JP6159067B2 - Styrene flame-retardant resin composition and molded article - Google Patents
Styrene flame-retardant resin composition and molded article Download PDFInfo
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本発明は、リン系難燃剤を用いたスチレン系難燃性樹脂組成物と、該組成物を用いた成形体に関する。 The present invention relates to a styrene-based flame retardant resin composition using a phosphorus-based flame retardant and a molded body using the composition.
ゴム変性スチレン系樹脂は広範囲の用途に使用されており、特に、難燃性樹脂はワープロ、パーソナルコンピュータ、プリンター、複写機等のＯＡ機器、テレビ、ＶＴＲ、オーディオ等の家電製品等を初めとする多岐の分野で使用されている。従来から、スチレン系樹脂に難燃性を付与するために、種々の難燃剤が提案されており、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使用されている。しかしながら、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に活発化していることなどから、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。こうしたハロゲン系難燃剤の代替難燃剤としてリン系難燃剤が検討されている。 Rubber-modified styrene resins are used in a wide range of applications. In particular, flame retardant resins are used in office automation equipment such as word processors, personal computers, printers, copiers, and home appliances such as televisions, VTRs, and audio. Used in various fields. Conventionally, various flame retardants have been proposed to impart flame retardancy to styrene resins, and among them, halogen-containing organic compounds that are inexpensive and excellent in balance of physical properties are often used. However, in recent years, the movement of regulating halogen-containing organic compounds has been activated mainly in Europe, and therefore, there is an increasing demand for flame retardant resins and flame retardant resin compositions that do not contain halogen elements. Phosphorus flame retardants have been studied as alternative flame retardants for such halogen flame retardants.
リン系難燃剤では難燃効果を発現するために炭化層形成成分を含有する樹脂と併用することが一般的である。ところがこの炭化層形成成分を含有する樹脂は成形収縮率及び成形品の反り特性がゴム変性スチレン系樹脂と大きく異なっているため、ゴム変性スチレン系樹脂に炭化層形成成分を含有する樹脂を配合し、リン系難燃剤を添加して難燃性樹脂組成物とすると、係る難燃性樹脂組成物を成形した際に、成形時の収縮率や成形品の反りがハロゲン系難燃剤を用いた場合よりも大きくなってしまう。 In general, a phosphorus-based flame retardant is used in combination with a resin containing a carbonized layer forming component in order to exhibit a flame retardant effect. However, since the resin containing the carbonized layer forming component is greatly different from the rubber-modified styrenic resin in terms of molding shrinkage and warping properties of the molded product, a resin containing the carbonized layer forming component is blended with the rubber-modified styrene resin. When a flame retardant resin composition is formed by adding a phosphorus flame retardant, when the flame retardant resin composition is molded, the shrinkage rate at the time of molding or the warpage of the molded product is when a halogen flame retardant is used. Will be bigger than.
特許文献１には、スチレン系樹脂、ポリフェニレンエーテル系樹脂、有機リン酸エステル、タルク等を含む樹脂組成物が記載され、該組成物は特定の無機化合物を特定割合で配合することで、高強度、高寸法精度、低反り性、及び良好な難燃性を有することが開示されている。しかしながら、反りについては具体的に示されていない。 Patent Document 1 describes a resin composition containing a styrene resin, a polyphenylene ether resin, an organic phosphate ester, talc, and the like, and the composition contains a specific inorganic compound at a specific ratio, thereby providing high strength. It has been disclosed to have high dimensional accuracy, low warpage and good flame retardancy. However, the warpage is not specifically shown.
一方、最近トナーカートリッジ容器は本体のコンセプトから起因するコンパクト化が要求され、ユーザーが交換作業を行う設計となっている。こうした要請からユーザーが直接手に触れることとなるトナーカートリッジ容器には、後述するＵＬ９４でＶ−２以上の高度な難燃性が求められている。具体的にはＵＬ９４でＶ−２は燃焼物の滴下が認められているが、この滴下物の消炎時間を可能な限り短時間に抑制した材料が待望されている。 On the other hand, recently, the toner cartridge container is required to be compact due to the concept of the main body, and is designed to be replaced by the user. The toner cartridge container that is directly touched by the user due to such a request is required to have a high flame retardancy of V-2 or higher according to UL 94 described later. Specifically, dripping of the combustion substance is recognized in V94 in UL94, but a material that suppresses the flame extinguishing time of the dripping substance as short as possible is desired.
しかしながらリン系難燃剤を用いた難燃性樹脂では、滴下物の消炎時間が長くなることがあり、試験片の消炎時間はＵＬ９４でＶ−２の規格内であっても、滴下物の消炎時間が比較的長い傾向にあった。 However, flame retardant resins using phosphorus-based flame retardants may increase the flame extinguishing time of the drop, and even when the flame extinguishing time of the test piece is within the V-2 standard of UL94, the flame extinguishing time of the drop. Tended to be relatively long.
特許文献２には、スチレン系樹脂、１分子中に少なくとも１つのメルカプト基を有する化合物又はその塩、リン酸エステル等のリン化合物を含有してなる難燃性スチレン系樹脂組成物が記載され、滴下物の消炎時間が大幅に短縮できることが開示されている。 Patent Document 2 describes a flame retardant styrene resin composition comprising a styrene resin, a compound having at least one mercapto group in one molecule or a salt thereof, and a phosphorus compound such as a phosphate ester, It is disclosed that the flame extinguishing time of the dripping material can be greatly shortened.
また特許文献３には、耐衝撃性ポリスチレンを少なくとも５０質量％含有する樹脂成分、特定構造のリン含有化合物、金属酸化物よりなる難燃性樹脂組成物が記載され、難燃助剤として金属酸化物を用いることにより、滴下物の消炎時間が３０秒以内であるポリスチレン樹脂組成物を提供できることが開示されている。 Patent Document 3 describes a flame-retardant resin composition comprising a resin component containing at least 50% by mass of impact-resistant polystyrene, a phosphorus-containing compound having a specific structure, and a metal oxide. It is disclosed that a polystyrene resin composition having a flame extinguishing time of 30 seconds or less can be provided by using a product.
しかしながら、特許文献２，３に開示された組成物はいずれもポリフェニレンエーテル系樹脂を含んでおらず、耐熱性が不足しており使用範囲が限定されるため、実用性に乏しい。また、特許文献２の樹脂組成物は、難燃助剤として１分子中に少なくとも１つのメルカプト基を有する化合物又はその塩が必須であり、メルカプト基に起因する臭気がユーザーより忌避されるため、最終消費者が使用する製品部材の原料としては適さない。 However, none of the compositions disclosed in Patent Documents 2 and 3 contain a polyphenylene ether resin, have insufficient heat resistance, and have a limited range of use. In addition, the resin composition of Patent Document 2 requires a compound having at least one mercapto group in one molecule or a salt thereof as a flame retardant aid, and the odor caused by the mercapto group is avoided by the user. It is not suitable as a raw material for product parts used by end consumers.
本発明の課題は、滴下物の燃焼を抑制可能な高度な難燃性と強度、耐熱性を備え、組成に起因する成形収縮率と反りを従来と同程度に抑えた、ハロゲン系難燃剤を用いないスチレン系難燃性樹脂組成物を提供し、該組成物を用いて難燃性、強度に優れた成形体を提供することにある。 An object of the present invention is to provide a halogen-based flame retardant that has high flame retardancy, strength, and heat resistance capable of suppressing the combustion of dripping material, and has suppressed the molding shrinkage and warpage caused by the composition to the same extent as before. An object of the present invention is to provide a styrene-based flame retardant resin composition that is not used, and to provide a molded article having excellent flame retardancy and strength using the composition.
本発明は、（Ａ）ゴム変性スチレン系樹脂と（Ｂ）ポリフェニレンエーテル系樹脂と（Ｃ）縮合リン酸エステルと（Ｄ）タルクとを配合してなるスチレン系難燃性樹脂組成物であって、
上記（Ａ）ゴム変性スチレン系樹脂と（Ｂ）ポリフェニレンエーテル系樹脂との合計量を１００質量部とした時、（Ｂ）ポリフェニレンエーテル系樹脂が１０〜３０質量部であり、（Ｄ）タルクが０．１〜１０質量部であり、
上記（Ｃ）縮合リン酸エステルに由来するリン添加量の上記（Ｂ）ポリフェニレンエーテル系樹脂に対する質量部の比が０．０２６〜０．０７２であり、
スチレン系難燃性樹脂組成物中に含まれるゴム状重合体の含有量が３．５〜８．５質量％であることを特徴とする。
The present invention is a styrene flame-retardant resin composition comprising (A) a rubber-modified styrene resin, (B) a polyphenylene ether resin, (C) a condensed phosphate ester and (D) talc. ,
When the total amount of the (A) rubber-modified styrene resin and the (B) polyphenylene ether resin is 100 parts by mass, the (B) polyphenylene ether resin is 10 to 30 parts by mass, and (D) talc is 0.1 to 10 parts by mass,
(C) The ratio of the mass part with respect to said (B) polyphenylene ether-type resin of the phosphorus addition amount derived from condensed phosphate ester is 0.026-0.072,
The content of the rubber-like polymer contained in the styrene-based flame retardant resin composition is 3.5 to 8.5% by mass.
また、本発明は、上記スチレン系難燃性樹脂組成物を成形して得られることを特徴とする成形体を提供する。 Moreover, this invention provides the molded object characterized by being obtained by shape | molding the said styrene-type flame retardant resin composition.
本発明によれば、滴下物の燃焼を抑制可能な高度な難燃性と強度、耐熱性を備え、成形収縮率と成形品の反りを従来のハロゲン系難燃剤を用いた樹脂組成物と同程度に抑えた、リン系難燃剤を用いた難燃性樹脂組成物が提供される。また、本発明のスチレン系難燃性樹脂組成物はその高度な難燃性から、電気特性（耐トラッキング性）にも優れた特性を有している。よって、本発明のスチレン系難燃性樹脂組成物を用いることにより、難燃性、強度に優れた成形品を成形することができる。 According to the present invention, it has high flame retardancy, strength, and heat resistance capable of suppressing the combustion of dripping material, and has the same molding shrinkage and warpage of molded products as a resin composition using a conventional halogen flame retardant. Provided is a flame-retardant resin composition using a phosphorus-based flame retardant suppressed to a degree. In addition, the styrene-based flame retardant resin composition of the present invention has excellent electrical characteristics (tracking resistance) due to its high flame resistance. Therefore, by using the styrene-based flame retardant resin composition of the present invention, a molded product having excellent flame retardancy and strength can be molded.
本発明のスチレン系難燃性樹脂組成物は、（Ａ）ゴム変性スチレン系樹脂と（Ｂ）ポリフェニレンエーテル系樹脂と（Ｃ）縮合リン酸エステルと（Ｄ）タルクとを配合してなる。そして、上記（Ａ）ゴム変性スチレン系樹脂と（Ｂ）ポリフェニレンエーテル系樹脂との合計量を１００質量部とした時、（Ｂ）ポリフェニレンエーテル系樹脂が１０〜３０質量部であり、（Ｄ）タルクが０．１〜１０質量部である。また、組成物中のゴム状重合体の含有量は３．５〜８．５質量％である。以下に、各成分について詳細に説明する。 The styrene flame-retardant resin composition of the present invention is formed by blending (A) a rubber-modified styrene resin, (B) a polyphenylene ether resin, (C) a condensed phosphate ester, and (D) talc. And when the total amount of the (A) rubber-modified styrene resin and (B) polyphenylene ether resin is 100 parts by mass, (B) the polyphenylene ether resin is 10 to 30 parts by mass, and (D) Talc is 0.1 to 10 parts by mass. Moreover, content of the rubber-like polymer in a composition is 3.5-8.5 mass%. Below, each component is demonstrated in detail.
本発明で用いる（Ａ）ゴム変性スチレン系樹脂は、スチレン系単量体にゴム成分を溶解し、熱重合または過酸化物等の重合開始剤を用いて攪拌下で重合させた物であり、製造プロセスとしてはバッチ重合でも連続重合でも良い。スチレン系単量体としてはｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、２，４−ジメチルスチレン等が挙げられるが、スチレンが最も好適である。これらの単量体を用いて単独重合体としても良いし、２種以上を併用して使用することも出来る。またこれらの単量体と共重合可能なメタクリル酸、メタクリル酸メチル等を用いて共重合体としても良い。ゴム成分としては、ブタジエン、イソプレン等の単独重合体や、ブタジエンと共重合可能なスチレンやメタクリル酸メチル等との共重合体が用いられ、共重合体の分子構造はランダム構造でもブロック構造でも良く、分岐構造を有しても良い。またこうしたゴム変性スチレン系樹脂は、樹脂組成物としてのゴム成分量や衝撃強度、流動性を調節する目的で、ゴム成分を含まないポリスチレン（ＧＰＰＳ）と併用し用いても良い。難燃性樹脂組成物中のゴム状重合体は３．５〜８質量％であり、好ましくは４．５〜７質量％である。ゴム状重合体の量が３．５質量％より少ないと強度が低下し、８質量％より多いと成形品の反りが大きくなってしまい、いずれも好ましくない。尚、（Ａ）ゴム変性スチレン系樹脂は、ゴム成分として７０質量％以上が、シス−１，４結合を９０モル％以上の比率で含有するハイシスポリブタジエンゴムを用いたものが好ましい。１，４−シス結合含量が１０〜４０モル％であるローシスポリブタジエンゴムを用いた場合、離型性が低下するため、好ましくない。 The rubber-modified styrene resin (A) used in the present invention is a product obtained by dissolving a rubber component in a styrene monomer and polymerizing it with stirring using a polymerization initiator such as thermal polymerization or peroxide, The production process may be batch polymerization or continuous polymerization. Examples of the styrenic monomer include o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene and the like, and styrene is most preferable. These monomers may be used as a homopolymer, or two or more types may be used in combination. Moreover, it is good also as a copolymer using methacrylic acid, methyl methacrylate, etc. which can be copolymerized with these monomers. As the rubber component, homopolymers such as butadiene and isoprene, and copolymers with styrene and methyl methacrylate that can be copolymerized with butadiene are used, and the molecular structure of the copolymer may be a random structure or a block structure. , May have a branched structure. Further, such a rubber-modified styrene resin may be used in combination with polystyrene (GPPS) containing no rubber component for the purpose of adjusting the amount of rubber component, impact strength, and fluidity of the resin composition. The rubbery polymer in the flame retardant resin composition is 3.5 to 8% by mass, preferably 4.5 to 7% by mass. When the amount of the rubber-like polymer is less than 3.5% by mass, the strength is lowered, and when it is more than 8% by mass, the warpage of the molded product is increased. The (A) rubber-modified styrenic resin preferably uses a high-cis polybutadiene rubber containing 70% by mass or more of rubber components as a rubber component in a ratio of 90 mol% or more. When a low-cis polybutadiene rubber having a 1,4-cis bond content of 10 to 40 mol% is used, it is not preferable because releasability is lowered.
本発明の（Ｂ）ポリフェニレンエーテル系樹脂とは、下記に示す一般式（Ｉ）及び／又は（ＩＩ）で表される繰り返し単位を有する重合体である。 The (B) polyphenylene ether resin of the present invention is a polymer having a repeating unit represented by the following general formula (I) and / or (II).
ポリフェニレンエーテルの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）エーテル等のホモポリマーが挙げられる。この中では、ポリ（２，６−ジメチル−１，４−フェニレン）エーテルが特に好ましい。 Representative examples of polyphenylene ether polymers include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, and 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-1,4-phenylene) Homopolymers such as ether can be mentioned. Of these, poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferred.
本発明においては、（Ａ）ゴム変性スチレン系樹脂と（Ｂ）ポリフェニレンエーテル系樹脂との合計量を１００質量部とした時に、（Ｂ）ポリフェニレンエーテル系樹脂が１０〜３０質量部である。（Ｂ）ポリフェニレンエーテル系樹脂が１０質量部未満では滴下物の消炎時間が長くなり、また、３０質量部を超えると流動性の低下から成形加工性の悪化を引き起こすため、いずれも好ましくない。より好ましくは１０〜２０質量部、さらに望ましくは１０〜１５質量部である。 In the present invention, when the total amount of (A) the rubber-modified styrene resin and (B) the polyphenylene ether resin is 100 parts by mass, the (B) polyphenylene ether resin is 10 to 30 parts by mass. (B) When the polyphenylene ether-based resin is less than 10 parts by mass, the flame extinguishing time of the dropped product becomes long, and when it exceeds 30 parts by mass, the moldability is deteriorated due to a decrease in fluidity. More preferably, it is 10-20 mass parts, More desirably, it is 10-15 mass parts.
（Ｂ）ポリフェニレンエーテル系樹脂は、極限粘度が好ましくは０．２５〜０．５０ｄｌ／ｇ、更に好ましくは０．３０〜０．４０ｄｌ／ｇである。極限粘度が０．２５〜０．５０ｄｌ／ｇの範囲を外れると成形収縮率及び成形品の反りと難燃性及び強度のバランスが悪化するため好ましくない。 The (B) polyphenylene ether resin preferably has an intrinsic viscosity of 0.25 to 0.50 dl / g, more preferably 0.30 to 0.40 dl / g. If the intrinsic viscosity is out of the range of 0.25 to 0.50 dl / g, the balance between the molding shrinkage ratio, the warpage of the molded article, the flame retardancy, and the strength is not preferable.
本発明で用いる（Ｃ）縮合リン酸エステルとしては（Ｃ−１）レゾルシノールビス−ジフェニルホスフェートや（Ｃ−２）ビスフェノールＡビス−ジフェニルホスフェートが挙げられる。（Ｃ−１）レゾルシノールビス−ジフェニルホスフェートは例えば商品名「ＣＲ−７３３Ｓ」（大八化学工業社製）、（Ｃ−２）ビスフェノールＡビス−ジフェニルホスフェートは例えば商品名「ＣＲ−７４１」（大八化学工業社製）として知られているものである。好ましいのは（Ｃ−１）レゾルシノールビス−ジフェニルホスフェートであり、成形収縮率及び成形品の反りと難燃性及び物性のバランスに優れている。 Examples of the (C) condensed phosphate ester used in the present invention include (C-1) resorcinol bis-diphenyl phosphate and (C-2) bisphenol A bis-diphenyl phosphate. (C-1) Resorcinol bis-diphenyl phosphate is, for example, trade name “CR-733S” (manufactured by Daihachi Chemical Industry Co., Ltd.), and (C-2) Bisphenol A bis-diphenyl phosphate is, for example, trade name “CR-741” (large It is known as Hachi Chemical Industry Co., Ltd.). Preferable is (C-1) resorcinol bis-diphenyl phosphate, which has an excellent balance between molding shrinkage and warpage of the molded article, flame retardancy and physical properties.
本発明において、（Ｃ）縮合リン酸エステルに由来するリン添加量の（Ｂ）ポリフェニレンエーテル系樹脂に対する質量部の比は０．０２６〜０．０７２である。（Ｃ）縮合リン酸エステルが少ないと成形品の反り、滴下物の消炎時間が悪化し、多すぎると耐熱性が低下するため好ましくない。 In this invention, the ratio of the mass part with respect to (B) polyphenylene ether-type resin of (B) polyphenylene ether resin of the phosphorus addition amount derived from ( C) condensed phosphate ester is 0.026-0.072 . (C) When there is little condensed phosphate ester , the curvature of a molded article and the flame-extinguishing time of a dripped material will deteriorate, and when too large , heat resistance will fall , and it is unpreferable.
本発明では、無機化合物として（Ｄ）タルクを使用する。（Ｄ）タルクの添加量は、（Ａ）ゴム変性スチレン系樹脂と（Ｂ）ポリフェニレンエーテル系樹脂との合計量１００質量部に対し、０．１〜１０質量部である。０．１質量部未満では成形時の成形収縮率が大きくなり、１０質量部を超えるとシャルピー衝撃強度が低下し、いずれも好ましくない。より好ましくは１〜６質量部である。 In the present invention, (D) talc is used as the inorganic compound. The amount of (D) talc added is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of (A) rubber-modified styrene resin and (B) polyphenylene ether resin. If it is less than 0.1 parts by mass, the molding shrinkage during molding becomes large, and if it exceeds 10 parts by mass, the Charpy impact strength is lowered, which is not preferable. More preferably, it is 1-6 mass parts.
本発明のスチレン系難燃性樹脂組成物には、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、エラストマー成分（ＳＢＳや水添ＳＢＳ）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）ポリフェニレンエーテル系樹脂、（Ｃ）縮合リン酸エステル、及び（Ｄ）タルクを配合する際、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 styrene-based flame retardant resin composition of the present invention includes various additives such as dyes, pigments, anti-coloring agents, lubricants, antioxidants, anti-aging agents, light stabilizers, charging agents within the scope of the present invention. Known additives such as inhibitors, fillers and compatibilizers, colorants such as titanium oxide and carbon black, and modifiers such as elastomer components (SBS and hydrogenated SBS) 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 ( When blending B) polyphenylene ether resin, (C) condensed phosphate ester, and (D) talc, they can also be added in an extruder or molding machine.
本発明に係わるスチレン系難燃性樹脂組成物を得る方法は、特に限定される訳では無く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型ブレンダー、及びタンブラー型混合機等の混合装置で予め混合しておいた混合物を、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、及び二軸押出機等で溶融混練することが挙げられる。各原材料の添加方法としては、（Ａ）ゴム変性スチレン系樹脂、（Ｂ）ポリフェニレンエーテル系樹脂と（Ｄ）タルク、及び必要に応じて他の添加剤を直接上記のような混練機に投入し、更に、押出機等の溶融混練装置の途中から（Ｃ）縮合リン酸エステルを別途に添加して樹脂組成物を得てもよいし、本発明の趣旨を超えない範囲で予め樹脂等と（Ｃ）縮合リン酸エステルと（Ｄ）タルク等を混練してペレット状にしたマスターバッチを作製し、このマスターバッチと（Ａ）ゴム変性スチレン系樹脂を混練機に投入する方法でもよい。 The method for obtaining the styrene-based flame retardant resin composition according to the present invention is not particularly limited, and a known mixing technique can be applied. For example, a mixture previously mixed with a mixing apparatus such as a mixer-type mixer, V-type blender, and tumbler-type mixer is mixed with a Banbury mixer, kneader, roll, single-screw extruder, special single-screw extruder, and For example, melt kneading may be performed with a twin screw extruder. As the method of adding each raw material, (A) a rubber-modified styrene resin, (B) a polyphenylene ether resin and (D) talc, and other additives as required are directly charged into the kneader as described above. Furthermore, (C) a condensed phosphate ester may be added separately from the middle of a melt-kneading apparatus such as an extruder to obtain a resin composition, or resin and the like in advance within a range not exceeding the gist of the present invention ( A method may be used in which a master batch is prepared by kneading C) condensed phosphate ester and (D) talc or the like into pellets, and charging this master batch and (A) rubber-modified styrene resin into a kneader.
本発明のスチレン系難燃性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、好ましいのは射出成形であり、特にトナーカートリッジ容器の成形には射出成形が好適である。 There is no particular limitation on the molding method for obtaining a molded product from the styrene-based flame retardant resin composition of the present invention, but injection molding is preferable, and injection molding is particularly preferable for molding a toner cartridge container.
以下実施例により詳細を説明するが、本発明はこれに限定されるものではない。 Hereinafter, details will be described by way of examples, but the present invention is not limited thereto.
〔（Ａ）ゴム変性スチレン系樹脂〕
スチレンと不活性溶媒の混合液（エチルベンゼン）にゴム状重合体を溶解して得た重合体（ゴム変性したスチレン系樹脂）とスチレン樹脂を混合したものを用いた。ゴム変性スチレン系樹脂は、ゴム状重合体に１，４−シス結合を９０モル％以上の比率で含有するハイシス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１０．１質量％、ゴム状重合体のゲル含有量２５．３質量％、及びゴム状重合体の体積平均粒子径１．８０μｍであるゴム変性スチレン系樹脂と、還元粘度０．８０ｄｌ／ｇのスチレン樹脂を表１記載のゴム状重合体の質量％となる比率で配合した。ここで言う還元粘度、ゴム状重合体の質量％、ゴム状重合体のゲル含有量の質量％、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。
[(A) Rubber-modified styrene resin]
A mixture of a polymer (rubber-modified styrene resin) obtained by dissolving a rubber-like polymer in a mixed solution of styrene and an inert solvent (ethylbenzene) and a styrene resin was used. The rubber-modified styrene resin uses a high-cis polybutadiene rubber containing a 1,4-cis bond in a ratio of 90 mol% or more in a rubber-like polymer, and has a reduced viscosity of 0.77 dl / g in a matrix portion and a rubber-like weight. A rubber-modified styrenic resin having a coalescence content of 10.1% by mass, a gel content of the rubbery polymer of 25.3% by mass, and a volume average particle diameter of the rubbery polymer of 1.80 μm, and a reduced viscosity of 0.80 dl / G styrene resin was blended at a ratio of mass% of the rubber-like polymer described in Table 1. The reduced viscosity, the mass% of the rubber-like polymer, the mass% of the gel content of the rubber-like polymer, and the volume average particle diameter of the rubber-like polymer as measured herein were measured by the following methods.
〔還元粘度（ηsp／Ｃ）の測定〕
ゴム変性スチレン系樹脂１ｇ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）の試料溶液を作製した。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。またスチレン樹脂は上記の樹脂分と同様の測定方法で測定・算出した。
[Measurement of reduced viscosity (η sp / C)]
A mixed solvent of 15 ml of methyl ethyl ketone and 15 ml of acetone is added to 1 g of rubber-modified styrenic resin, and dissolved by shaking at a temperature of 25 ° C. for 2 hours. 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. The styrene resin was measured and calculated by the same measurement method as that for the above resin component.
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
η sp / C = (t 1 / t 0 −1) / C
t 0 : seconds of pure toluene flow t 1 : seconds of sample solution flow C: polymer concentration
〔ゴム状重合体含有量の測定〕
スチレン系難燃性樹脂組成物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)
Dissolve the styrenic flame retardant resin composition in chloroform, add a certain amount of iodine monochloride / carbon tetrachloride solution and leave it in the dark for about 1 hour, then add 15% potassium iodide solution and 50 ml of pure water. The excess iodine monochloride was titrated with 0.1N sodium thiosulfate / ethanol aqueous solution and calculated from the amount of iodine monochloride added.
〔ゲル含有量の測定〕
ゴム変性したスチレン系樹脂をトルエンに２．５％（質量／体積）の割合で加え、温度２５℃で２時間振とう溶解した後、遠心分離（回転数１００００〜１４０００ｒｐｍ、分離時間３０分）で不溶分（ゲル分）を沈降させ、デカンテーションにより上澄み液を除去してゲルを得た。次に、この膨潤ゲルを温度１００℃で２時間予備乾燥した後、温度１２０℃の真空乾燥機で１時間乾燥した。デシケータで常温まで冷却し、精秤して下式にて算出した。
[Measurement of gel content]
A rubber-modified styrenic resin is added to toluene at a rate of 2.5% (mass / volume), dissolved by shaking at a temperature of 25 ° C. for 2 hours, and then centrifuged (rotation speed: 10,000 to 14000 rpm, separation time 30 minutes). Insoluble matter (gel content) was allowed to settle, and the supernatant was removed by decantation to obtain a gel. Next, this swollen gel was preliminarily dried at a temperature of 100 ° C. for 2 hours, and then dried by a vacuum dryer at a temperature of 120 ° C. for 1 hour. It cooled to normal temperature with the desiccator, weighed precisely, and computed with the following formula.
ゲル分率（％）＝［（ｍ1−ｍ0）／Ｓ］×１００
ｍ0：遠心沈降管質量
ｍ1：乾燥ゲル＋遠心沈降管質量
Ｓ：試料樹脂質量
Gel fraction (%) = [(m 1 −m 0 ) / S] × 100
m 0 : Mass of centrifugal sedimentation tube m 1 : Mass of dried gel + centrifugal sedimentation tube S: Mass of sample resin
〔ゴム状重合体の体積平均粒子径の測定〕
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。
(Measurement of volume average particle diameter of rubbery polymer)
The rubber-modified styrene resin was completely dissolved in dimethylformamide and measured with a laser diffraction particle size distribution apparatus.
〔（Ｂ）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。
[(B) Polyphenylene ether resin]
The product name “PX100F” (manufactured by Mitsubishi Engineering Plastics Co., Ltd., intrinsic viscosity 0.38 dl / g) was used.
〔（Ｃ）縮合リン酸エステル〕
（Ｃ−１）レゾルシノールビス−ジフェニルホスフェート：
商品名「ＣＲ−７３３Ｓ」（大八化学工業社製、リン含有量１０．５質量％）を使用した。
[(C) condensed phosphate ester]
(C-1) Resorcinol bis-diphenyl phosphate:
The brand name “CR-733S” (manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus content 10.5% by mass) was used.
（Ｃ−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。
(C-2) Bisphenol A bis-diphenyl phosphate:
The brand name “CR-741” (manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus content 8.2 mass%) was used.
〔（Ｄ）タルク〕
商品名「ＫＰタルク」（富士タルク社製）を使用した。
[(D) Talc]
The trade name “KP Talc” (manufactured by Fuji Talc) was used.
〔スチレン系難燃性樹脂組成物の調製〕
表１に記載の質量部の（Ａ）ゴム変性スチレン系樹脂、（Ｂ）ポリフェニレンエーテル系樹脂、（Ｄ）タルクを秤量し、ヘンシェルミキサー（三井三池化工（株）製、ＦＭ２０Ｂ）で混合し、得られた混合物をスクリューフィーダ付き二軸押出機（日本製鋼所（株）製、ＴＥＭ２６ＳＳ）で混練した。更に表１に記載の質量部の（Ｃ）縮合リン酸エステルを、押出機の途中から別途に添加して、３００℃で混練して樹脂組成物のペレットを製造した。
[Preparation of Styrenic Flame Retardant Resin Composition]
(A) rubber-modified styrene resin, (B) polyphenylene ether resin, and (D) talc in parts by mass shown in Table 1 are weighed and mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd., FM20B). The obtained mixture was kneaded with a twin-screw extruder with a screw feeder (manufactured by Nippon Steel Works, TEM26SS). Furthermore, the (C) condensed phosphate ester in parts by mass shown in Table 1 was added separately from the middle of the extruder and kneaded at 300 ° C. to produce pellets of the resin composition.
押出し条件
シリンダー設定温度：２００℃（搬送部位）〜３００℃（混練部位）
スクリュー回転数：９００ｒｐｍ
押出速度：５０ｋｇ／ｈ
Extrusion conditions Cylinder set temperature: 200 ° C. (conveying part) to 300 ° C. (kneading part)
Screw rotation speed: 900rpm
Extrusion speed: 50 kg / h
〔成形収縮率〕
得られたペレットを温度７０℃×３時間で加熱乾燥後、平板金型（成形品寸法、縦／横／厚み：１００×１００×３ｍｍ）を射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）に取り付け、シリンダー温度２５０℃、金型温度２５℃で成形した。得られた試験片を温度２３℃、湿度５０％条件下で２４時間放置した後、流れ方向の平板寸法を測定し、成形収縮率を算出した。本発明では、従来のハロゲン系難燃剤を使用したスチレン系難燃性樹脂組成物の成形収縮率の上限である０．６２％以下を合格とした。
[Mold shrinkage]
The obtained pellets were dried by heating at a temperature of 70 ° C. for 3 hours, and then a flat plate mold (molded product dimensions, length / width / thickness: 100 × 100 × 3 mm) was injected into an injection molding machine (Nippon Steel Works, J100E). -P) and molded at a cylinder temperature of 250 ° C and a mold temperature of 25 ° C. The obtained test piece was allowed to stand for 24 hours under conditions of a temperature of 23 ° C. and a humidity of 50%, and then the plate size in the flow direction was measured to calculate the molding shrinkage. In the present invention, 0.62% or less, which is the upper limit of the molding shrinkage rate of a styrene-based flame retardant resin composition using a conventional halogen flame retardant, is regarded as acceptable.
〔成形品の反り〕
得られたペレットを温度７０℃×３時間で加熱乾燥後、箱型金型（成形品寸法、縦／横／深さ：１３０×６０×４５ｍｍ）を射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）に取り付け、シリンダー温度２２０℃、金型温度３０℃で成形した。得られた箱型成形品の長辺中央部の内反りを測定した。本発明では、従来のハロゲン系難燃剤を使用したスチレン系難燃性樹脂組成物の成形品の反りの上限である０．８１ｍｍ以下を合格とした。
[War of molded product]
The obtained pellets were heated and dried at a temperature of 70 ° C. for 3 hours, and then a box mold (molded product dimensions, length / width / depth: 130 × 60 × 45 mm) was formed by an injection molding machine (manufactured by Nippon Steel Works). , J100E-P), and was molded at a cylinder temperature of 220 ° C and a mold temperature of 30 ° C. The warpage of the center part of the long side of the obtained box-shaped molded product was measured. In this invention, 0.81 mm or less which is the upper limit of the curvature of the molded article of the styrene-type flame retardant resin composition using the conventional halogen flame retardant was set as the pass.
〔シャルピー衝撃強さ〕
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（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。この際、シリンダー温度２０５℃、金型温度４５℃とした。
[Charpy impact strength]
The obtained pellets were dried by heating at a temperature of 70 ° C. for 3 hours, and then an A-type test piece (dumbbell) described in JIS K 7139 was molded by an injection molding machine (manufactured by Nippon Steel Works, Ltd., J100E-P). did. At this time, the cylinder temperature was 205 ° C. and the mold temperature was 45 ° C.
上記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）を入れた試験片を用いて、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であり、８ＫＪ／ｍ2以上を合格とした。 Measurement was performed based on JIS K 7111-1, using a test piece cut out from the center of the dumbbell piece and cut into a notch (type A, r = 0.25 mm). When the strength is less than 8 KJ / m 2 , the strength of the molded product is insufficient, and 8 KJ / m 2 or more is regarded as acceptable.
〔荷重たわみ温度〕
上記シャルピー衝撃強さの測定方法に記載した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。耐熱性が７２℃未満だとプリンター、ＦＡＸ、複写機内部で使用するにあたり、トナーカートリッジ容器の耐熱性が不足するため、７２℃以上を満たす組成物を合格とした。
[Load deflection temperature]
Measurement was performed based on JIS K 7191-2 (A method, flatwise) using a test piece cut out from the center of the dumbbell piece described in the Charpy impact strength measurement method. When the heat resistance is less than 72 ° C., the toner cartridge container has insufficient heat resistance when used inside a printer, FAX, or copying machine.
〔燃焼性〕
燃焼性の評価用試験片は、射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）にて、１２７×１２．７×２．０ｍｍの燃焼用試験片を成形した。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号の垂直燃焼試験方法（ＵＬ９４）に基づき、燃焼試験を行った。この試験方法でＶ−２以上の評価となった場合を合格とし、Ｖ−２に満たなかった場合は不合格である。滴下物の消炎時間は１回目と２回目の接炎で滴下した総滴下物の平均消炎時間（試験片５本）の平均値を示した。３０秒以下が合格である。
〔Combustion quality〕
The test piece for evaluation of combustibility was formed as a 127 × 12.7 × 2.0 mm combustion test piece with an injection molding machine (manufactured by Nippon Steel Works, J100E-P). A combustion test was performed based on the vertical combustion test method (UL94) of Subject No. 94 of US Underwriters Laboratories. When this test method results in an evaluation of V-2 or higher, the test is accepted, and when it is less than V-2, the test is rejected. The flame extinguishing time of the dropped product was the average value of the average flame extinguishing time (5 test pieces) of the total dropped product dropped by the first and second flame contact. 30 seconds or less pass.
（Ａ）ゴム変性スチレン系樹脂、（Ｂ）ポリフェニレンエーテル系樹脂、（Ｃ）縮合リン酸エステル、（Ｄ）タルクの各配合量と共に評価結果を表１に示す。 Table 1 shows the evaluation results together with the blending amounts of (A) rubber-modified styrene resin, (B) polyphenylene ether resin, (C) condensed phosphate ester, and (D) talc.
表１の実施例１〜７は本発明のスチレン系難燃性樹脂組成物であり、本願発明の組成及び規定量を満たすことにより、組成に起因する成形収縮率及び成形品の反りを抑制し、更に難燃性と強度に対する高度なバランスを有していることがわかる。 Examples 1 to 7 in Table 1 are styrene-based flame retardant resin compositions of the present invention. By satisfying the composition and specified amount of the present invention, molding shrinkage due to the composition and warpage of the molded product are suppressed. Further, it can be seen that it has a high balance between flame retardancy and strength.
しかし本発明の規定を満足しない比較例１〜７で得られたスチレン系難燃性樹脂組成物では、何れかに優れることはあっても、その全てに優れていることはないことがわかる。 However, it can be seen that the styrene-based flame retardant resin compositions obtained in Comparative Examples 1 to 7 that do not satisfy the provisions of the present invention are excellent in any one, but not all.
例えば、（Ｂ）ポリフェニレンエーテル系樹脂の配合量が少なすぎる比較例１では、荷重たわみ温度が低く、滴下物の消炎時間が長くなってしまい、多すぎる比較例２，７では成形品の反りが大きくなってしまう。また、（Ｃ）タルクを用いなかった比較例３では、成形収縮率が大きくなり、荷重たわみ温度が低く、滴下物の消炎時間が長くなり、タルクの配合量が多すぎる比較例４ではシャルピー衝撃強度が低下してしまった。さらに、ゴム状重合体の含有量が少なすぎる比較例５ではシャルピー衝撃強度が低く、多すぎる比較例６では成形品の反りが大きくなってしまった。 For example, in Comparative Example 1 in which the blending amount of the (B) polyphenylene ether resin is too small, the deflection temperature under load is low and the flame extinguishing time of the dropped product becomes long. It gets bigger. Further, (C) In Comparative Example 3 in which talc was not used, the molding shrinkage ratio was large, the deflection temperature under load was low, the flame extinguishing time of the drop was increased, and in Comparative Example 4 in which the amount of talc was too large, Charpy impact was observed. The strength has decreased. Furthermore, in Comparative Example 5 in which the content of the rubbery polymer is too small, the Charpy impact strength is low, and in Comparative Example 6 in which the content is too large, the warpage of the molded product is large.
本発明のスチレン系難燃性樹脂組成物の特性は特にトナーカートリッジ容器に好適であり、この利点を生かしてプリンター、ＦＡＸ、複写機の内部部品として使用されるトナーカートリッジ容器のノンハロゲン化の進展に寄与することができる。 The characteristics of the styrene-based flame retardant resin composition of the present invention are particularly suitable for toner cartridge containers, and by taking advantage of this advantage, the development of non-halogenated toner cartridge containers used as internal parts of printers, fax machines, and copiers is promoted. Can contribute.
Claims (4)
上記（Ａ）ゴム変性スチレン系樹脂と（Ｂ）ポリフェニレンエーテル系樹脂との合計量を１００質量部とした時、（Ｂ）ポリフェニレンエーテル系樹脂が１０〜３０質量部であり、（Ｄ）タルクが０．１〜１０質量部であり、
上記（Ｃ）縮合リン酸エステルに由来するリン添加量の上記（Ｂ）ポリフェニレンエーテル系樹脂に対する質量部の比が０．０２６〜０．０７２であり、
スチレン系難燃性樹脂組成物中に含まれるゴム状重合体の含有量が３．５〜８．５質量％であることを特徴とするスチレン系難燃性樹脂組成物。 (A) a styrene flame retardant resin composition comprising a rubber-modified styrene resin, (B) a polyphenylene ether resin, (C) a condensed phosphate ester and (D) talc,
When the total amount of the (A) rubber-modified styrene resin and the (B) polyphenylene ether resin is 100 parts by mass, the (B) polyphenylene ether resin is 10 to 30 parts by mass, and (D) talc is 0.1 to 10 parts by mass,
(C) The ratio of the mass part with respect to said (B) polyphenylene ether-type resin of the phosphorus addition amount derived from condensed phosphate ester is 0.026-0.072,
A styrenic flame retardant resin composition, wherein the content of the rubber-like polymer contained in the styrenic flame retardant resin composition is 3.5 to 8.5% by mass.
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