present invention is excellent in thermal coloring stability and chemical resistance when the resin is dissolved. Example 4
From this, it can be seen that the same effect can be obtained when another copolymerizable vinyl monomer is used as a component. Example 5,
6 shows that the same effect can be obtained when one or more vinyl cyanide-based monomers and aromatic vinyl-based monomers other than acrylonitrile and styrene are used as constituent units. However, since the copolymers of Comparative Examples 1 and 6 were out of the copolymer composition range described in the claims of the present invention, Comparative Example 1 was inferior in chemical resistance, and Comparative Example 6 was Poor thermal coloring stability. From Examples 1, 7 and 8, it can be seen that the copolymer within the ηsp / c range described in the claims of the present invention has excellent thermal coloring stability and chemical resistance when the resin is melted. In Comparative Example 3, the oligomer ratio in the copolymer exceeded 0.6% by weight. Therefore, compared to the embodiment,
At the time of molding the resin composition using the copolymer of Comparative Example 3, the mold was significantly stained, which was not practical for molding.
【００５４】次に、本発明の高ニトリル含有ビニル系共
重合体の製造方法について、実施例と比較例との差異に
ついて説明する。実施例１〜１０から、本発明の請求項
記載の製造方法範囲内で製造された共重合体が、樹脂溶
融時の熱着色安定性および耐薬品性に優れていることが
判る。実施例１〜６および９は、単量体構成単位、重合
開始剤種および量を変更したものである。実施例７およ
び８は、連鎖移動剤量を可変させてηsp/cを変更したも
の、実施例１０は懸濁安定剤種を無機懸濁安定剤に変更
したものである。Next, the method for producing the vinyl copolymer having a high nitrile content of the present invention will be described with reference to differences between the examples and the comparative examples. Examples 1 to 10 show that the copolymers produced within the scope of the production method described in the claims of the present invention have excellent thermal coloring stability and chemical resistance when the resin is melted. In Examples 1 to 6 and 9, the monomer constitutional unit, the type and the amount of the polymerization initiator were changed. In Examples 7 and 8, ηsp / c was changed by changing the amount of the chain transfer agent. In Example 10, the type of suspension stabilizer was changed to an inorganic suspension stabilizer.
【００５５】比較例１は重合開始から重合率１０％経過
時点までの残存単量体中シアン化ビニル系単量体成分割
合が７０重量％未満であるため、実施例に比べ耐薬品性
に劣っている。比較例２は重合開始から重合完了までの
残存単量体中シアン化ビニル系単量体成分割合が９５重
量％以上であるために、シアン化ビニル系単量体の３連
シーケンスの割合が１０重量％を越え、実施例に比べ樹
脂熱処理後のＹＩ値が著しく高く、樹脂溶融時の熱着色
安定性に劣っている。比較例３は、塊状重合方式にて重
合を行なったため、共重合体中のオリゴマー割合が０．
６重量％を越えている。故に実施例に比べ、比較例３の
共重合体を用いた樹脂組成物の成形時、金型の汚れが著
しく、成形加工上実用的ではない。比較例４は比較例１
と同様に、重合開始から重合率１０％経過時点までの残
存単量体中シアン化ビニル系単量体成分割合が７０重量
％未満であるため、実施例に比べ耐薬品性に劣ってい
る。また、共重合体のηsp/cが０．８０dl/gを越えてい
るため、実施例に比べＭＦＲが著しく低く、成形加工性
に劣っている。比較例５は比較例１と同様に、重合開始
から重合率１０％経過時点までの残存単量体中シアン化
ビニル系単量体成分割合が７０重量％未満であるため、
実施例に比べ耐薬品性に劣っている。比較例６は比較例
２と同様に、重合開始から重合完了までの残存単量体中
シアン化ビニル系単量体成分割合が９５重量％以上であ
るために、シアン化ビニル系単量体の３連シーケンスの
割合が１０重量％を越え、実施例に比べ樹脂熱処理後の
ＹＩ値が著しく高く、樹脂溶融時の熱着色安定性に劣っ
ている。Comparative Example 1 was inferior in chemical resistance as compared with the Examples since the ratio of the vinyl cyanide monomer component in the residual monomer from the start of polymerization to the point of the polymerization rate of 10% was less than 70% by weight. ing. In Comparative Example 2, since the ratio of the vinyl cyanide monomer component in the residual monomer from the start of the polymerization to the completion of the polymerization was 95% by weight or more, the ratio of the triple sequence of the vinyl cyanide monomer was 10%. %, The YI value after heat treatment of the resin is remarkably high and the thermal coloring stability at the time of melting the resin is inferior to that of the examples. In Comparative Example 3, since the polymerization was carried out by the bulk polymerization method, the oligomer ratio in the copolymer was 0.1%.
It exceeds 6% by weight. Therefore, when the resin composition using the copolymer of Comparative Example 3 is molded as compared with the examples, the mold is significantly stained, which is not practical for molding. Comparative Example 4 is Comparative Example 1
Similarly to the above, since the ratio of the vinyl cyanide-based monomer component in the residual monomer from the start of polymerization to the point when the polymerization rate has passed 10% is less than 70% by weight, the chemical resistance is inferior to the examples. Further, since ηsp / c of the copolymer exceeds 0.80 dl / g, the MFR is remarkably low as compared with the examples, and the molding processability is poor. In Comparative Example 5, as in Comparative Example 1, the proportion of the vinyl cyanide-based monomer component in the residual monomer from the start of the polymerization to the point at which the polymerization rate passed by 10% was less than 70% by weight.
It is inferior in chemical resistance as compared with the examples. In Comparative Example 6, as in Comparative Example 2, since the ratio of the vinyl cyanide-based monomer component in the residual monomer from the start of the polymerization to the completion of the polymerization was 95% by weight or more, the amount of the vinyl cyanide-based monomer was The ratio of the triple sequence exceeds 10% by weight, the YI value after heat treatment of the resin is remarkably high, and the thermal coloring stability at the time of melting the resin is inferior to the examples.
【００５６】実施例、および比較例より次のことが明ら
かである。すなわち、本発明により得られた共重合体を
使用した樹脂組成物は、成形加工性はもとより、金型汚
れが少なく、耐薬品性に優れかつ溶融時の熱着色安定性
が優れている。これは、重合中の残存単量体中シアン化
ビニル系単量体成分割合を制御して水系懸濁重合するこ
とによって、３連シーケンス割合が一定値以下でオリゴ
マー量の少ない新規な共重合体を使用することにより初
めて実現されるものである。The following is clear from the examples and comparative examples. That is, the resin composition using the copolymer obtained by the present invention has not only moldability but also less mold stain, excellent chemical resistance, and excellent thermal coloring stability during melting. This is a novel copolymer having a tri-sequence ratio of less than a certain value and a small amount of oligomer by controlling the ratio of vinyl cyanide monomer component in the residual monomer during polymerization and conducting aqueous suspension polymerization. This is realized for the first time by using.
【００５７】[0057]
【表１】 [Table 1]
【表２】 [Table 2]
【表３】 [Table 3]
【００５８】[0058]
【発明の効果】本発明の高ニトリル含有ビニル系共重合
体は、シアン化ビニル系単量体を高い割合で含有し、オ
リゴマー量が少なく、かつシアン化ビニル単量体成分の
３連シーケンス割合が非常に少ないため、金型汚れが少
なく、溶融時の熱着色安定性が良好で、かつ耐薬品性に
もすぐれている。また本発明の製造方法は、水系懸濁重
合法により重合開始〜重合終了までの残存単量体中シア
ン化ビニル単量体成分割合を一定割合以下に制御しつ
つ、重合前半の残存単量体中シアン化ビニル単量体成分
割合を高い割合に維持する点が特徴である。これにより
初めて前述の高ニトリル含有ビニル系共重合体を製造す
ることができる。また本発明の高ニトリル含有ビニル系
共重合体は、ゴム成分をブレンド・溶融混合することに
より耐衝撃性熱可塑性樹脂組成物として、耐薬品性・耐
衝撃性を必要とする種々の成形加工用途に供され、特に
電気冷蔵庫用樹脂材料として好適である。The high nitrile-containing vinyl copolymer of the present invention contains a high proportion of a vinyl cyanide monomer, has a low oligomer amount, and has a triple sequence ratio of a vinyl cyanide monomer component. Is extremely small, so that mold stains are small, thermal coloring stability during melting is good, and chemical resistance is also excellent. Further, the production method of the present invention is an aqueous suspension polymerization method, while controlling the vinyl cyanide monomer component ratio in the residual monomer from the start of polymerization to the end of polymerization to a certain ratio or less, the remaining monomer in the first half of the polymerization The feature is that the ratio of the vinyl cyanide monomer component is maintained at a high ratio. Thereby, the above-mentioned high nitrile-containing vinyl copolymer can be produced for the first time. Further, the high nitrile-containing vinyl copolymer of the present invention can be used in various molding applications requiring chemical resistance and impact resistance as an impact-resistant thermoplastic resin composition by blending and melt-mixing a rubber component. And is particularly suitable as a resin material for electric refrigerators.
【図１】 実施例および比較例について、重合開始〜重
合完了までの残存単量体中のシアン化ビニル系単量体成
分割合の経時変化を重合率換算しグラフ化したものであ
る。BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a graph showing the change with time of the ratio of a vinyl cyanide-based monomer component in a residual monomer from the start of polymerization to the completion of polymerization in Examples and Comparative Examples in terms of polymerization rate.
Claims (8)
重量％，芳香族ビニル系単量体（Ｂ）７５〜４５重量％
およびこれらと共重合可能な他のビニル系単量体（Ｃ）
０〜２０重量％を構成単位とする共重合体であって、シ
アン化ビニル系単量体の３連シーケンスの割合が該共重
合体中１０重量％以下であることを特徴とする高ニトリ
ル含有ビニル系共重合体。1. A vinyl cyanide monomer (A) 25 to 55.
% By weight, 75 to 45% by weight of an aromatic vinyl monomer (B)
And other vinyl monomers copolymerizable therewith (C)
A copolymer containing 0 to 20% by weight of a structural unit, wherein the ratio of a triple sequence of a vinyl cyanide monomer is 10% by weight or less in the copolymer. Vinyl copolymer.
の割合が該共重合体中８重量％以下であることを特徴と
する請求項１記載の高ニトリル含有ビニル系共重合体。2. The high nitrile-containing vinyl copolymer according to claim 1, wherein the ratio of the triple sequence of the vinyl cyanide monomer is 8% by weight or less in the copolymer.
重量％，芳香族ビニル系単量体（Ｂ）７０〜５５重量％
（Ｂ）およびこれらと共重合可能な他のビニル系単量体
（Ｃ）０〜２０重量％を構成単位とする共重合体である
請求項１または２記載の高ニトリル含有ビニル系共重合
体。3. A vinyl cyanide monomer (A) 30 to 45.
% By weight, 70 to 55% by weight of an aromatic vinyl monomer (B)
The high nitrile-containing vinyl copolymer according to claim 1 or 2, which is a copolymer containing (B) and another vinyl monomer (C) copolymerizable therewith in an amount of 0 to 20% by weight. .
０ｄｌ／ｇであることを特徴とする請求項１、２または
３記載の高ニトリル含有ビニル系共重合体。4. A copolymer having a reduced viscosity of 0.20 to 0.8.
4. The high nitrile-containing vinyl copolymer according to claim 1, wherein the copolymer is 0 dl / g.
％以下であることを特徴とする請求項１、２、３または
４記載の高ニトリル含有ビニル系共重合体。5. The high nitrile-containing vinyl copolymer according to claim 1, wherein the proportion of the oligomer in the copolymer is 0.6% by weight or less.
％，芳香族ビニル系単量体７５〜４５重量％およびこれ
らと共重合可能な他のビニル系単量体０〜２０重量％か
らなる単量体を重合するに際し、重合開始から重合終了
までの残存単量体中のシアン化ビニル系単量体成分割合
を９５重量％以下にし、かつ重合開始から少なくとも重
合率１０％経過時点までの残存単量体中のシアン化ビニ
ル系単量体成分割合を７０重量％以上９５重量％以下に
して水系懸濁重合することを特徴とする請求項１〜５の
いずれかに記載の高ニトリル含有ビニル系共重合体の製
造方法。6. A method comprising 25 to 55% by weight of a vinyl cyanide monomer, 75 to 45% by weight of an aromatic vinyl monomer and 0 to 20% by weight of another vinyl monomer copolymerizable therewith. In the polymerization of the resulting monomer, the proportion of the vinyl cyanide monomer component in the residual monomer from the start of the polymerization to the end of the polymerization is set to 95% by weight or less, and from the start of the polymerization to at least 10% of the polymerization rate. The aqueous suspension polymerization according to claim 1, wherein the proportion of the vinyl cyanide-based monomer component in the remaining monomer is 70% by weight or more and 95% by weight or less .
The method for producing a high nitrile-containing vinyl copolymer according to any one of the above .
ことを特徴とする、請求項６記載の高ニトリル含有ビニ
ル系共重合体の製造方法。7. The process for producing a high nitrile-containing vinyl copolymer according to claim 6, wherein an azo polymerization initiator is used as the polymerization initiator.
ることを特徴とする請求項６または７記載の高ニトリル
含有ビニル系共重合体の製造方法。8. The process for producing a high nitrile-containing vinyl copolymer according to claim 6, wherein an organic polymer compound is used as the dispersion stabilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06264241A JP3141707B2 (en) | 1994-10-27 | 1994-10-27 | High nitrile-containing vinyl copolymer and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06264241A JP3141707B2 (en) | 1994-10-27 | 1994-10-27 | High nitrile-containing vinyl copolymer and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08127626A JPH08127626A (en) | 1996-05-21 |
| JP3141707B2 true JP3141707B2 (en) | 2001-03-05 |
Family
ID=17400453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06264241A Expired - Fee Related JP3141707B2 (en) | 1994-10-27 | 1994-10-27 | High nitrile-containing vinyl copolymer and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3141707B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015004144A (en) * | 2013-06-21 | 2015-01-08 | ユニチカ株式会社 | Printed laminated nonwoven fabric |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010100240A (en) * | 2000-03-23 | 2001-11-14 | 히라이 가쯔히꼬 | Thermoplastic resin composition and its extrusion moldings |
| JP2005062305A (en) * | 2003-08-08 | 2005-03-10 | Fuji Xerox Co Ltd | Method of manufacturing particle for display device, particle for the display device, and image display medium using the same and image forming device |
| JP6151638B2 (en) * | 2010-05-13 | 2017-06-21 | ダウ グローバル テクノロジーズ エルエルシー | Styrene-acrylonitrile copolymer foam with minimal yellowing |
| JP2012177088A (en) * | 2011-02-04 | 2012-09-13 | Toray Ind Inc | Thermoplastic resin composition, and molding thereof |
-
1994
- 1994-10-27 JP JP06264241A patent/JP3141707B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015004144A (en) * | 2013-06-21 | 2015-01-08 | ユニチカ株式会社 | Printed laminated nonwoven fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08127626A (en) | 1996-05-21 |
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