JP2016155944A - Styrene resin composition and molding prepared therewith - Google Patents
Styrene resin composition and molding prepared therewith Download PDFInfo
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本発明はスチレン系樹脂組成物およびそれからなる成形品に関するものである。 The present invention relates to a styrenic resin composition and a molded article comprising the same.
スチレン系樹脂はその優れた成形性性を生かし、ワープロ、パーソナルコンピュータ、プリンター、複写機等のＯＡ機器、ＴＶ、オーディオ等の家電等多くの製品に使用されてきた。中でも大型機器では、内部機構の大型／複雑化と共に放熱が大きくなるため、より高度な耐熱性が要求される。更に近年、成形体の薄肉／軽量化の要求がまずます強くなり、流動性と耐熱性をより高度にバランスする材料が求められている。 Styrene-based resins have been used in many products such as word processors, personal computers, OA equipment such as printers, copiers, and home appliances such as TVs and audios, taking advantage of their excellent moldability. In particular, large-scale equipment requires higher heat resistance because heat dissipation increases as the internal mechanism becomes larger / complex. Furthermore, in recent years, the demand for thin / lightweight molded articles has become increasingly strong, and materials that have a higher balance between fluidity and heat resistance have been demanded.
本発明は、ゴム変性スチレン系樹脂に特定のスチレン系樹脂組成物を希釈し、スチレン系樹脂組成物およびそれからなる成形体を提供する。 The present invention provides a styrene resin composition and a molded article comprising the same by diluting a rubber-modified styrene resin with a specific styrene resin composition.
本発明者は、（Ａ）ゴム変性スチレン系樹脂に（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂を有するスチレン系樹脂組成物とする事により本発明を完成させた。 The present inventor makes (A) a rubber-modified styrene resin with a styrene resin composition having (B) a styrene resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component amount of 2.0% by mass or less. This completes the present invention.
また、本発明は上記スチレン系樹脂組成物を射出成形して得られる成形体を提供する。 Moreover, this invention provides the molded object obtained by injection-molding the said styrene resin composition.
本発明によれば、ゴム変性スチレン系樹脂に特定のスチレン系樹脂組成物を希釈して用いることで、スチレン系樹脂組成物を提供することができる According to the present invention, a styrene resin composition can be provided by diluting and using a specific styrene resin composition in a rubber-modified styrene resin.
本発明において使用する（Ａ）ゴム変性スチレン系樹脂とは、芳香族ビニル化合物系単量体を重合したものにゴム状重合体を加えてゴム変性を行ったものである。重合方法としては公知の方法、例えば、塊状重合法、塊状・懸濁二段重合法、溶液重合法等により製造することができる。芳香族ビニル化合物系単量体は、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン等の公知のものが使用できるが、好ましくはスチレンである。また、これらの芳香族ビニル化合物系単量体と共重合可能なアクリロニトリル、（メタ）アクリル酸、（メタ）アクリル酸エステル等のスチレン系単量体や無水マレイン酸等以外の単量体も、樹脂組成物の性能を損なわない程度のものであれば良い。さらに本発明ではジビニルベンゼン等の架橋剤をスチレン系単量体に対し添加して重合したものであっても差し支えない。 The (A) rubber-modified styrene resin used in the present invention is a rubber-modified styrene resin obtained by polymerizing an aromatic vinyl compound monomer and adding a rubber-like polymer. As the polymerization method, it can be produced by a known method, for example, a bulk polymerization method, a bulk / suspension two-stage polymerization method, a solution polymerization method or the like. As the aromatic vinyl compound monomer, known monomers such as styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene can be used, and styrene is preferable. In addition, monomers other than styrene-based monomers such as acrylonitrile, (meth) acrylic acid, (meth) acrylic acid ester and maleic anhydride which can be copolymerized with these aromatic vinyl compound-based monomers, What is necessary is just a grade which does not impair the performance of a resin composition. Furthermore, in the present invention, a polymer obtained by adding a crosslinking agent such as divinylbenzene to a styrene monomer may be used.
本発明の（Ａ）ゴム変性スチレン系樹脂のゴム変性に用いるゴム状重合体としては、ポリブタジエン、スチレン−ブタジエンのランダムまたはブロック共重合体、ポリイソプレン、ポリクロロプレン、スチレン−イソプレンのランダム、ブロック又はグラフト共重合体、エチレン−プロピレンゴム、エチレン−プロピレン−ジエンゴムなどが挙げられるが、特にポリブタジエン、スチレン−ブタジエンのランダム、ブロック又はグラフト共重合体が好ましい。また、これらは一部水素添加されていても差し支えない。 As the rubber-like polymer used for rubber modification of the rubber-modified styrene resin of the present invention, polybutadiene, styrene-butadiene random or block copolymer, polyisoprene, polychloroprene, styrene-isoprene random, block or Graft copolymers, ethylene-propylene rubbers, ethylene-propylene-diene rubbers and the like can be mentioned. Random, block or graft copolymers of polybutadiene and styrene-butadiene are particularly preferable. These may be partially hydrogenated.
このような（Ａ）ゴム変性スチレン系樹脂の例として、耐衝撃性ポリスチレン（ＨＩＰＳ）、ＡＢＳ樹脂（アクリロニトリル−ブタジエン−スチレン共重合体）、ＡＡＳ樹脂（アクリロニトリル−アクリルゴム−スチレン共重合体）、ＡＥＳ樹脂（アクリロニトリル−エチレンプロピレン−スチレン共重合体）、ＭＢＳ樹脂（メチルメタクリレート−ブタジエン−スチレン共重合体）等が挙げられる。 Examples of such (A) rubber-modified styrene resin include impact polystyrene (HIPS), ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylenepropylene-styrene copolymer), MBS resin (methyl methacrylate-butadiene-styrene copolymer) and the like can be mentioned.
（Ａ）ゴム変性スチレン系樹脂中の芳香族ビニル重合体の分子量については特に制限はないが、還元粘度(ηｓｐ／Ｃ)で０．５〜１．０が好ましい。１．０を超えると、スチレン系樹脂組成物とした際の流動性が低く過ぎて成形に支障をきたし、０．５未満だと実用的に十分な強度が発揮できない等の問題がある。 (A) Although there is no restriction | limiting in particular about the molecular weight of the aromatic vinyl polymer in rubber-modified styrene resin, 0.5-1.0 are preferable at a reduced viscosity ((eta) sp / C). If it exceeds 1.0, the fluidity of the styrenic resin composition is so low that it hinders molding, and if it is less than 0.5, there is a problem that practically sufficient strength cannot be exhibited.
（Ａ）ゴム変性スチレン系樹脂中のゴム状重合体の含有量については特に制限はないが、３〜１０質量％が好ましい。ゴム状重合体の含有量が３質量％未満だと樹脂組成物の耐衝撃性が低下しやすくなり、１０質量％を超えると樹脂組成物の耐熱性が低下しやすくなる。 (A) Although there is no restriction | limiting in particular about content of the rubber-like polymer in rubber-modified styrene-type resin, 3-10 mass% is preferable. When the content of the rubber-like polymer is less than 3% by mass, the impact resistance of the resin composition tends to decrease, and when it exceeds 10% by mass, the heat resistance of the resin composition tends to decrease.
（Ａ）ゴム変性スチレン系樹脂中のゴム状重合体の平均粒子径については特に制限はないが、０．４〜５．０μｍ質量％が好ましく、特に好ましくは１．０〜４．０μｍ質量％が好ましい。ゴム状重合体の平均粒子径が０．４μｍ未満だと耐衝撃性が得られず、５．０μｍを超えても耐衝撃性は低下する。 (A) Although there is no restriction | limiting in particular about the average particle diameter of the rubber-like polymer in rubber-modified styrene resin, 0.4-5.0 micrometers mass% is preferable, Especially preferably, 1.0-4.0 micrometers mass% Is preferred. If the average particle diameter of the rubbery polymer is less than 0.4 μm, impact resistance cannot be obtained, and even if it exceeds 5.0 μm, the impact resistance decreases.
本発明において使用する（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂とは、芳香族ビニル化合物系単量体を重合して得られるものであり、ゴム状重合体を含まないものである。重合方法としては公知の方法、例えば、塊状重合法、塊状・懸濁二段重合法、溶液重合法等により製造することができる。芳香族ビニル化合物系単量体は、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン等の公知のものが使用できるが、好ましくはスチレンである。また、これらの芳香族ビニル化合物系単量体と共重合可能なアクリロニトリル、（メタ）アクリル酸、（メタ）アクリル酸エステル等のスチレン系単量体や無水マレイン酸等以外の単量体も、樹脂組成物の性能を損なわない程度であれば良い。さらに本発明ではジビニルベンゼン等の架橋剤をスチレン系単量体に対し添加して重合したものであっても差し支えない。 The (B) styrene resin having a weight average molecular weight of 180,000 or less and a methanol soluble component amount of 2.0% by mass or less used in the present invention is obtained by polymerizing an aromatic vinyl compound monomer. And does not contain a rubbery polymer. As the polymerization method, it can be produced by a known method, for example, a bulk polymerization method, a bulk / suspension two-stage polymerization method, a solution polymerization method or the like. As the aromatic vinyl compound monomer, known monomers such as styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene can be used, and styrene is preferable. In addition, monomers other than styrene-based monomers such as acrylonitrile, (meth) acrylic acid, (meth) acrylic acid ester and maleic anhydride which can be copolymerized with these aromatic vinyl compound-based monomers, What is necessary is just a grade which does not impair the performance of a resin composition. Furthermore, in the present invention, a polymer obtained by adding a crosslinking agent such as divinylbenzene to a styrene monomer may be used.
このような（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂の例として、ポリスチレン（ＧＰＰＳ）、ＡＳ樹脂（アクリロニトリル−スチレン共重合体）、ＭＳ樹脂（メチルメタクリレート−スチレン共重合体）等が挙げられる。 Examples of such (B) styrene resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component amount of 2.0% by mass or less include polystyrene (GPPS), AS resin (acrylonitrile-styrene copolymer), MS resin (methyl methacrylate-styrene copolymer) and the like can be mentioned.
（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂中の芳香族ビニル重合体の分子量については重量平均分子量１８万以下であり、望ましくは１６万以下、更には１０万〜１６万が好ましい。１８万を超えると、希釈した際の流動性が低すぎて成形に支障をきたし、１０万未満だと実用的に充分な強度が発揮できない等の問題がある。 (B) The molecular weight of the aromatic vinyl polymer in the styrene resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component amount of 2.0% by mass or less is 180,000 or less, preferably 16 10,000 or less, and more preferably 100,000 to 160,000. If it exceeds 180,000, the fluidity at the time of dilution is too low to hinder molding, and if it is less than 100,000, practically sufficient strength cannot be exhibited.
（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂中のメタノール可溶成分量とは樹脂中の低分子量成分の含有量であり、２．０質量％以下、望ましくは１．６質量％以下が好ましい。２．０質量％を超えると、充分な耐熱性が得られず、また揮発成分の金型付着が増加し成形サイクルの悪化につながる等の問題がある。 (B) The amount of methanol soluble component in a styrene resin having a weight average molecular weight of 180,000 or less and a methanol soluble component amount of 2.0% by mass or less is the content of low molecular weight components in the resin. 0 mass% or less, desirably 1.6 mass% or less is preferable. If it exceeds 2.0% by mass, there is a problem that sufficient heat resistance cannot be obtained, and adhesion of the volatile component to the mold increases, leading to deterioration of the molding cycle.
（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂の添加量については、望ましくは１〜４０質量部、更には１〜３０質量部が好ましい。このとき（Ａ）ゴム変性スチレン系樹脂と（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂の合計を１００質量部とする。（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂が４０質量部を超えるとゴム含有量が少なくなり実用的に充分な強度が発揮できず、１質量部未満だと希釈の効果が得られない。 (B) The addition amount of the styrene resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component amount of 2.0% by mass or less is preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass. . At this time, the total of (A) the rubber-modified styrene resin and (B) the styrene resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component amount of 2.0% by mass or less is 100 parts by mass. (B) When the styrene resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component content of 2.0% by mass or less exceeds 40 parts by mass, the rubber content decreases and practically sufficient strength cannot be exhibited. If it is less than 1 part by mass, the effect of dilution cannot be obtained.
本発明の（Ｃ）ポリフェニレンエーテル系樹脂とは、下記化１に示す構造単位を主鎖に有する重合体であって、単独重合体又は共重合体のいずれでもよい。 The (C) polyphenylene ether resin of the present invention is a polymer having a structural unit represented by the following chemical formula 1 in the main chain, and may be either a homopolymer or a copolymer.
（Ｃ）ポリフェニレンエーテル系樹脂の単独重合体の代表例としては、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−エチル−１，４−フェニレン）エーテル、ポリ（２，６−ジエチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２，６−ジ−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ｎ−ブチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−イソプロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ヒドロキシエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル等が挙げられる。共重合体の例としては、２，６−ジメチルフェノール／２，３，６−トリメチルフェノール共重合体、２，６−ジメチルフェノール／２，３，６−トリエチルフェノール共重合体、２，６−ジエチルフェノール／２，３，６−トリメチルフェノール共重合体、２，６−ジプロピルフェノール／２，３，６−トリメチルフェノール共重合体等の２，６−ジアルキルフェノール／２，３，６−トリアルキルフェノール共重合体、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）にスチレンをグラフト重合させたグラフト共重合体、２，６−ジメチルフェノール／２，３，６−トリメチルフェノール共重合体にスチレンをグラフト重合させたグラフト共重合体等が挙げられる。 (C) Typical examples of homopolymers of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,4-phenylene) ether. Poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1) , 4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl) -6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1, - phenylene) ether. Examples of the copolymer include 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6- 2,6-dialkylphenol / 2,3,6-trimethyl such as diethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer Alkylphenol copolymer, graft copolymer obtained by graft polymerization of styrene to poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer And graft copolymers obtained by graft polymerization of styrene.
（Ｃ）ポリフェニレンエーテル系樹脂として、好ましくは、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、２，６−ジメチルフェノール／２，３，６−トリメチルフェノールランダム共重合体であり、特に好ましくはポリ（２，６−ジメチル−１，４−フェニレン）エーテルである。 (C) The polyphenylene ether-based resin is preferably poly (2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol random copolymer, Particularly preferred is poly (2,6-dimethyl-1,4-phenylene) ether.
（Ｃ）ポリフェニレンエーテル系樹脂の極限粘度について特に制限はないが、クロロホルム中で測定した３０℃の極限粘度が望ましくは０．２〜０．８ｄｌ／ｇ、更に好ましくは０．３〜０．６ｄｌ／ｇである。（Ｃ）ポリフェニレンエーテル系樹脂の極限粘度が０．２ｄｌ／ｇ未満だと成形体の機械的強度が低下し、また、０．８ｄｌ／ｇを超えると成形性が悪化するため好ましくない。 (C) The intrinsic viscosity of the polyphenylene ether resin is not particularly limited, but the intrinsic viscosity at 30 ° C. measured in chloroform is preferably 0.2 to 0.8 dl / g, more preferably 0.3 to 0.6 dl. / G. (C) If the intrinsic viscosity of the polyphenylene ether-based resin is less than 0.2 dl / g, the mechanical strength of the molded product is lowered, and if it exceeds 0.8 dl / g, the moldability deteriorates, which is not preferable.
（Ｃ）ポリフェニレンエーテル樹脂の添加量について特に制限はないが、（Ａ）ゴム変性スチレン系樹脂と（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂の合計量に対して５０質量部以下とすることが望ましい。５０質量部を超える量を添加すると成形性が悪化する。 (C) Although there is no restriction | limiting in particular about the addition amount of polyphenylene ether resin, (A) rubber modified styrene resin and (B) styrene with a weight average molecular weight of 180,000 or less and a methanol soluble component amount of 2.0 mass% or less The total amount of the resin is preferably 50 parts by mass or less. If an amount exceeding 50 parts by mass is added, moldability deteriorates.
（Ｄ）成分の難燃剤は、臭素系難燃剤、リン系難燃剤、塩素系難燃剤等が挙げられる。 Examples of the flame retardant of component (D) include brominated flame retardants, phosphorus-based flame retardants, and chlorine-based flame retardants.
臭素系難燃剤としては、トリス（ポリブロモフェノキシ）トリアジン化合物、臭素化ジフェニルアルカン化合物、臭素化フタルイミド化合物、臭素化ポリスチレン、臭素化ポリアクリレート、臭素化ポリフェニレンエーテル、臭素化ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂の分子鎖末端のグリシジル基の一部又は全部を封止した変性物等が挙げられ、トリス（ポリブロモフェノキシ）トリアジン化合物、臭素化ジフェニルアルカン化合物、臭素化フタルイミド化合物が好適に使用される。 Brominated flame retardants include tris (polybromophenoxy) triazine compound, brominated diphenylalkane compound, brominated phthalimide compound, brominated polystyrene, brominated polyacrylate, brominated polyphenylene ether, brominated bisphenol A type epoxy resin, bromine Examples include modified products in which part or all of the glycidyl group at the molecular chain end of the bisphenol A type epoxy resin is sealed, and tris (polybromophenoxy) triazine compounds, brominated diphenylalkane compounds, and brominated phthalimide compounds are preferred. Used for.
リン系難燃剤としては、赤リン、有機リン酸エステル化合物、ホスファゼン化合物、ホスフィン酸塩類、ホスフォン酸塩類、ホスホルアミド化合物等が挙げられ、特に下記化２で表される芳香族ジオールビス（ジアリールホスフェート）化合物が好適に使用される。 Examples of phosphorus-based flame retardants include red phosphorus, organic phosphate ester compounds, phosphazene compounds, phosphinates, phosphonates, phosphoramide compounds and the like, and in particular, aromatic diol bis (diaryl phosphate) compounds represented by the following chemical formula 2 Are preferably used.
芳香族ジオールビス（ジアリールホスフェート）化合物としては、特にビスフェノールＡビス（ジアリールホスフェート）化合物、ベンゼンジオールビス（ジアリールホスフェート）化合物から選択された少なくとも一種の縮合リン酸エステルが好ましく用いられる。 As the aromatic diol bis (diaryl phosphate) compound, at least one condensed phosphate selected from bisphenol A bis (diaryl phosphate) compounds and benzenediol bis (diaryl phosphate) compounds is particularly preferably used.
本発明で使用するビスフェノールＡビス（ジアリールホスフェート）化合物は、上記化３の（Ｘ５）で表される化合物である。 The bisphenol A bis (diaryl phosphate) compound used in the present invention is a compound represented by (X5) in Chemical Formula 3 above.
ビスフェノールＡビス（ジアリールホスフェート）化合物として具体的には、ビスフェノールＡのビス（ジフェニルホスフェート）、ビス（ジトリルホスフェート）、（ジキシレニルホスフェート）化合物等が挙げられるが、好ましくは、ビスフェノールＡビス（ジフェニルホスフェート）化合物である。 Specific examples of the bisphenol A bis (diaryl phosphate) compound include bisphenol A bis (diphenyl phosphate), bis (ditolyl phosphate), and (dixylenyl phosphate) compounds. Preferably, the bisphenol A bis ( Diphenyl phosphate) compound.
本発明で使用するベンゼンジオールビス（ジアリールホスフェート）化合物は、上記化３の（Ｘ１）、（Ｘ２）、又は（Ｘ３）から選ばれる化合物である。 The benzenediol bis (diaryl phosphate) compound used in the present invention is a compound selected from (X1), (X2), or (X3) of the above Chemical Formula 3.
ベンゼンジオールビス（ジアリールホスフェート）化合物として具体的には、ヒドロキノン、レゾルシノール、カテコール等のビス（ジフェニルホスフェート）、ビス（ジトリルホスフェート）、（ジキシレニルホスフェート）化合物等が挙げられるが、好ましくはレゾルシノールビス（ジフェニルホスフェート）である。 Specific examples of the benzenediol bis (diaryl phosphate) compound include bis (diphenyl phosphate) such as hydroquinone, resorcinol and catechol, bis (ditolyl phosphate), and (dixylenyl phosphate) compounds, and preferably resorcinol. Bis (diphenyl phosphate).
（Ｄ）難燃剤の添加量について特に制限はないが、（Ａ）ゴム変性スチレン系樹脂と（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂の合計量に対して３〜３０質量部用いるのが好ましい。（Ｄ）難燃剤が３質量部より少ないと難燃性を確保できず、３０質量部より多いと耐熱性が低下する。 (D) Although there is no restriction | limiting in particular about the addition amount of a flame retardant, (A) Rubber modified styrene resin and (B) Styrene type | system | group of weight average molecular weight 180,000 or less and methanol soluble component amount 2.0 mass% or less It is preferable to use 3 to 30 parts by mass with respect to the total amount of the resin. (D) When there are few flame retardants than 3 mass parts, a flame retardance cannot be ensured, and when there are more than 30 mass parts, heat resistance will fall.
（Ｅ）難燃助剤としては例えば酸化アンチモン系化合物として三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、アンチモン酸ソーダ等、ホウ素系化合物としてホウ酸亜鉛、メタホウ酸バリウム、無水ホウ酸亜鉛、無水ホウ酸等、スズ系化合物としてスズ酸亜鉛、ヒドロキシスズ酸亜鉛等、モリブデン系化合物として酸化モリブデン、モリブデン酸アンモニウム等、ジルコニウム系化合物として酸化ジルコニウム、水酸化ジルコニウム等、また亜鉛系化合物として硫化亜鉛等が挙げられるが、なかでも酸化アンチモン系化合物、特に三酸化アンチモンを使用することが好ましい。 (E) Examples of flame retardant aids include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, etc. as antimony oxide compounds, zinc borate, barium metaborate, anhydrous zinc borate, anhydrous Boric acid, etc., tin-based compounds such as zinc stannate and hydroxyhydroxystannate, molybdenum-based compounds such as molybdenum oxide and ammonium molybdate, zirconium-based compounds such as zirconium oxide and zirconium hydroxide, and zinc-based compounds such as zinc sulfide Among them, it is preferable to use an antimony oxide compound, particularly antimony trioxide.
（Ｅ）難燃助剤の添加量について特に制限はないが、（Ａ）ゴム変性スチレン系樹脂と（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂の合計量に対して１０質量部以下で用いるのが好ましい。（Ｅ）難燃助剤が１０質量部を超えるとグローイングが発生し、難燃性が低下する。 (E) Although there is no restriction | limiting in particular about the addition amount of a flame retardant adjuvant, (A) rubber modified styrene resin and (B) weight average molecular weight 180,000 or less and methanol soluble component amount 2.0 mass% or less It is preferably used in an amount of 10 parts by mass or less based on the total amount of the styrene resin. (E) When the amount of the flame retardant aid exceeds 10 parts by mass, glowing occurs, and the flame retardancy decreases.
また、本発明の樹脂組成物には、本発明の要旨を超えない範囲で各種添加物、例えば染顔料、着色防止剤、滑剤、酸化防止剤、老化防止剤、光安定剤、帯電防止剤、充填剤、相溶化剤等の公知の添加剤、酸化チタンやカーボンブラックなどの着色剤などの改質剤を添加できる。これらの添加方法は特に限定される訳では無く、公知の方法、例えば、使用する（Ａ）ゴム変性スチレン系樹脂の重合開始前、重合途中の反応液に対して、または重合終了後、及び（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂を配合する際、更には、押出機や成形機においても添加することができる。 The resin composition of the present invention includes various additives within a range not exceeding the gist of the present invention, such as dyes and pigments, coloring agents, lubricants, antioxidants, anti-aging agents, light stabilizers, antistatic agents, Known additives such as fillers and compatibilizers, and modifiers such as colorants such as titanium oxide and carbon black can be added. These addition methods are not particularly limited. For example, (A) the rubber-modified styrenic resin to be used may be used before the start of polymerization, with respect to the reaction solution in the middle of the polymerization, or after the completion of the polymerization, and ( B) When blending a styrene resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component amount of 2.0% by mass or less, it can be added in an extruder or a molding machine.
本発明の樹脂組成物の混合方法は、公知の混合技術を適用することが出来る。例えばミキサー型混合機、Ｖ型他ブレンダー、及びタンブラー型混合機等の混合装置であらかじめ予備混合しておいた混合物を、更に溶融混練することで均一な樹脂組成物とすることが出来る。溶融混練にも特に制限はなく公知の溶融技術を適用出来る。好適な溶融混練装置として、バンバリー型ミキサー、ニーダー、ロール、単軸押出機、特殊単軸押出機、及び二軸押出機等がある。更に押出機等の溶融混練装置の途中から難燃剤等の添加剤を別途に添加する方法がある。 A known mixing technique can be applied to the method for mixing the resin composition of the present invention. For example, it is possible to obtain a uniform resin composition by further melt-kneading a mixture preliminarily mixed with a mixing apparatus such as a mixer type mixer, V type other blender, and tumbler type mixer. There is no particular limitation on melt kneading, and a known melting technique can be applied. Suitable melt kneaders include Banbury mixers, kneaders, rolls, single screw extruders, special single screw extruders, and twin screw extruders. Furthermore, there is a method of separately adding an additive such as a flame retardant from the middle of a melt-kneading apparatus such as an extruder.
本発明の樹脂組成物から成形品を得る成形法は射出成形が好ましい。 The molding method for obtaining a molded product from the resin composition of the present invention is preferably injection molding.
以下に本発明を実施例及び比較例によって詳しく説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
実施例及び比較例では（Ａ）ゴム変性スチレン系樹脂としてゴム変性ポリスチレン樹脂（ＨＩＰＳ）を使用した。ゴム変性ポリスチレン樹脂は、ゴム状重合体にポリブタジエンゴムを使用し、マトリックス部分の還元粘度０．７７ｄｌ／ｇ、ゴム状重合体含有量６．４質量％、及び体積平均粒子径３．０μｍ、メルトフローレート（ＭＦＲ）４ｇ／１０ｍｉｎであるゴム変性ポリスチレン樹脂を使用した。ここで言う還元粘度、ゴム状重合体含有量、ゴム状重合体の体積平均粒子径は以下の方法で測定した。 In Examples and Comparative Examples, (A) rubber-modified polystyrene resin (HIPS) was used as the rubber-modified styrene resin. The rubber-modified polystyrene resin uses polybutadiene rubber as the rubber-like polymer, the reduced viscosity of the matrix portion is 0.77 dl / g, the rubber-like polymer content is 6.4% by mass, the volume average particle diameter is 3.0 μm, the melt A rubber-modified polystyrene resin having a flow rate (MFR) of 4 g / 10 min was used. The reduced viscosity, the rubbery polymer content, and the volume average particle diameter of the rubbery polymer mentioned here were measured by the following methods.
還元粘度（ηｓｐ／Ｃ）の測定：（Ａ）ゴム変性スチレン系樹脂１ｇをそれぞれ別々にメチルエチルケトン１５ｍｌとアセトン１５ｍｌの混合溶媒を加え、温度２５℃で２時間振とう溶解した後、遠心分離で不溶分を沈降させ、デカンテーションにより上澄み液を取り出し、５００ｍｌのメタノールを加えて樹脂分を析出させ、不溶分を濾過乾燥する。同操作で得られた樹脂分をトルエンに溶解してポリマー濃度０．４％（質量／体積）の試料溶液を作成した。この試料溶液、及び純トルエンを３０℃の恒温でウベローデ型粘度計により溶液流下秒数を測定して、下式にて算出した。
ηｓｐ／Ｃ＝（ｔ１／ｔ０−１）／Ｃ
ｔ０：純トルエン流下秒数
ｔ１：試料溶液流下秒数
Ｃ ：ポリマー濃度
Measurement of reduced viscosity (ηsp / C): (A) 1 g of rubber-modified styrene resin was separately added to a mixed solvent of 15 ml of methyl ethyl ketone and 15 ml of acetone, dissolved by shaking at a temperature of 25 ° C. for 2 hours, and then insoluble by centrifugation. The fraction is allowed to settle, the supernatant is removed by decantation, 500 ml of methanol is added to precipitate the resin, and the insoluble matter is filtered and dried. The resin component obtained by the same operation was dissolved in toluene to prepare a sample solution having a polymer concentration of 0.4% (mass / volume). The sample solution and pure toluene were measured at a constant temperature of 30 ° C. using a Ubbelohde viscometer, and the number of seconds during which the solution flowed was measured.
ηsp / C = (t1 / t0-1) / C
t0: Pure toluene flow down seconds
t1: Sample solution flow down seconds
C: Polymer concentration
ゴム状重合体含有量の測定：（Ａ）ゴム変性スチレン系樹脂をそれぞれ別々にクロロホルムに溶解させ、一定量の一塩化ヨウ素／四塩化炭素溶液を加え暗所に約１時間放置後、１５質量％のヨウ化カリウム溶液と純水５０ｍｌを加え、過剰の一塩化ヨウ素を０．１Ｎチオ硫酸ナトリウム／エタノール水溶液で滴定し、付加した一塩化ヨウ素量から算出した。 Measurement of rubbery polymer content: (A) Each rubber-modified styrenic resin was dissolved separately in chloroform, and a certain amount of iodine monochloride / carbon tetrachloride solution was added and left in the dark for about 1 hour, then 15 mass % Potassium iodide solution and 50 ml of pure water were added, and excess iodine monochloride was titrated with 0.1N sodium thiosulfate / ethanol aqueous solution and calculated from the amount of added iodine monochloride.
ゴム状重合体の体積平均粒子径の測定：（Ａ）ゴム変性スチレン系樹脂をジメチルホルムアミドに完全に溶解させ、レーザー回析方式粒度分布装置にて測定した。
測定装置：コールター製レーザー回析方式粒子アナライザーＬＳ−２３０型
Measurement of volume average particle diameter of rubbery polymer: (A) A rubber-modified styrene resin was completely dissolved in dimethylformamide and measured with a laser diffraction particle size distribution apparatus.
Measuring device: Coulter laser diffraction particle analyzer LS-230
（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂は、（Ｂ−１）として重量平均分子量１４万、メタノール可溶成分量１．４質量％、ＭＦＲ２２ｇ／１０ｍｉｎであるスチレン重合体、（Ｂ−２）として重量平均分子量１１万、メタノール可溶成分量０．７質量％、ＭＦＲ３４ｇ／１０ｍｉｎであるスチレン重合体を使用した。ここで言う重量平均分子量、メタノール可溶成分量は以下の方法で測定した。 (B) A styrene resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component amount of 2.0% by mass or less is (B-1) as a weight-average molecular weight of 140,000 and a methanol-soluble component amount of 1.4 mass. %, MFR 22 g / 10 min styrene polymer, and (B-2) used was a weight average molecular weight 110,000, methanol soluble component amount 0.7 mass%, MFR 34 g / 10 min styrene polymer. The weight average molecular weight and the amount of methanol-soluble component mentioned here were measured by the following methods.
重量平均分子量の測定：重量平均分子量（Ｍｗ）は、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）を用いて、次の条件で測定した。
ＧＰＣ機種：昭和電工株式会社製Ｓｈｏｄｅｘ ＧＰＣ−１０１
カラム：ポリマーラボラトリーズ社製 ＰＬｇｅｌ １０μｍ ＭＩＸＥＤ−Ｃ
移動相：クロロホルム
試料濃度：０．２質量％
温度：オーブン４０℃
検出器：示差屈折計
本発明における各成分の分子量測定は、単分散ポリスチレンの溶出曲線より各溶出時間における分子量を算出し、ポリスチレン換算の分子量として算出したものである。
Measurement of weight average molecular weight: The weight average molecular weight (Mw) was measured under the following conditions using gel permeation chromatography (GPC).
GPC model: Shodex GPC-101 manufactured by Showa Denko KK
Column: Polymer Laboratories PLgel 10 μm MIXED-C
Mobile phase: Chloroform Sample concentration: 0.2% by mass
Temperature: Oven 40 ° C
Detector: Differential refractometer The molecular weight measurement of each component in the present invention is performed by calculating the molecular weight at each elution time from the elution curve of monodisperse polystyrene, and calculating the molecular weight in terms of polystyrene.
メタノール可溶成分量の測定：試料を溶媒に溶解し、１０倍量の貧溶媒でポリスチレンを再沈させ、再沈ポリスチレンの質量を求め、残分をメタノール可溶成分量とした。
測定条件
試料量：１ｇ、溶媒：ＭＥＫ４０ｍｌ、貧溶媒：メタノール４００ｍｌ
Measurement of methanol-soluble component amount: The sample was dissolved in a solvent, polystyrene was reprecipitated with 10 times the amount of poor solvent, the mass of the reprecipitated polystyrene was determined, and the residue was defined as the methanol-soluble component amount.
Measurement conditions Sample amount: 1 g, solvent: MEK 40 ml, poor solvent: methanol 400 ml
比較例として（Ｂ−１）、（Ｂ−２）に変えて（Ｂ−３）重量平均分子量１９万、メタノール可溶成分量１．３質量％、ＭＦＲ７ｇ／１０ｍｉｎであるスチレン重合体、（Ｂ−４）重量平均分子量１７万、メタノール可溶成分量４．８質量％、ＭＦＲ２８ｇ／１０ｍｉｎであるスチレン重合体を使用した。 As a comparative example, instead of (B-1) and (B-2), (B-3) a styrene polymer having a weight average molecular weight of 190,000, a methanol-soluble component amount of 1.3% by mass, and an MFR of 7 g / 10 min, (B -4) A styrene polymer having a weight average molecular weight of 170,000, a methanol-soluble component amount of 4.8% by mass, and an MFR of 28 g / 10 min was used.
（Ｃ）ポリフェニレンエーテル系樹脂
商品名ＰＸ１００Ｆ（三菱エンジニアリングプラスチックス社製、極限粘度０．３８ｄｌ／ｇ）を使用した。
(C) Polyphenylene ether resin trade name PX100F (manufactured by Mitsubishi Engineering Plastics Co., Ltd., intrinsic viscosity 0.38 dl / g) was used.
（Ｄ）難燃剤
（Ｄ−１）デカブロモジフェニルエタン化合物
商品名ＳＡＹＴＥＸ８０１０（アルベマール社製）を使用した。
(D) Flame retardant (D-1) Decabromodiphenylethane compound trade name SAYTEX8010 (manufactured by Albemarle) was used.
（Ｄ−２）ビスフェノールＡビス−ジフェニルホスフェート
商品名ＣＲ−７４１（大八化学工業社製、リン含有量８．２質量％）を使用した。
(D-2) Bisphenol A bis-diphenyl phosphate trade name CR-741 (manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus content 8.2 mass%) was used.
（Ｅ）難燃助剤
商品名ＡＴ−３ＣＮ（鈴裕化学社製、三酸化アンチモン）を使用した。
(E) Flame retardant aid trade name AT-3CN (manufactured by Suzuhiro Chemical Co., Ltd., antimony trioxide) was used.
次に、本発明の樹脂組成物の混合方法を述べる。（Ａ）ゴム変性スチレン系樹脂、（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂、（Ｃ）ポリフェニレンエーテル系樹脂、（Ｄ）難燃剤、（Ｅ）難燃助剤を表１に示す量にて配合し、これら全成分をヘンシェルミキサー（三井三池化工社製、ＦＭ２０Ｂ）にて予備混合し、二軸押出機（東芝機械社製、ＴＥＭ２６ＳＳ）に供給してストランドとし、水冷してからペレタイザーへ導きペレット化した。この際、シリンダー温度２３０℃、供給量３０ｋｇ／時間とした。なお、比較例についても、同様の操作を行った。 Next, a method for mixing the resin composition of the present invention will be described. (A) rubber-modified styrene resin, (B) styrene resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component amount of 2.0% by mass or less, (C) a polyphenylene ether resin, and (D) a flame retardant. , (E) Flame retardant aids were blended in the amounts shown in Table 1, and all these components were premixed with a Henschel mixer (Mitsui Miike Chemicals, FM20B), and a twin screw extruder (Toshiba Machine Co., Ltd., TEM26SS) to form a strand, which was cooled with water, led to a pelletizer and pelletized. At this time, the cylinder temperature was 230 ° C. and the supply amount was 30 kg / hour. The same operation was performed for the comparative example.
なお、実施例、比較例に示された各種物性値等の評価・測定は以下の方法により実施した。 In addition, evaluation and measurement of various physical property values shown in Examples and Comparative Examples were performed by the following methods.
（１）試験片作成
射出成形機：日本製鋼所株式会社製Ｊ１００Ｅ−Ｐ
得られたペレットを温度７０℃×３時間で加熱乾燥後、射出成形機にて、ＪＩＳ Ｋ ７１３９に記載のＡ型試験片（ダンベル）を成形した。
(1) Test piece making injection molding machine: J100E-P made by Nippon Steel Works
The obtained pellets were heated and dried at a temperature of 70 ° C. for 3 hours, and then A-type test pieces (dumbbells) described in JIS K 7139 were molded using an injection molding machine.
（２）流動性：メルトフローレート（ＭＦＲ）
得られたペレットをＪＩＳＫ７２１０に基づき測定を行った。
試験温度：２００℃
試験荷重：４９Ｎ
プリンター、ＦＡＸ、複写機内部等の家電筐体部材で使用するにあたり、メルトフローレート８ｇ／１０ｍｉｎ未満だと流動性が不足し成形不可となる懸念があるため、８ｇ／１０ｍｉｎ以上を満たす組成物を合格とした。
(2) Fluidity: Melt flow rate (MFR)
The obtained pellet was measured based on JISK7210.
Test temperature: 200 ° C
Test load: 49N
When used in household appliance housing members such as printers, fax machines, copiers, etc., there is a concern that if the melt flow rate is less than 8 g / 10 min, the fluidity is insufficient and molding becomes impossible, so a composition satisfying 8 g / 10 min or more is required. Passed.
なお原料とする（Ａ）ゴム変性スチレン系樹脂、（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂のメルトフローレートから計算される本願組成のスチレン系樹脂組成物のメルトフローレートを記載した。
計算式を下記に示す。
原料より計算されるスチレン系樹脂組成物のメルトフローレート［ｇ／１０ｍｉｎ］
＝１０＾（ＬＯＧ（（Ａ）ＭＦＲ）×（Ａ）質量比率＋ＬＯＧ（（Ｂ）ＭＦＲ）×（Ｂ）質量比率）
（Ａ）ＭＦＲ：（Ａ）ゴム変性スチレン系樹脂のメルトフローレート［ｇ／１０ｍｉｎ］
（Ａ）質量比率：（Ａ）ゴム変性スチレン系樹脂の添加量［部］÷（（Ａ）ゴム変性スチレン系樹脂の添加量［部］＋（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂の添加量［部］）
（Ｂ）ＭＦＲ：（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂のメルトフローレート［ｇ／１０ｍｉｎ］
（Ｂ）質量比率：（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂の添加量［部］÷（（Ａ）ゴム変性スチレン系樹脂の添加量［部］＋（Ｂ）重量平均分子量１８万以下、および、メタノール可溶成分量２．０質量％以下のスチレン系樹脂の添加量［部］）
The composition of the present application calculated from the melt flow rate of (A) rubber-modified styrene resin as raw material, (B) styrene resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component content of 2.0% by mass or less. The melt flow rate of the styrene resin composition was described.
The calculation formula is shown below.
Melt flow rate of styrene resin composition calculated from raw materials [g / 10 min]
= 10 ^ (LOG ((A) MFR) × (A) mass ratio + LOG ((B) MFR) × (B) mass ratio))
(A) MFR: (A) Melt flow rate of rubber-modified styrene resin [g / 10 min]
(A) Mass ratio: (A) Addition amount of rubber-modified styrene resin [parts] ÷ ((A) Addition amount of rubber-modified styrene resin [parts] + (B) Weight average molecular weight 180,000 or less, and methanol Addition amount of styrene-based resin having a soluble component amount of 2.0% by mass or less [parts])
(B) MFR: (B) Melt flow rate [g / 10 min] of a styrene resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component amount of 2.0% by mass or less.
(B) Mass ratio: (B) Addition amount of styrene resin with a weight average molecular weight of 180,000 or less and a methanol soluble component amount of 2.0 mass% or less [parts] ÷ ((A) of rubber-modified styrene resin Addition amount [parts] + (B) Addition amount of styrene-based resin having a weight average molecular weight of 180,000 or less and a methanol-soluble component amount of 2.0% by mass or less [parts])
（３）耐熱性：荷重たわみ温度（ＨＤＴ）
上記ダンベル片の中央より切り出した試験片を用いて、ＪＩＳ Ｋ ７１９１−２（Ａ法、フラットワイズ）に基づいて測定を行った。プリンター、ＦＡＸ、複写機内部等の家電筐体部材で使用するにあたり、耐熱性が７３℃未満だと耐熱性が不足し熱変形が生じる懸念があるため、７３℃以上を満たす組成物を合格とした。
(3) Heat resistance: deflection temperature under load (HDT)
Measurement was performed based on JIS K 7191-2 (Method A, flatwise) using a test piece cut out from the center of the dumbbell piece. When used in household appliance housing members such as printers, fax machines, copiers, etc., if the heat resistance is less than 73 ° C., there is a concern that the heat resistance will be insufficient and thermal deformation will occur. did.
（４）耐金型汚染性
射出成形機：日本製鋼所株式会社製Ｊ１００Ｅ−Ｐ
得られたペレットを温度７０℃×３時間で加熱乾燥後、射出成形機（２３０℃）で、ＪＩＳ Ｋ ７１３９に記載のＡ型試験片（ダンベル）を成形した際、以下の評価基準に従って評価した：
○：１００ショット連続成形後に金型に付着がない。
×：１００ショット連続成形後に金型に付着がある。
(4) Mold-resistant contamination injection molding machine: J100E-P manufactured by Nippon Steel Works
The obtained pellets were dried by heating at a temperature of 70 ° C. for 3 hours, and then evaluated according to the following evaluation criteria when an A-type test piece (dumbbell) described in JIS K 7139 was molded by an injection molding machine (230 ° C.). :
○: There is no adhesion to the mold after 100 shots of continuous molding.
X: There is adhesion to the mold after 100 shots of continuous molding.
下記表１に結果を示した。 The results are shown in Table 1 below.
表１の実施例より、本発明のスチレン系樹脂組成物は、流動性、耐熱性および耐金型汚染性に優れていることがわかる。 From the examples in Table 1, it can be seen that the styrene resin composition of the present invention is excellent in fluidity, heat resistance and mold stain resistance.
一方、表１の比較例より、本発明の規定を満足しないスチレン系難燃樹脂組成物は、流動性、耐熱性および耐金型汚染性に劣る。 On the other hand, from the comparative example of Table 1, the styrene flame retardant resin composition that does not satisfy the provisions of the present invention is inferior in fluidity, heat resistance, and mold contamination resistance.
特に実施例１と、本願請求項を満たさない（Ｂ−３）、（Ｂ−４）スチレン系重合体を組み合わせて原料組成から計算したＭＦＲが実施例１と同等となるように配合した比較例２を比べると、流動性、耐熱性、耐金型汚染性共に実施例１が比較例２より優れており、優位性は明らかである。
In particular, Example 1 and Comparative Examples in which (B-3) and (B-4) styrene polymers not satisfying the claims of this application were combined so that the MFR calculated from the raw material composition was equivalent to Example 1. Comparing 2, Example 1 is superior to Comparative Example 2 in terms of fluidity, heat resistance, and mold contamination resistance, and the superiority is clear.
Claims (6)
The molded object obtained by injection-molding the resin composition of any one of Claims 1-5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019059818A (en) * | 2017-09-26 | 2019-04-18 | 東洋スチレン株式会社 | Flame-retardant styrene resin composition, and molding and method for producing molding |
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| JPS57170950A (en) * | 1981-04-16 | 1982-10-21 | Mitsui Toatsu Chem Inc | Improved rubber-moldified styrene resin composition |
| JPH09241332A (en) * | 1996-03-07 | 1997-09-16 | Idemitsu Petrochem Co Ltd | Rubber-modified aromatic vinyl resin composition and its production |
| JPH11323063A (en) * | 1998-05-11 | 1999-11-26 | Denki Kagaku Kogyo Kk | Flame-retardant resin composition |
| JP2004010739A (en) * | 2002-06-06 | 2004-01-15 | Denki Kagaku Kogyo Kk | Rubber-modified styrenic resin composition and molded product thereof |
| JP2005054097A (en) * | 2003-08-06 | 2005-03-03 | Denki Kagaku Kogyo Kk | Method for producing heat-resistant thermoplastic resin and heat-resistance imparting agent composed of the heat-resistant thermoplastic resin |
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| JPS57170950A (en) * | 1981-04-16 | 1982-10-21 | Mitsui Toatsu Chem Inc | Improved rubber-moldified styrene resin composition |
| JPH09241332A (en) * | 1996-03-07 | 1997-09-16 | Idemitsu Petrochem Co Ltd | Rubber-modified aromatic vinyl resin composition and its production |
| JPH11323063A (en) * | 1998-05-11 | 1999-11-26 | Denki Kagaku Kogyo Kk | Flame-retardant resin composition |
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| JP2019059818A (en) * | 2017-09-26 | 2019-04-18 | 東洋スチレン株式会社 | Flame-retardant styrene resin composition, and molding and method for producing molding |
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