JP2016030807A - Styrenic flame-retardant resin composition and molding comprising the same - Google Patents
Styrenic flame-retardant resin composition and molding comprising the same Download PDFInfo
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Abstract
Description
本発明は、スチレン系難燃性樹脂組成物およびその組成物から得られる成形体に関するものである。詳しくはハロゲン含有有機化合物およびポリフェニレンエーテルを含有せず難燃性に優れ、耐熱性、耐衝撃性の物性バランスに優れ、電子・電気機器、ＯＡ機器等に好適なスチレン系難燃性樹脂組成物およびその組成物から得られる成形体に関するものである。 The present invention relates to a styrene-based flame retardant resin composition and a molded product obtained from the composition. Specifically, it does not contain halogen-containing organic compounds and polyphenylene ether, and has excellent flame retardancy, excellent balance of physical properties of heat resistance and impact resistance, and is suitable for electronic / electrical equipment, OA equipment, etc. And a molded body obtained from the composition.
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。 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.
この様にスチレン系樹脂は優れた成形性を有するが、他方では燃え易く製品としての安全性に不安があった。そこで、この燃え易さを解消するため、従来からスチレン系樹脂への難燃性を付与目的として種々の難燃剤が提案されてきた。中でも安価で物性バランスに優れているハロゲン含有有機化合物が多く用いられている。代表的なものとして、テトラブロモビスフェノールＡ、デカブロモジフェニルエーテル、デカブロモジフェニルエタン、臭素化エポキシ、及び臭素化エポキシ樹脂等がある。
また、上記ハロゲン含有有機化合物の難燃性を向上させる難燃助剤として、三酸化アンチモンが一般に用いられる。
As described above, the styrenic resin has excellent moldability, but on the other hand, it is flammable and there is anxiety about safety as a product. Therefore, in order to eliminate this flammability, various flame retardants have been proposed for the purpose of imparting flame retardancy to styrene resins. Of these, halogen-containing organic compounds that are inexpensive and have excellent physical property balance are often used. Typical examples include tetrabromobisphenol A, decabromodiphenyl ether, decabromodiphenylethane, brominated epoxy, and brominated epoxy resin.
Further, antimony trioxide is generally used as a flame retardant aid for improving the flame retardancy of the halogen-containing organic compound.
しかしながら、ハロゲン含有有機化合物は加工時にハロゲン化水素ガスが発生し金型腐食等の不具合発生の可能性があることや、自然環境に悪影響を及ぼすことが考えられるため、ハロゲン含有有機化合物を使用しない難燃化方法が検討されている。更に近年、ハロゲン含有有機化合物を規制する動きが欧州を中心として活発に行われており、ハロゲン元素を含まない難燃樹脂、難燃樹脂組成物の需要が高まっている。 However, since halogen-containing organic compounds generate hydrogen halide gas during processing, which may cause defects such as mold corrosion, and may adversely affect the natural environment, do not use halogen-containing organic compounds. Flame retardant methods are being studied. Furthermore, in recent years, movements for regulating halogen-containing organic compounds have been actively carried out mainly in Europe, and the demand for flame retardant resins and flame retardant resin compositions containing no halogen element is increasing.
ハロゲン含有有機化合物の代替難燃剤としては主にリン系難燃剤が検討されている。例えばスチレン系樹脂の難燃樹脂組成物としては、スチレン系樹脂とリン系難燃剤からなる難燃性スチレン系樹脂組成物（特開２００１−２０７０１２号公報）、スチレン系樹脂、リン系難燃剤、無機充填剤、ゴムからなる難燃性スチレン系樹脂組成物（特開２０００−１０３９３２号公報）等を挙げることができる。 As an alternative flame retardant for halogen-containing organic compounds, phosphorus-based flame retardants are mainly studied. For example, as a flame retardant resin composition of a styrene resin, a flame retardant styrene resin composition comprising a styrene resin and a phosphorus flame retardant (Japanese Patent Laid-Open No. 2001-207012), a styrene resin, a phosphorus flame retardant, Examples thereof include a flame retardant styrene resin composition comprising an inorganic filler and rubber (Japanese Patent Laid-Open No. 2000-103932).
しかし、従来のリン系難燃剤の使用は耐熱性もしくは耐衝撃性を低下させる。そこで、ポリフェニレンエーテルを配合して耐熱性を向上させた難燃性スチレン系樹脂組成物が検討されているが（特開平１１−２０９６００号公報）、耐衝撃性低下の問題については現在解決されていない。 However, the use of conventional phosphorus flame retardants reduces heat resistance or impact resistance. Therefore, a flame-retardant styrene-based resin composition having improved heat resistance by blending polyphenylene ether has been studied (Japanese Patent Laid-Open No. 11-209600), but the problem of reduced impact resistance is currently being solved. Absent.
また、ポリフェニレンエーテルを配合することにより、押出時におけるポリフェニレンエーテル由来の樹脂焼けやリサイクル工程での分別作業に多量のエネルギーを要するといった問題が新たに生じている。 In addition, by adding polyphenylene ether, a new problem has arisen in that a large amount of energy is required for the baking of the resin derived from polyphenylene ether at the time of extrusion and the separation work in the recycling process.
本発明は、この様な現状を鑑み、上記問題点を解決するため、ハロゲン含有有機化合物およびポリフェニレンエーテルを含有せず難燃性、耐熱性、および衝撃性に優れたスチレン系難燃樹性脂組成物を提供するものである。 In view of such a current situation, the present invention solves the above-mentioned problems, and does not contain a halogen-containing organic compound and polyphenylene ether, and has excellent flame retardancy, heat resistance, and impact resistance. A composition is provided.
本発明者は、上記課題について鋭意検討した結果、スチレン系樹脂にホスファゼン組成物を配合する事により本発明を完成させた。 As a result of intensive studies on the above problems, the present inventors have completed the present invention by blending a phosphazene composition with a styrene resin.
本発明は（Ａ）スチレン系樹脂と（Ｂ）ホスファゼン組成物からなり、ハロゲン含有有機化合物およびポリフェニレンエーテルを含まないスチレン系難燃樹性脂組成物であることを特徴とする。 The present invention is characterized in that it is a styrene-based flame-retardant resin composition comprising (A) a styrene-based resin and (B) a phosphazene composition, which does not contain a halogen-containing organic compound and polyphenylene ether.
また、本発明は上記スチレン系難燃樹性脂組成物を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 shape | molding the said styrene-type flame retardant resinous fat composition.
本発明は、ハロゲン含有有機化合物およびポリフェニレンエーテルを含有せず難燃性、耐熱性および耐衝撃性に優れた、スチレン系難燃性樹脂組成物を提供するものである。また、この樹脂組成物を射出成形して自己消炎性が要求される成形体を得ることが出来る。更にこの難燃性樹脂組成物を用いて得られる成形体は、トナーカートリッジ、プリンター、パソコン等の筐体等の電子・電気機器、ＯＡ機器等に好適に使用することができる。 The present invention provides a styrene-based flame retardant resin composition which does not contain a halogen-containing organic compound and polyphenylene ether and is excellent in flame retardancy, heat resistance and impact resistance. In addition, a molded product requiring self-extinguishing properties can be obtained by injection molding the resin composition. Furthermore, a molded article obtained using this flame retardant resin composition can be suitably used for electronic / electrical equipment such as a housing of a toner cartridge, printer, personal computer, etc., OA equipment, and the like.
本発明において使用する（Ａ）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、必要に応じてゴム状重合体を加えてゴム変性を行ってもよい。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 (A) styrenic resin used in the present invention is obtained by polymerizing an aromatic vinyl compound monomer, and rubber modification may be performed by adding a rubbery polymer as necessary. . 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）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。 Examples of the rubber-like polymer used for rubber modification of the styrene resin of the present invention (A) include polybutadiene, styrene-butadiene random or block copolymers, polyisoprene, polychloroprene, styrene-isoprene random, block or graft copolymers. Polymers, ethylene-propylene rubber, ethylene-propylene-diene rubber and the like can be mentioned, and polybutadiene and styrene-butadiene random, block or graft copolymers are particularly preferable. These may be partially hydrogenated.
このような（Ａ）スチレン系樹脂の例として、ポリスチレン（ＧＰＰＳ）、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）、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）、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) styrene resin include polystyrene (GPPS), high impact polystyrene (HIPS), ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), MS resin (methyl methacrylate-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylenepropylene-styrene copolymer), MBS resin (methyl methacrylate-butadiene-styrene copolymer) Polymer) and the like.
（Ａ）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ないが、還元粘度(ηsp／Ｃ)で０．５０〜１．００が好ましい。１．００を超えると、難燃性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、０．５０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 a styrene-type resin, 0.50-1.00 are preferable at a reduced viscosity ((eta) sp / C). If it exceeds 1.00, the fluidity of the flame-retardant resin composition is too low, which hinders molding, and if it is less than 0.50, practically sufficient strength cannot be exhibited.
（Ａ）スチレン系樹脂中のゴム状重合体の含有量は、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) As for content of the rubber-like polymer in a styrene 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）スチレン系樹脂中のゴム状重合体の平均粒子径は、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未満だと耐衝撃性は得られず、４．０μｍを超えると耐衝撃性が低下する。 (A) The average particle diameter of the rubber-like polymer in the styrene-based resin is preferably 0.4 to 5.0 μm mass%, particularly preferably 1.0 to 4.0 μm mass%. If the average particle size of the rubber-like polymer is less than 0.4 μm, impact resistance cannot be obtained, and if it exceeds 4.0 μm, impact resistance decreases.
（Ｂ）ホスファゼン組成物は、下記式（１）で表される環状ホスファゼン化合物および／または、下記式（２）で表される線状ホスファゼン化合物である。
（Ｂ）ホスファゼン組成物中の環状ホスファゼン化合物と線状ホスファゼン化合物の比率は、環状ホスファゼン化合物が９０質量％以上であることが好ましい。特に好ましくは、環状ホスファゼン１００質量％である。環状ホスファゼン化合物は線状ホスファゼン化合物と比較してリン含有量が高いため、環状ホスファゼン化合物が９０質量％未満だと難燃性に劣るため好ましくない。 (B) The ratio of the cyclic phosphazene compound to the linear phosphazene compound in the phosphazene composition is preferably 90% by mass or more for the cyclic phosphazene compound. Particularly preferred is 100% by mass of cyclic phosphazene. Since the cyclic phosphazene compound has a higher phosphorus content than the linear phosphazene compound, if the cyclic phosphazene compound is less than 90% by mass, the flame retardancy is inferior.
（Ｂ）ホスファゼン組成物中の環状ホスファゼン化合物について、三量体を６０質量％以上含有することが好ましく、特に好ましくは７０質量％以上である。三量体が６０質量％未満だとスチレン系難燃樹脂組成物の外観が悪化するため好ましくない。 (B) About the cyclic phosphazene compound in a phosphazene composition, it is preferable to contain 60 mass% or more of a trimer, Most preferably, it is 70 mass% or more. When the trimer is less than 60% by mass, the appearance of the styrene-based flame retardant resin composition is deteriorated, which is not preferable.
（Ｂ）ホスファゼン組成物の融点については、９０℃以上が好ましい。特に好ましくは１００℃以上である。融点が９０℃未満だと耐熱性に劣るため好ましくない。 (B) About melting | fusing point of a phosphazene composition, 90 degreeC or more is preferable. Especially preferably, it is 100 degreeC or more. If the melting point is less than 90 ° C., the heat resistance is poor, such being undesirable.
（Ｂ）ホスファゼン組成物の添加量は、（Ａ）スチレン系樹脂１００質量部に対して５〜１７質量部が好ましい。 (B) As for the addition amount of a phosphazene composition, 5-17 mass parts is preferable with respect to 100 mass parts of (A) styrene resin.
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）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）ホスファゼン組成物を配合する際、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, and are known methods, for example, (A) the styrene-based resin to be used before the start of polymerization, with respect to the reaction solution during the polymerization, or after the end of the polymerization, and (B) When the phosphazene composition is blended, it can also 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には特に制限は無いが、好ましくは射出成形である。 Although there is no restriction | limiting in particular in the shaping | molding method which obtains a molded article from the resin composition of this invention, Preferably it is injection molding.
以下に本発明を参考例、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 by reference examples, examples and comparative examples, but the present invention is not limited thereto.
実施例及び比較例では（Ａ）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３．０２μｍ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 styrene resin. The rubber-modified polystyrene resin uses polybutadiene rubber as the rubber-like polymer, and has a reduced viscosity of 0.77 dl / g in the matrix portion, a rubber-like polymer content of 6.4% by mass, and a volume average particle size of 3.02 μm. A rubber-modified polystyrene resin 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）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 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 mixture is allowed to settle, the supernatant is removed by decantation, 500 ml of methanol is added to precipitate the resin component, and the insoluble component 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）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) Styrene resins were separately dissolved in chloroform, a certain amount of iodine monochloride / carbon tetrachloride solution was added, and the mixture was left in the dark for about 1 hour. 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 iodine monochloride added.
ゴム状重合体の体積平均粒子径の測定：（Ａ）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: (A) A 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）ホスファゼン組成物には、伏見製薬所社製の商品名ＦＰ−１１０[環状三量体含有量：７０質量％、環状四〜十量体含有量：３０質量％、融点：１０８℃]を使用した。 (B) For the phosphazene composition, trade name FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. [cyclic trimer content: 70% by mass, cyclic tetramer to decamer content: 30% by mass, melting point: 108 ° C.] It was used.
（Ｂ）ホスファゼン組成物の代わりに、縮合リン酸エステルで４，４’―ビフェノールビス（ジ−２，６−キシレニルホスフェート）である大八化学工業株式会社製の商品名ＰＸ−２０２[略称：４ＢＤＸ、融点：１８５℃]を用いた。 (B) Instead of the phosphazene composition, the product name PX-202 [manufactured by Daihachi Chemical Industry Co., Ltd., which is 4,4′-biphenol bis (di-2,6-xylenyl phosphate) as a condensed phosphate ester Abbreviation: 4BDX, melting point: 185 ° C.] was used.
（Ｂ）ホスファゼン組成物の代わりに、縮合リン酸エステルで４，４’―ビフェノールビス（ジフェニルホスフェート）であるＡＤＥＫＡ社製の商品名ＦＰ−８００[略称：４ＢＤＰ、融点：７５℃]を用いた。 (B) Instead of the phosphazene composition, a product name FP-800 [abbreviation: 4BDP, melting point: 75 ° C.] manufactured by ADEKA, which is 4,4′-biphenol bis (diphenyl phosphate) as a condensed phosphate ester, was used. .
（Ｂ）ホスファゼン組成物の代わりに、縮合リン酸エステルでビスフェノールＡビス（ジフェニルホスフェート）である大八化学社製の商品名ＣＲ−７４１[略称：ＢＤＰ、融点：５℃]を用いた。 (B) Instead of the phosphazene composition, trade name CR-741 [abbreviation: BDP, melting point: 5 ° C.] manufactured by Daihachi Chemical Co., Ltd., which is a condensed phosphate ester and bisphenol A bis (diphenyl phosphate), was used.
（Ｂ）ホスファゼン組成物の代わりに、縮合リン酸エステルでレゾルシノールビス（ジフェニルホスフェート）である大八化学社製の商品名ＣＲ−７３３Ｓ[略称：ＲＤＰ、融点：−１３℃]を用いた。 (B) Instead of the phosphazene composition, trade name CR-733S [abbreviation: RDP, melting point: −13 ° C.] manufactured by Daihachi Chemical Co., which is a condensed phosphate ester and resorcinol bis (diphenyl phosphate) was used.
次に、本発明の樹脂組成物の混合方法を述べる。（Ａ）スチレン系樹脂、（Ｂ）環状ホスファゼン組成物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、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) Styrenic resin and (B) cyclic phosphazene composition were blended in the amounts shown in the table, and all these components were premixed with a Henschel mixer (FM20B, manufactured by Mitsui Miike Chemical Co., Ltd.) The product was supplied to Toshiba Machine Co., Ltd. (TEM26SS) to form a strand, which was cooled with water and led to a pelletizer to be 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）耐熱性：耐熱性の評価尺度としたビカット軟化温度は、ＪＩＳ Ｋ ７２０６に準拠し、昇温速度５０℃／ｈｒ、試験荷重５０Ｎで試験を行った。ビカット軟化温度は８０℃未満であると耐熱性が不十分となり熱変形することがあるので、８０℃以上を満たす組成物を合格とした。 (1) Heat resistance: Vicat softening temperature as an evaluation scale for heat resistance was tested according to JIS K 7206 at a heating rate of 50 ° C./hr and a test load of 50 N. If the Vicat softening temperature is less than 80 ° C., the heat resistance becomes insufficient and heat deformation may occur.
（２）耐衝撃性：耐衝撃性の評価尺度としたシャルピー衝撃強度は、ＪＩＳ Ｋ ７１１１−１に基づき測定を行った。強度が８ＫJ／ｍ２未満だと成形品の強度が不十分なので、８ＫJ／ｍ２以上を満たす組成物を合格とした。なお、シャルピー衝撃強度用試験片は、射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）にて、ＪＩＳ Ｋ ７１３９に記載のＡ型試験片（ダンベル）を成形した。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。 (2) Impact resistance: Charpy impact strength as an evaluation scale of impact resistance was measured based on JIS K 7111-1. Since strength is insufficient strength of the molded article with less than 8 kJ / m 2, it was evaluated as acceptable composition that satisfies 8 kJ / m 2 or more. In addition, the test piece for Charpy impact strength shape | molded the A-type test piece (dumbbell) as described in JISK7139 with the injection molding machine (Nippon Steel Works Co., Ltd. J100E-P). And it cut out from the center part of this dumbbell piece, the notch (type A, r = 0.25mm) was put by cutting, and it used for the test.
（３）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（以下、ＵＬ９４とも略記する）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。
Ｖ−２：合格
ＮＧ：Ｖ−２レベルに未達
なお、評価用試験片は、射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）にて、１２７×１２.７×１．５ｍｍの燃焼用試験片を成形した。
(3) Flame retardancy: The flame retardancy was measured in accordance with the vertical burning test method of Subject No. 94 (hereinafter also abbreviated as UL94) of the United States Underwriters Laboratories, with a specimen thickness of 1.5 mm. The flammability was evaluated. The evaluation results are shown as follows.
V-2: Passed NG: Not reached V-2 level Note that the test piece for evaluation was 127 × 12.7 × 1.5 mm using an injection molding machine (manufactured by Nippon Steel Works, J100E-P). A test piece for combustion was molded.
下記表１〜３に結果を示した。 The results are shown in Tables 1 to 3 below.
表１の実施例より、本発明のスチレン系難燃樹脂組成物は、難燃性、耐熱性および衝撃性に優れていることがわかる。 From the Example of Table 1, it turns out that the styrene-type flame retardant resin composition of this invention is excellent in a flame retardance, heat resistance, and impact property.
一方、表２および表３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、難燃性、耐熱性および衝撃性に劣る。 On the other hand, from the comparative examples in Tables 2 and 3, styrene-based flame retardant resin compositions that do not satisfy the provisions of the present invention are inferior in flame retardancy, heat resistance, and impact resistance.
（Ｂ）ホスファゼン組成物の代わりに別のリン系化合物を用いると、耐衝撃性もしくは耐熱性に劣る（比較例１〜４）。また、（Ｂ）ホスファゼン組成物の代わりに別のリン系化合物を用いた場合、その配合量が少ないと耐衝撃性および耐熱性は合格するものの難燃性に劣る（比較例５、６）。 (B) When another phosphorus compound is used instead of the phosphazene composition, the impact resistance or heat resistance is poor (Comparative Examples 1 to 4). In addition, when another phosphorus compound is used in place of the (B) phosphazene composition, if the blending amount is small, the impact resistance and heat resistance pass but the flame retardancy is poor (Comparative Examples 5 and 6).
本発明のスチレン系難燃樹脂組成物は、難燃性、耐熱性および衝撃性に優れているため、ＯＡ機器や家電部材等の電子機器分野での利用が有利になる。
Since the styrene-based flame retardant resin composition of the present invention is excellent in flame retardancy, heat resistance, and impact resistance, it is advantageous to use it in the field of electronic equipment such as OA equipment and home appliance members.
Claims (4)
The molded object obtained by shape | molding the styrene-type flame retardant resin composition in any one of Claims 1-3.
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| JP2017186438A (en) * | 2016-04-05 | 2017-10-12 | 東洋スチレン株式会社 | Styrene resin composition |
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