JP2016204399A - Tracking-resistant resin composition and injection-molded article comprising the same - Google Patents
Tracking-resistant resin composition and injection-molded article comprising the same Download PDFInfo
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本発明は、耐トラッキング性樹脂組成物およびその組成物から得られる射出成形体に関するものである。 The present invention relates to a tracking resistant resin composition and an injection molded product obtained from the composition.
非晶性樹脂はその優れた成形性を生かし、パーソナルコンピュータ、プリンター、複写機、ＴＶ、オーディオ等の電子機器など多くの製品に用いられてきた。 Amorphous resins have been used in many products such as electronic devices such as personal computers, printers, copiers, TVs and audios, taking advantage of their excellent moldability.
一方、非晶性樹脂は燃え易く、この問題を解決するため種々検討が行われてきた（特許文献１および２参照）。しかし、これらの手法を用いても耐トラッキング性は向上しない。 On the other hand, amorphous resins are flammable, and various studies have been made to solve this problem (see Patent Documents 1 and 2). However, the tracking resistance is not improved even if these methods are used.
本発明は、耐トラッキング性に優れる新規な樹脂組成物およびその射出成形体を提供するものである。 The present invention provides a novel resin composition excellent in tracking resistance and an injection-molded product thereof.
（１）．（Ａ）非晶性樹脂、及び（Ｂ）臭素化フタルイミド化合物とを含有することを特徴とする耐トラッキング性樹脂組成物。
（２）．（Ａ）非晶性樹脂１００質量部に対して、（Ｂ）臭素化フタルイミド化合物３〜２３質量部を含有することを特徴とする耐トラッキング性樹脂組成物。
（３）．（Ａ）非晶性樹脂１００質量部に対して、（Ｂ）臭素化フタルイミド化合物３〜２３質量部、及び（Ｃ）難燃助剤０．１〜７質量部を含有することを特徴とする耐トラッキング性樹脂組成物。
（４）．（Ｃ）難燃助剤が三酸化アンチモンであることを特徴とする前記（３）に記載の耐トラッキング性樹脂組成物。
（５）．（Ａ）非晶性樹脂がゴム変性スチレン系樹脂であることを特徴とする前記（１）〜（４）のいずれか１項に記載の耐トラッキング性樹脂組成物。
（６）．前記（１）〜（５）のいずれか１項に記載の耐トラッキング性樹脂組成物を射出成形して得られることを特徴とする成形体。
(1). A tracking resistant resin composition comprising (A) an amorphous resin and (B) a brominated phthalimide compound.
(2). (A) A tracking-resistant resin composition containing 3 to 23 parts by mass of (B) a brominated phthalimide compound with respect to 100 parts by mass of an amorphous resin.
(3). (A) It contains 3 to 23 parts by mass of a brominated phthalimide compound and (C) 0.1 to 7 parts by mass of a flame retardant aid with respect to 100 parts by mass of an amorphous resin. Tracking resistant resin composition.
(4). (C) The tracking resistant resin composition as described in (3) above, wherein the flame retardant aid is antimony trioxide.
(5). (A) The tracking-resistant resin composition according to any one of (1) to (4), wherein the amorphous resin is a rubber-modified styrene resin.
(6). A molded article obtained by injection-molding the tracking resistant resin composition according to any one of (1) to (5).
本発明は、耐トラッキング性、難燃性および耐衝撃性に優れる耐トラッキング性樹脂組成物を提供するものである。また、この耐トラッキング性樹脂組成物を射出成形して耐トラッキング性が要求される成形体を得ることが出来る。更にこの耐トラッキング性樹脂組成物を用いて得られる成形体は、電子機器・ＯＡ機器・分電盤等の電子機器外装およびカーエアコン・カーナビゲーション・カーオーディオの自動車用電装品等に好適に使用することができる。 The present invention provides a tracking resistant resin composition having excellent tracking resistance, flame retardancy and impact resistance. In addition, a molded product requiring tracking resistance can be obtained by injection molding the tracking resistant resin composition. Furthermore, molded products obtained using this tracking-resistant resin composition can be suitably used for electronic equipment exteriors such as electronic equipment, OA equipment, distribution boards, etc., and car electrical equipment for car air conditioners, car navigation systems, car audios, etc. can do.
本発明において使用する（Ａ）非晶性樹脂とは、非晶性を有する重合体であれば、特に限定されず、ポリスチレン（ＧＰＰＳ）樹脂、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）、無水マレイン酸−スチレン共重合体、（メタ）アクリル酸エステル・スチレン共重合体等のスチレン系樹脂；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）等のゴム変性スチレン系樹脂；ポリ塩化ビニル、エチレン・塩化ビニル重合体、ポリ塩化ビニリデン等の塩化ビニル系樹脂；ポリメタクリル酸メチル（ＰＭＭＡ）等の（メタ）アクリル酸エステルの１ 種以上を用いた（共）重合体等のアクリル系樹脂；ポリカーボネート樹脂（ＰＣ）；ポリアリレート樹脂；ポリフェニレンエーテル；ポリイミド、ポリアミドイミド、ポリエーテルイミド等のイミド系樹脂；ポリスルホン、ポリエーテルスルホン等のスルホン系樹脂；ウレタン系樹脂；フェノキシ樹脂；ポリ乳酸樹脂等が挙げられる。これらは、１種単独であるいは２種以上を組み合わせて用いることができる。これらのうち、スチレン系樹脂、ゴム変性スチレン系樹脂、アクリル系樹脂、塩化ビニル系樹脂、ポリカーボネート系樹脂、ポリフェニレンエーテルが好ましく、特に好ましくはゴム変性スチレン系樹脂、アクリル系樹、ポリカーボネート系樹脂、ポリフェニレンエーテルである。 The (A) amorphous resin used in the present invention is not particularly limited as long as it is a non-crystalline polymer. Polystyrene (GPPS) resin, AS resin (acrylonitrile-styrene copolymer), MS resin Styrenic resins such as (methyl methacrylate-styrene copolymer), maleic anhydride-styrene copolymer, (meth) acrylic acid ester / styrene copolymer; 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), etc. Rubber-modified styrene resin; polyvinyl chloride, ethylene Vinyl chloride resins such as vinyl chloride polymers and polyvinylidene chloride; acrylic resins such as (co) polymers using one or more (meth) acrylic acid esters such as polymethyl methacrylate (PMMA); polycarbonate resins (PC); polyarylate resin; polyphenylene ether; imide resins such as polyimide, polyamideimide and polyetherimide; sulfone resins such as polysulfone and polyethersulfone; urethane resin; phenoxy resin; . These can be used alone or in combination of two or more. Of these, styrene resins, rubber-modified styrene resins, acrylic resins, vinyl chloride resins, polycarbonate resins, and polyphenylene ether are preferable, and rubber-modified styrene resins, acrylic resins, polycarbonate resins, and polyphenylenes are particularly preferable. Ether.
上記、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、ゴム状重合体を加えてゴム変性を行ったスチレン系樹脂をゴム変性スチレン系樹脂と呼ぶ。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 above-mentioned styrene resin is obtained by polymerizing an aromatic vinyl compound monomer, and a styrene resin that has been rubber-modified by adding a rubbery polymer is called a rubber-modified styrene resin. 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.
上記、ゴム変性スチレン系樹脂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し、単独あるいは２種以上を組み合わせて用いても差し支えない。 Examples of the rubbery polymer used in the rubber-modified styrene resin include polybutadiene, styrene-butadiene random or block copolymers, polyisoprene, polychloroprene, styrene-isoprene random, block or graft copolymers, ethylene- Propylene rubber, ethylene-propylene-diene rubber and the like can be mentioned, and polybutadiene, styrene-butadiene random, block or graft copolymers are particularly preferable. These may be partially hydrogenated, or may be used alone or in combination of two or more.
上記、ゴム変性スチレン系樹脂中のゴム状重合体の含有量は、３〜１５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、１５質量％を超えると樹脂組成物の耐熱性が低下するため好ましくない。 The content of the rubber-like polymer in the rubber-modified styrene resin is preferably 3 to 15% by mass. When the content of the rubbery polymer is less than 3% by mass, the impact resistance of the resin composition is lowered, and when it exceeds 15% by mass, the heat resistance of the resin composition is lowered, which is not preferable.
上記、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は、０．１〜５．０μｍ質量％が好ましく、特に好ましくは１．０〜４．０μｍ質量％である。ゴム状重合体の平均粒子径は、０．１μｍ未満だと樹脂組成物の耐衝撃性が得られず、４．０μｍを超えると樹脂組成物の耐衝撃性が低下するため好ましくない。 The average particle size of the rubbery polymer in the rubber-modified styrene resin is preferably 0.1 to 5.0 μm mass%, particularly preferably 1.0 to 4.0 μm mass%. If the average particle size of the rubbery polymer is less than 0.1 μm, the impact resistance of the resin composition cannot be obtained, and if it exceeds 4.0 μm, the impact resistance of the resin composition is lowered, which is not preferable.
（Ａ）非晶性樹脂の分子量は、重量平均分子量（Ｍｗ）で１万〜５０万が好ましい。特に好ましくは、３万〜４０万である。Ｍｗは、１万未満だと樹脂組成物の耐熱性及び衝撃強度が低下するため好ましくなく、５０万を超えると流動性低下を引き起こし樹脂組成物の成形性が悪化するため好ましくない。 (A) The molecular weight of the amorphous resin is preferably 10,000 to 500,000 in terms of weight average molecular weight (Mw). Particularly preferred is 30,000 to 400,000. If Mw is less than 10,000, the heat resistance and impact strength of the resin composition are lowered, which is not preferable, and if it exceeds 500,000, fluidity is lowered and the moldability of the resin composition is deteriorated.
本発明で用いる（Ｂ）臭素化フタルイミド化合物はトラッキング防止剤であり、下記一般式（１）で表される構造を有している。
具体的には、メチレン−ビス−フタルイミド、エチレン−ビス−フタルイミド、プロピレン−ビス−フタルイミド、ブチレン−ビス−フタルイミド、ペンチレン−ビス−フタルイミド、ヘキシレン−ビス−フタルイミド等のジブロモ置換体、トリブロモ置換体、テトラブロモ置換体、ペンタブロモ置換体、ヘキサブロモ置換体、ヘプタブロモ置換体、オクタブロモ置換体が挙げられる。好ましくは、エチレン−ビス−フタルイミド、プロピレン−ビス−フタルイミド、ブチレン−ビス−フタルイミド、ペンチレン−ビス−フタルイミド、ヘキシレン−ビス−フタルイミドのオクタブロモ置換体である。特に好ましくは、エチレン−ビス−テトラブロモフタルイミドである。 Specifically, dibromo substitution products such as methylene-bis-phthalimide, ethylene-bis-phthalimide, propylene-bis-phthalimide, butylene-bis-phthalimide, pentylene-bis-phthalimide, hexylene-bis-phthalimide, tribromo substitution, Examples include tetrabromo-substituted, pentabromo-substituted, hexabromo-substituted, heptabromo-substituted, and octabromo-substituted. Preferred are octabromo-substituted products of ethylene-bis-phthalimide, propylene-bis-phthalimide, butylene-bis-phthalimide, pentylene-bis-phthalimide, and hexylene-bis-phthalimide. Particularly preferred is ethylene-bis-tetrabromophthalimide.
（Ｂ）臭素化フタルイミド化合物の添加量は、（Ａ）非晶性樹脂１００質量部に対して３〜２３質量部が好ましい。特に好ましくは５〜２０質量部である。（Ｂ）臭素化フタルイミド化合物の添加量は、３質量部未満だと樹脂組成物に耐トラッキング性を付与できず、２３質量部以上であると樹脂組成物の耐衝撃性が劣るため好ましくない。 (B) As for the addition amount of a brominated phthalimide compound, 3-23 mass parts is preferable with respect to 100 mass parts of (A) amorphous resin. Especially preferably, it is 5-20 mass parts. (B) If the addition amount of the brominated phthalimide compound is less than 3 parts by mass, the resin composition cannot be provided with tracking resistance, and if it is 23 parts by mass or more, the impact resistance of the resin composition is inferior.
（Ｃ）難燃助剤は、（Ｂ）臭素化フタルイミド化合物の難燃性を高める働きをするものであり、例えば、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酸化第二スズ、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。なかでも三酸化アンチモンを使用することが特に好ましい。 (C) The flame retardant aid functions to enhance the flame retardancy of the (B) brominated phthalimide compound. For example, antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate as antimony compounds. Etc., zinc borate, barium metaborate, anhydrous zinc borate, anhydrous boric acid, etc. as boron compounds, stannic oxide, zinc stannate, zinc hydroxystannate, etc. as tin compounds, molybdenum oxide as molybdenum compounds, Ammonium molybdate and the like, zirconium-based compounds such as zirconium oxide and zirconium hydroxide, and zinc-based compounds include zinc sulfide and the like. Among them, it is particularly preferable to use antimony trioxide.
（Ｃ）難燃助剤の添加量は、（Ａ）非晶性樹脂１００質量部に対して０．１〜２０質量部が好ましい。（Ｃ）難燃助剤の添加量が、（Ａ）非晶性樹脂に対して２０質量部を超えると樹脂組成物の耐衝撃性が劣るため好ましくない。 (C) As for the addition amount of a flame retardant adjuvant, 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) amorphous resin. (C) When the addition amount of a flame retardant adjuvant exceeds 20 mass parts with respect to (A) amorphous resin, since the impact resistance of a resin composition is inferior, it is unpreferable.
また、本発明の耐トラッキング性樹脂組成物には、本発明の要旨を超えない範囲で各種添加物、例えば難燃剤、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）非晶性樹脂の重合開始前、重合途中の反応液に対して、または重合終了後、及び（Ｂ）臭素化フタルイミド化合物もしくは（Ｃ）難燃助剤を配合する際、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。 In addition, the tracking resistant resin composition of the present invention includes various additives within a range not exceeding the gist of the present invention, such as flame retardants, dyes and pigments, coloring inhibitors, lubricants, antioxidants, anti-aging agents, and light stability. Known additives such as an agent, an antistatic agent, a filler and a compatibilizing agent, and a modifier such as a colorant such as titanium oxide and carbon black can be added. These addition methods are not particularly limited, and known methods, for example, (A) the amorphous resin to be used, before the start of polymerization, with respect to the reaction solution in the middle of polymerization, or after the completion of polymerization, and (B When a brominated phthalimide compound or (C) a flame retardant aid is blended, it can also be added in an extruder or a molding machine.
本発明の耐トラッキング性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臭素化フタルイミド化合物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 of mixing the tracking resistant 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. Further, there is a method in which an additive such as a brominated phthalimide compound is added separately 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）非晶性樹脂として（Ａ１）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、重量平均分子量（Ｍｗ）２３万、ゴム状重合体含有量８．５質量％、及び体積平均粒子径２．５３μｍであるゴム変性ポリスチレン樹脂を使用した。ここで言う重量平均分子量、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 (A) amorphous resin. The rubber-modified polystyrene resin uses a polybutadiene rubber as a rubber-like polymer, has a weight-average molecular weight (Mw) of 230,000, a rubber-like polymer content of 8.5% by mass, and a volume-average particle diameter of 2.53 μm. Polystyrene resin was used. The weight average molecular weight, the rubbery polymer content, and the volume average particle diameter of the rubbery polymer mentioned here were measured by the following methods.
重量平均分子量の測定：（Ａ１）ゴム変性ポリスチレン樹脂（ＨＩＰＳ）の重量平均分子量（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。なお、本実施例で使用したゴム変性ポリスチレン樹脂（ＨＩＰＳ）はポリスチレン樹脂のマトリクス相にゴム状分散粒子が分散した形態であり、分子量はマトリクス相の分子量を意味する。そのため分子量測定に用いる試料は５０％メチルエチルケトン／５０％アセトン混合溶液にＨＩＰＳを溶解させ、遠心分離機（コクサン社製Ｈ−２０００Ｂ（ローター：Ｈ））にてゴム状分散粒子を除去し、メタノールに再沈殿させたポリマー物を使用した。
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 ５μｍ ＭＩＸＥＤ−Ｃ
移動相：テトラヒドロフラン
試料濃度：０．２質量％
温度：オーブン４０℃、注入口３５℃、検出器３５℃
検出器：示差屈折計
本発明の分子量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: (A1) The weight average molecular weight (Mw) of rubber-modified polystyrene resin (HIPS) was measured under the following conditions using gel permeation chromatography (GPC). The rubber-modified polystyrene resin (HIPS) used in this example is a form in which rubber-like dispersed particles are dispersed in a matrix phase of polystyrene resin, and the molecular weight means the molecular weight of the matrix phase. Therefore, the sample used for the molecular weight measurement was prepared by dissolving HIPS in a 50% methyl ethyl ketone / 50% acetone mixed solution, removing rubber-like dispersed particles with a centrifuge (Hoku2000 H-2000B (rotor: H)), and adding methanol to methanol. A re-precipitated polymer was used.
GPC model: Shodex GPC-101 manufactured by Showa Denko KK
Column: Polymer Laboratories PLgel 5 μm MIXED-C
Mobile phase: tetrahydrofuran
Sample concentration: 0.2% by mass
Temperature: 40 ° C oven, 35 ° C inlet, 35 ° C detector
Detector: Differential refractometer The molecular weight of the present invention is calculated as the molecular weight in terms of polystyrene by calculating the molecular weight at each elution time from the elution curve of monodisperse polystyrene.
ゴム状重合体含有量の測定：（Ａ１）ゴム変性スチレン系樹脂を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: (A1) A rubber-modified styrenic resin was dissolved in chloroform, a certain amount of iodine monochloride / carbon tetrachloride solution was added and left in the dark for about 1 hour, and then 15% by mass of iodine. A potassium iodide solution and 50 ml of pure water were added, and excess iodine monochloride was titrated with a 0.1N sodium thiosulfate / ethanol aqueous solution, and the amount was calculated from the amount of iodine monochloride added.
ゴム状重合体の体積平均粒子径の測定：（Ａ１）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 rubber-like polymer: (A1) 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）臭素化フタルイミド化合物には、（Ｂ１）エチレン−ビス−テトラブロモフタルイミドであるアルベマール社製商品名ＳＡＹＴＥＸ ＢＴ−９３Ｗを使用した。 (B) The brand name SAYTEX BT-93W manufactured by Albemarle, which is (B1) ethylene-bis-tetrabromophthalimide, was used as the brominated phthalimide compound.
比較例として、（Ｂ）臭素化フタルイミド化合物の代わりに、既存のハロゲン系難燃剤である（Ｂ２）デカブロモジフェニルエタンであるアルベマール社製の商品名ＳＡＹＴＥＸ ８０１０を使用した。 As a comparative example, the brand name SAYTEX 8010 manufactured by Albemarle, which is (B2) decabromodiphenylethane, which is an existing halogen flame retardant, was used instead of (B) the brominated phthalimide compound.
比較例として、（Ｂ）臭素化フタルイミド化合物の代わりに、既存のハロゲン系難燃剤である（Ｂ３）２，４，６−トリス（２，４，６−トリブロモフェノキシ）−１，３，５−トリアジンである第一工業製薬社製の商品名ピロガード ＳＲ２４５を使用した。 As a comparative example, (B3) 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5 which is an existing halogen flame retardant instead of (B) brominated phthalimide compound -The trade name Piroguard SR245 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which is a triazine, was used.
（Ｃ）難燃助剤には、（Ｃ１）三酸化アンチモンである鈴裕化学社製の商品名ＡＴ−３ＣＮを使用した。 (C) As a flame retardant aid, (C1) trade name AT-3CN manufactured by Suzuhiro Chemical Co., which is 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）非晶性樹脂、（Ｂ）臭素化フタルイミド化合物および（Ｃ）難燃助剤を表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、押出機のシリンダー温度は２３０℃、供給量は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) Amorphous resin, (B) Brominated phthalimide compound and (C) Flame retardant aid are blended in the amounts shown in the table, and all these components are mixed with a Henschel mixer (Mitsui Miike Chemical Industries, FM20B) Preliminarily mixed, supplied to a twin screw extruder (Toshiki Machine Co., Ltd., TEM26SS) to form a strand, cooled with water, led to a pelletizer and pelletized. At this time, the cylinder temperature of the extruder 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）耐トラッキング性：耐トラッキング性の測定は、米国アンダーライターズ・ラボラトリーズ社のサブジェクト７４６Ａ号（ＵＬ７４６Ａ）の試験方法に準拠し、ＰＬＣ値で評価した。評価結果は下記の様に表記した。
ランク０以上：合格
ランク１以下：不合格
なお、評価用試験片（１００ｍｍ×１００ｍｍ×３ｍｍ）は、射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）を用いて作製した。この際、射出成形機のシリンダー温度は２２０℃、金型温度は４５℃とした。
(1) Tracking resistance: The tracking resistance was measured by a PLC value in accordance with the test method of Subject 746A (UL746A) manufactured by Underwriters Laboratories, USA. The evaluation results are shown as follows.
Rank 0 or higher: Pass rank 1 or lower: Failed A test piece for evaluation (100 mm × 100 mm × 3 mm) was produced using an injection molding machine (manufactured by Nippon Steel Works, Ltd., J100E-P). At this time, the cylinder temperature of the injection molding machine was 220 ° C., and the mold temperature was 45 ° C.
（２）難燃性：難燃性の測定は、米国アンダーライターズ・ラボラトリーズ社のサブジェクト９４号（ＵＬ９４）の垂直燃焼試験方法に準拠し、試験片厚さ１．５ｍｍの燃焼性を評価した。評価結果は下記の様に表記した。
５ＶＢ：合格
Ｖ−０：合格
Ｖ−１：合格
Ｖ−２：合格
ＮＧ：Ｖ−２レベルに未達
なお、燃焼用試験片（１２７×１２.７×１．５ｍｍ）は、射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）を用いて作製した。この際、射出成形機のシリンダー温度は２２０℃、金型温度は４５℃とした。
(2) Flame retardancy: The flame retardancy was measured in accordance with the vertical burn test method of Subject No. 94 (UL94) of US Underwriters Laboratories, Inc., and the flame retardance of a test piece thickness of 1.5 mm was evaluated. . The evaluation results are shown as follows.
5VB: Passed V-0: Passed V-1: Passed V-2: Passed NG: Not reached the V-2 level The test piece for combustion (127 × 12.7 × 1.5 mm) is an injection molding machine ( It was produced using Nippon Steel Works, Ltd. (J100E-P). At this time, the cylinder temperature of the injection molding machine was 220 ° C., and the mold temperature was 45 ° C.
（３）耐衝撃性：耐衝撃性の評価尺度としたシャルピー衝撃値は、ＪＩＳ Ｋ ７１１１−１に基づき測定を行った。シャルピー衝撃値が１０．０ｋJ／ｍ２未満だと成形品としての耐衝撃性が不十分なので、シャルピー衝撃値が１０．０ｋJ／ｍ２以上の組成物を合格とした。なお、評価用試験片（ＪＩＳ Ｋ ７１３９に記載のＡ型試験片（ダンベル）は、射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）を用いて、を作製した。この際、射出成形機のシリンダー温度は２２０℃、金型温度は４５℃とした。そして、このダンベル片の中央部より切り出し、切削でノッチ（タイプＡ、ｒ＝０．２５ｍｍ）を入れ、試験に用いた。 (3) Impact resistance: Charpy impact value as an evaluation scale of impact resistance was measured based on JIS K 7111-1. When the Charpy impact value is less than 10.0 kJ / m 2 , the impact resistance as a molded product is insufficient, and therefore a composition having a Charpy impact value of 10.0 kJ / m 2 or more was regarded as acceptable. In addition, the test piece for evaluation (A type test piece (dumbbell) described in JIS K 7139 was produced using an injection molding machine (manufactured by Nippon Steel Works, Ltd., J100E-P). The cylinder temperature of the molding machine was 220 ° C., and the mold temperature was 45 ° C. Then, the dumbbell piece was cut out from the central portion, cut into a notch (type A, r = 0.25 mm), and used for the test.
下記表１〜２に結果を示した。 The results are shown in Tables 1 and 2 below.
表１の実施例より、本発明の難燃樹脂組成物は、耐トラッキング性、難燃性および耐衝撃性に優れている。 From the examples in Table 1, the flame retardant resin composition of the present invention is excellent in tracking resistance, flame resistance and impact resistance.
一方、表２の比較例より、本発明の規定を満足しない難燃樹脂組成物は、耐トラッキング性、難燃性もしくは耐衝撃性に劣る。 On the other hand, from the comparative example of Table 2, the flame retardant resin composition that does not satisfy the provisions of the present invention is inferior in tracking resistance, flame resistance or impact resistance.
（Ｂ１）臭素化フタルイミド化合物を配合しないと、耐トラッキング性および難燃性に劣る（比較例１）。また、（Ｂ１）の代わりに、ハロゲン系難燃剤（Ｂ２）を用いると耐トラッキング性および耐衝撃性に劣り、ハロゲン系難燃剤（Ｂ３）を用いると、耐トラッキング性に劣る（比較例２およ３）。 (B1) Unless a brominated phthalimide compound is blended, the tracking resistance and flame retardancy are poor (Comparative Example 1). In addition, when halogen-based flame retardant (B2) is used instead of (B1), tracking resistance and impact resistance are poor, and when halogen-based flame retardant (B3) is used, tracking resistance is poor (Comparative Example 2). Yo 3).
本発明の耐トラッキング性樹脂組成物は、耐トラッキング性、難燃性および耐衝撃性に優れるため、電子機器・ＯＡ機器等の電子機器外装およびカーエアコン・カーナビゲーション・カーオーディオ等の自動車等の電装分野での利用が有利になる。
Since the tracking-resistant resin composition of the present invention is excellent in tracking resistance, flame retardancy and impact resistance, the exterior of electronic equipment such as electronic equipment and OA equipment, and automobiles such as car air conditioners, car navigation and car audio, etc. Use in the electrical equipment field is advantageous.
Claims (6)
A molded article obtained by injection-molding the tracking resistant resin composition according to any one of claims 1 to 5.
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