JP2011057848A - Polystyrene-based resin composition - Google Patents
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本発明は、剛性が高く、透明性に優れ、家庭用品や電気製品等の成形材料に用いられるポリスチレン系樹脂組成物に関する。 The present invention relates to a polystyrene resin composition having high rigidity, excellent transparency, and used for molding materials such as household goods and electrical products.
ポリスチレン系樹脂は、安価で、透明性、成形性、剛性に優れた樹脂として、家庭用品、電気製品等の成形材料として広く用いられ、射出成形、或いはシートからの真空、圧空成形等により成形品が得られている。しかしながら、成形材料としてより高い剛性が要求されており、従来は、タルクやガラス繊維等の無機フィラーを添加した樹脂組成物の検討が実施されてきたが、ポリスチレン系樹脂の特徴である透明性が確保できないという問題があり、使用展開が広がっていない。 Polystyrene resins are inexpensive and have excellent transparency, moldability, and rigidity, and are widely used as molding materials for household goods and electrical products. Molded products are produced by injection molding or vacuum or pressure molding from sheets. Is obtained. However, higher rigidity is required as a molding material, and conventionally, studies have been conducted on resin compositions to which inorganic fillers such as talc and glass fiber have been added, but the transparency characteristic of polystyrene resins has been studied. There is a problem that it cannot be secured, and the use development has not spread.
特許文献１には、層状ケイ酸塩を有機化処理してケイ酸塩の層間距離を拡大した後、ナイロン等の樹脂に添加することにより、樹脂の剛性や機械的特性を向上させる方法が開示されている。 Patent Document 1 discloses a method for improving the rigidity and mechanical properties of a resin by adding a layered silicate to a resin such as nylon after organically treating a layered silicate to increase the interlayer distance of the silicate. Has been.
また、特許文献２には、アクリル樹脂に層状ケイ酸塩を添加することで、耐熱性が高く、線膨張率及び吸湿性が低い透明樹脂組成物とする方法が開示されている。 Patent Document 2 discloses a method of forming a transparent resin composition having high heat resistance and low linear expansion coefficient and hygroscopicity by adding a layered silicate to an acrylic resin.
しかしながら、ポリスチレン系樹脂においては、層状ケイ酸塩をそのままポリスチレン系樹脂に添加して組成物としても、透明性を維持しつつ十分に剛性を高めるには至っていない。 However, in a polystyrene resin, even when layered silicate is added to the polystyrene resin as it is as a composition, the rigidity has not been sufficiently increased while maintaining transparency.
本発明の課題は、係る問題を解決し、ポリスチレン系樹脂において、その特徴である透明性を維持しつつ、剛性をより高めることにある。 An object of the present invention is to solve such problems and to increase the rigidity of the polystyrene-based resin while maintaining the characteristic transparency.
本発明は、ベンジルジメチルステアリルアンモニウム塩で処理することにより、ベンジルジメチルステアリルアンモニウム塩を層間に有するベントナイト（Ａ）と、メタクリル酸単位を２質量％以上含有する芳香族ビニル化合物−メタクリル酸系共重合体（Ｂ）と、ステアリン酸金属塩及びラウリン酸金属塩から選択される少なくとも一種（Ｃ）とからなり、（Ｂ）１００質量部に対して（Ａ）が２〜５質量部、（Ｃ）が３〜１０質量部であることを特徴とするポリスチレン系樹脂組成物である。 In the present invention, by treatment with benzyldimethylstearylammonium salt, bentonite (A) having a benzyldimethylstearylammonium salt between layers and an aromatic vinyl compound-methacrylic acid-based copolymer containing 2% by mass or more of methacrylic acid units. Composed of (B) and at least one (C) selected from metal stearate and metal laurate, (B) 100 parts by mass (A) 2-5 parts by mass, (C) Is 3 to 10 parts by mass of a polystyrene-based resin composition.
本発明においては、上記（Ｂ）がメタクリル酸単位を２〜１２質量％含有することが好ましい。 In the present invention, the (B) preferably contains 2 to 12% by mass of methacrylic acid units.
本発明によれば、ポリスチレン系樹脂に特定の処理を施した特定の層状ケイ酸塩と特定の高級脂肪酸金属塩を添加した組成物とすることにより、ポリスチレン系樹脂の透明性を維持しつつ剛性を高めた樹脂材料が提供される。 According to the present invention, the composition is obtained by adding a specific layered silicate obtained by performing a specific treatment to a polystyrene resin and a specific higher fatty acid metal salt, thereby maintaining rigidity of the polystyrene resin. There is provided a resin material having an improved resistance.
本発明のポリスチレン系樹脂組成物は、少なくとも、樹脂成分にフィラー成分と分散剤成分とを均一に混合してなり、フィラー成分として、ベンジルジメチルステアリルアンモニウム塩で処理することにより、ベンジルジメチルステアリルアンモニウム塩を層間に有するベントナイト（Ａ）を、樹脂成分として、メタクリル酸単位を２質量％以上含有する芳香族ビニル化合物−メタクリル酸系共重合体（Ｂ）を、分散剤成分として、ステアリン酸金属塩或いはラウリン酸金属塩（Ｃ）を用いることを特徴とする。 The polystyrene-based resin composition of the present invention comprises at least a filler component and a dispersant component uniformly mixed with a resin component, and is treated with benzyldimethylstearylammonium salt as a filler component, thereby obtaining a benzyldimethylstearylammonium salt. A bentonite (A) having an intermolecular layer as a resin component, an aromatic vinyl compound-methacrylic acid copolymer (B) containing 2% by mass or more of a methacrylic acid unit as a dispersant component, a stearic acid metal salt or A metal salt of lauric acid (C) is used.
本発明に用いられるベントナイトは、層間に交換性陽イオンを有するケイ酸塩鉱物であり、通常、厚さが約１ｍｍ、平均アスペクト比がおよそ５０〜２００程度の微細な薄片状結晶がイオン結合により凝集してなる層状ケイ酸塩の一つである。そして、本発明においては、係るベントナイトをベンジルジメチルステアリルアンモニウム塩で処理することにより、層間に存在する陽イオンをイオン交換し、ベンジルジメチルステアリルアンモニウム塩を有するフィラー成分とすることにより、ポリスチレン系樹脂との高い親和性を得ている。以下、本発明で用いられるベンジルジメチルステアリルアンモニウム塩で処理したベントナイトを未処理のベントナイトと区別して「処理化ベントナイト」と記す。 Bentonite used in the present invention is a silicate mineral having exchangeable cations between layers. Usually, fine flaky crystals having a thickness of about 1 mm and an average aspect ratio of about 50 to 200 are formed by ionic bonding. It is one of the layered silicates formed by aggregation. And, in the present invention, by treating the bentonite with benzyldimethylstearylammonium salt, ion exchange of cations existing between the layers, and using as a filler component having benzyldimethylstearylammonium salt, Has a high affinity. Hereinafter, bentonite treated with benzyldimethylstearylammonium salt used in the present invention is referred to as “treated bentonite” in distinction from untreated bentonite.
上記ベントナイトの処理方法としては、ベントナイトを水に分散させて加熱、攪拌して膨潤させた後、ベンジルジメチルステアリルアンモニウム塩を適量加えて加熱溶解させ、攪拌することでベントナイトの結晶層間の金属イオンをジステアリルジベンジルアンモニウムイオンで置換し、脱水、ろ過、水洗、再度脱水、乾燥することで得られる。 As a method for treating the bentonite, bentonite is dispersed in water, heated and stirred to swell, then an appropriate amount of benzyldimethylstearylammonium salt is added and dissolved by heating, and the metal ions between the bentonite crystal layers are stirred. It is obtained by replacing with distearyl dibenzylammonium ion, dehydrating, filtering, washing with water, dehydrating again and drying.
本発明に用いられるベントナイトの陽イオン交換容量は特に限定されないが、５０〜２００ｍｍ当量／１００ｇであることが好ましい。５００ｍｍ当量／１００ｇ未満の場合には、結晶層間にイオン交換によりインターカレートされるベンジルジメチルステアリルアンモニウム塩の量が少ないために、層間が十分に非極性化されない場合がある。一方、２００ｍｍ当量／１００ｇを超える場合には、ベントナイトの層間の結合力が強固となり、結晶薄片を剥離することが困難な場合がある。尚、イオン交換容量とは、例えば「粘土ハンドブック」（日本粘土学会、１９６７年、技報堂出版発行）などに記載されている方法で測定される値であり、ベントナイト１００ｇ当たりの陽イオン交換容量（当量）で表される。 The cation exchange capacity of bentonite used in the present invention is not particularly limited, but is preferably 50 to 200 mm equivalent / 100 g. In the case of less than 500 mm equivalent / 100 g, the amount of benzyldimethylstearylammonium salt intercalated between the crystal layers by ion exchange is small, so the layers may not be sufficiently nonpolarized. On the other hand, when it exceeds 200 mm equivalent / 100 g, the bond strength between bentonite layers becomes strong, and it may be difficult to peel off the crystal flakes. The ion exchange capacity is a value measured by a method described in, for example, “Clay Handbook” (Japan Clay Society, 1967, published by Gihodo Publishing Co., Ltd.), and the cation exchange capacity per 100 g of bentonite (equivalent amount). ).
本発明で使用する芳香族ビニル化合物−メタクリル酸系共重合体（Ｂ）は、芳香族ビニル化合物とメタクリル酸との共重合体であり、芳香族ビニル化合物としては、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｐ−メチルスチレンが挙げられ、好ましくはスチレンである。係る共重合体（Ｂ）は、メタクリル酸以外に、共重合可能な単量体、例えばアクリロニトリル、メタクリル酸エステル、アクリル酸、無水マレイン酸等を本発明の効果を損なわない範囲で１種または２種以上、共重合していても良い。 The aromatic vinyl compound-methacrylic acid copolymer (B) used in the present invention is a copolymer of an aromatic vinyl compound and methacrylic acid. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, Examples include o-methylstyrene and p-methylstyrene, and styrene is preferable. The copolymer (B) is a copolymerizable monomer other than methacrylic acid, such as acrylonitrile, methacrylic acid ester, acrylic acid, maleic anhydride, etc., as long as the effects of the present invention are not impaired. More than one species may be copolymerized.
上記芳香族ビニル化合物−メタクリル酸系共重合体（Ｂ）は、メタクリル酸単位を２質量％以上含有している。好ましくは、２〜１２質量％、より好ましくは４〜１０質量％である。芳香族ビニル化合物−メタクリル酸系共重合体（Ｂ）のメタクリル酸含有量が２質量％未満の場合は、処理化ベントナイト（Ａ）の分散が不十分で透明性に劣る。また、共重合体（Ｂ）のメタクリル酸含有量が１２質量％を超えると、溶融時の流動性が著しく低下し、成形加工性が悪化する場合や、ゲル状の組成物が発生し、成型加工性や外観に悪影響を及ぼす可能性がある。 The aromatic vinyl compound-methacrylic acid copolymer (B) contains 2% by mass or more of methacrylic acid units. Preferably, it is 2-12 mass%, More preferably, it is 4-10 mass%. When the methacrylic acid content of the aromatic vinyl compound-methacrylic acid copolymer (B) is less than 2% by mass, the dispersion of the treated bentonite (A) is insufficient and the transparency is poor. Further, when the methacrylic acid content of the copolymer (B) exceeds 12% by mass, the fluidity at the time of melting is remarkably lowered and the molding processability is deteriorated, or a gel-like composition is generated and the molding is performed. There is a possibility of adversely affecting the workability and appearance.
芳香族ビニル化合物−メタクリル酸系共重合体（Ｂ）の重合方法としては、塊状重合法、懸濁重合法、溶液重合法等公知のスチレン重合方法が挙げられる。溶媒として例えばベンゼン、トルエン、エチルベンゼン及びキシレン等のアルキルベンゼン類やアセトンやメチルエチルケトン等のケトン類、ヘキサンやシクロヘキサン等の脂肪族炭化水素等が使用できる。また、必要に応じて、脂肪族メルカプタン、芳香族メルカプタン、ペンタフェニルエタン、α−メチルスチレンダイマー及びテルピノーレン等の連鎖移動剤を使用できる。 Examples of the polymerization method of the aromatic vinyl compound-methacrylic acid copolymer (B) include known styrene polymerization methods such as bulk polymerization, suspension polymerization, and solution polymerization. Examples of the solvent include alkylbenzenes such as benzene, toluene, ethylbenzene and xylene, ketones such as acetone and methyl ethyl ketone, and aliphatic hydrocarbons such as hexane and cyclohexane. Moreover, chain transfer agents, such as aliphatic mercaptan, aromatic mercaptan, pentaphenylethane, α-methylstyrene dimer and terpinolene, can be used as necessary.
また、芳香族ビニル化合物−メタクリル酸系共重合体（Ｂ）には、必要に応じて種々の添加剤を配合することができる。添加剤の種類はプラスチックに一般的に用いられるものであれば特に制限はないが、酸化防止剤、難燃剤、滑剤、加工助剤、ブロッキング防止剤、帯電防止剤、防曇剤、耐光性向上剤、軟化剤、可塑剤、無機補強剤、架橋剤、顔料、染料、その他或いはこれらの混合物が挙げられる。例えば、ステアリン酸、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウム等の高級脂肪酸及びその塩やエチレンビスステアリルアミド等の滑剤、流動パラフィン等の可塑剤が含まれていても良い。 Moreover, various additives can be mix | blended with an aromatic vinyl compound-methacrylic acid type copolymer (B) as needed. The type of additive is not particularly limited as long as it is generally used for plastics, but it is antioxidant, flame retardant, lubricant, processing aid, anti-blocking agent, antistatic agent, antifogging agent, light resistance improvement. Agents, softeners, plasticizers, inorganic reinforcing agents, crosslinking agents, pigments, dyes, and the like, or mixtures thereof. For example, higher fatty acids such as stearic acid, zinc stearate, calcium stearate, magnesium stearate and salts thereof, lubricants such as ethylenebisstearylamide, and plasticizers such as liquid paraffin may be included.
本発明で用いる芳香族ビニル化合物−メタクリル酸系共重合体（Ｂ）は、重量平均分子量が１０〜４０万であり、Ｚ平均分子量（Ｍｚ）と重量平均分子量（Ｍｗ）の比（Ｍｚ／Ｍｗ）が１．９〜４．０であることが好ましい。より好ましくは、重量平均分子量が１５〜３５万であり、Ｚ平均分子量（Ｍｚ）と重量平均分子量（Ｍｗ）の比（Ｍｚ／Ｍｗ）が２．０〜３．５である。重量平均分子量が４０万を超える場合、芳香族ビニル化合物−メタクリル酸系共重合体の流動性が低下し、成形性が悪くなり実用的ではない。 The aromatic vinyl compound-methacrylic acid copolymer (B) used in the present invention has a weight average molecular weight of 100,000 to 400,000, and a ratio (Mz / Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw). ) Is preferably 1.9 to 4.0. More preferably, the weight average molecular weight is from 1 to 350,000, and the ratio (Mz / Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw) is from 2.0 to 3.5. When the weight average molecular weight exceeds 400,000, the fluidity of the aromatic vinyl compound-methacrylic acid copolymer is lowered, and the moldability is deteriorated, which is not practical.
上記重量平均分子量（Ｍｗ）、Ｚ平均分子量（Ｍｚ）は、東ソー（株）社製、ＨＬＣ−８０２Ａ型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。
（イ）カラム：東ソー（株）カラム
（ロ）移動相：テトラヒドロフラン
（ハ）試料濃度：０．３質量％
（ニ）測定温度：３８℃
（ホ）検出器：示差屈折計
The said weight average molecular weight (Mw) and Z average molecular weight (Mz) were measured on the following conditions using the Tosoh Corp. make, HLC-802A type | mold gel permeation chromatography (GPC).
(B) Column: Tosoh Corporation Column (b) Mobile phase: Tetrahydrofuran (c) Sample concentration: 0.3% by mass
(D) Measurement temperature: 38 ° C
(E) Detector: Differential refractometer
尚、分子量はポリスチレン換算の値で、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。 The molecular weight is a value in terms of polystyrene. The molecular weight at each elution time is calculated from the elution curve of monodisperse polystyrene, and is calculated as the molecular weight in terms of polystyrene.
芳香族ビニル化合物−メタクリル酸系共重合体（Ｂ）中のメタクリル酸含有量は、該共重合体（Ｂ）０．５ｇを秤量し、トルエン／エタノール＝８／２（体積比）の混合溶液に溶解後、水酸化カリウム０．１ｍｏｌ／Ｌエタノール溶液にて中和滴定を行い、終点を検出し、水酸化カリウムエタノール溶液の使用量より、メタクリル酸の質量基準の含有量を算出したものである。 The content of methacrylic acid in the aromatic vinyl compound-methacrylic acid copolymer (B) is 0.5 g of the copolymer (B), and a mixed solution of toluene / ethanol = 8/2 (volume ratio). After dissolution, the solution was neutralized with 0.1 mol / L ethanol solution of potassium hydroxide, the end point was detected, and the content of methacrylic acid based on mass was calculated from the amount of potassium hydroxide ethanol solution used. is there.
本発明で用いられるステアリン酸金属塩及びラウリル酸金属塩から選択される少なくとも一種（Ｃ）（以下、「高級脂肪酸金属塩（Ｃ）」と記す。）は、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸鉛、ラウリン酸バリウムなどが用いられる。これらは一種のみでも、或いは２種以上を併用しても良い。 At least one (C) selected from metal stearate and metal laurate used in the present invention (hereinafter referred to as “higher fatty acid metal salt (C)”) is zinc stearate, calcium stearate, stearic acid. Magnesium, lead stearate, barium laurate and the like are used. These may be used alone or in combination of two or more.
本発明のポリスチレン系樹脂組成物においては、芳香族ビニル化合物−メタクリル酸系共重合体（Ｂ）１００質量部に対して、処理化ベントナイト（Ａ）を２〜５質量部、高級脂肪酸金属塩（Ｃ）を３〜１０質量部用いる。処理化ベントナイト（Ａ）が２質量部未満では剛性に劣り、５質量部を超えた場合には透明性に劣る。また、高級脂肪酸金属塩（Ｃ）が３質量部未満或いは１０質量部を超えた場合には、いずれも透明性に劣るものとなる。 In the polystyrene resin composition of the present invention, 2 to 5 parts by mass of treated bentonite (A), higher fatty acid metal salt (100 parts by mass of aromatic vinyl compound-methacrylic acid copolymer (B) ( 3 to 10 parts by mass of C) is used. When the treated bentonite (A) is less than 2 parts by mass, the rigidity is poor, and when it exceeds 5 parts by mass, the transparency is inferior. Moreover, when the higher fatty acid metal salt (C) is less than 3 parts by mass or more than 10 parts by mass, both are inferior in transparency.
本発明のポリスチレン系樹脂組成物の製造方法としては特に限定されず、上記（Ｂ）中に（Ａ）、（Ｃ）成分がそれぞれ均一に分散するように混合しうる方法であれば好ましく用いることができる。 It does not specifically limit as a manufacturing method of the polystyrene type-resin composition of this invention, Preferably it will be used if it can mix so that (A) and (C) component may each disperse | distribute uniformly in said (B). Can do.
以下、実施例を挙げて本発明を更に詳しく説明するが本発明はかかる実施例によりその範囲を限定されるものではない。以下に実施例及び比較例に現れる略号の意味を示す。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited the range by this Example. The meanings of the abbreviations appearing in the examples and comparative examples are shown below.
〔樹脂成分〕
ＧＰ：スチレン単独重合体（東洋スチレン（株）製「トーヨースチロール ＭＷ１」）
(Resin component)
GP: Styrene homopolymer (“Toyostyrene MW1” manufactured by Toyo Styrene Co., Ltd.)
Ｓｔ−ＭＡ（１％）：スチレン−メタクリル酸共重合体（メタクリル酸単位１質量％）
完全混合型撹拌槽である第１反応器と第２反応器及び静的混合器付プラグフロー型反応器である第３反応器を直列に接続して重合工程を構成した。スチレン９０．２質量％、エチルベンゼン９．０質量％、メタクリル酸０．８質量％の混合溶液を作製し、スチレンとメタクリル酸の合計量に対して２，２−ビス（４，４−ｔ−ブチルパーオキシシクロヘキシル）プロパンを質量基準で２００ｐｐｍ混合し、原料溶液とした。２，２−ビス（４，４−ｔ−ブチルパーオキシシクロヘキシル）プロパンは、日本油脂（株）製「パーテトラＡ」を使用した。この原料溶液を毎時１３．５ｋｇの割合で第１反応器へ連続的に供給した。各反応器の容量は、第１反応器を３９リットル、第２反応器を３９リットル、第３反応器を１６リットルとした。各反応器の反応温度は、第１反応器で１２０℃、第２反応器で１２５℃、第３反応器では、流れの方向に沿って温度勾配をつけ、中間部分で１３５℃、出口部分で１４０℃となるよう調整した。続いて、第３反応器より連続的に取り出した重合体を含む溶液を直列に２段より構成される予熱器付き真空脱揮槽に導入し、未反応スチレン及びエチルベンゼンを分離した後、ストランド状に押し出して冷却した後、切断してペレットとした。尚、１段目の予熱器の温度は２００℃に設定し、真空脱揮槽の圧力は６．６５×１０4Ｐａとし、２段目の予熱器の温度は２５０℃に設定し、真空脱揮槽の圧力は６６５Ｐａとした。
St-MA (1%): Styrene-methacrylic acid copolymer (methacrylic acid unit 1% by mass)
The polymerization reactor was configured by connecting in series a first reactor that was a complete mixing tank, a second reactor, and a third reactor that was a plug flow reactor with a static mixer. A mixed solution of 90.2% by mass of styrene, 9.0% by mass of ethylbenzene and 0.8% by mass of methacrylic acid was prepared, and 2,2-bis (4,4-t-) was added to the total amount of styrene and methacrylic acid. Butylperoxycyclohexyl) propane was mixed at 200 ppm on a mass basis to obtain a raw material solution. For 2,2-bis (4,4-t-butylperoxycyclohexyl) propane, “Pertetra A” manufactured by NOF Corporation was used. This raw material solution was continuously supplied to the first reactor at a rate of 13.5 kg per hour. The capacity of each reactor was 39 liters for the first reactor, 39 liters for the second reactor, and 16 liters for the third reactor. The reaction temperature of each reactor is 120 ° C in the first reactor, 125 ° C in the second reactor, 125 ° C in the third reactor, with a temperature gradient along the flow direction, 135 ° C in the middle part, and at the outlet part. The temperature was adjusted to 140 ° C. Subsequently, the solution containing the polymer continuously taken out from the third reactor was introduced into a vacuum devolatilization tank with a preheater constituted of two stages in series, and after separating unreacted styrene and ethylbenzene, a strand shape After being extruded and cooled, it was cut into pellets. The temperature of the first stage preheater is set to 200 ° C., the pressure of the vacuum devolatilization tank is set to 6.65 × 10 4 Pa, the temperature of the second stage preheater is set to 250 ° C., and vacuum degassing is performed. The pressure in the volatilization tank was 665 Pa.
Ｓｔ−ＭＡ（４％）：スチレン−メタクリル酸共重合体（メタクリル酸単位４質量％）
完全混合型撹拌槽である第１反応器と第２反応器及び静的混合器付プラグフロー型反応器である第３反応器を直列に接続して重合工程を構成した。スチレン９０．２質量％、エチルベンゼン９．０質量％、メタクリル酸０．８質量％の混合溶液を作製し、スチレンとメタクリル酸の合計量に対して２，２−ビス（４，４−ｔ−ブチルパーオキシシクロヘキシル）プロパンを質量基準で２００ｐｐｍ混合し、原料溶液とした。２，２−ビス（４，４−ｔ−ブチルパーオキシシクロヘキシル）プロパンは、日本油脂（株）製「パーテトラＡ」を使用した。この原料溶液を毎時１３．５ｋｇの割合で第１反応器へ連続的に供給した。各反応器の容量は、第１反応器を３９リットル、第２反応器を３９リットル、第３反応器を１６リットルとした。各反応器の反応温度は、第１反応器で１２０℃、第２反応器で１２５℃、第３反応器では、流れの方向に沿って温度勾配をつけ、中間部分で１３５℃、出口部分で１４０℃となるよう調整した。続いて、第３反応器より連続的に取り出した重合体を含む溶液を直列に２段より構成される予熱器付き真空脱揮槽に導入し、未反応スチレン及びエチルベンゼンを分離した後、ストランド状に押し出して冷却した後、切断してペレットとした。尚、１段目の予熱器の温度は２００℃に設定し、真空脱揮槽の圧力は６．６５×１０4Ｐａとし、２段目の予熱器の温度は２５０℃に設定し、真空脱揮槽の圧力は６６５Ｐａとした。
St-MA (4%): Styrene-methacrylic acid copolymer (methacrylic acid unit 4% by mass)
The polymerization reactor was configured by connecting in series a first reactor that was a complete mixing tank, a second reactor, and a third reactor that was a plug flow reactor with a static mixer. A mixed solution of 90.2% by mass of styrene, 9.0% by mass of ethylbenzene and 0.8% by mass of methacrylic acid was prepared, and 2,2-bis (4,4-t-) was added to the total amount of styrene and methacrylic acid. Butylperoxycyclohexyl) propane was mixed at 200 ppm on a mass basis to obtain a raw material solution. For 2,2-bis (4,4-t-butylperoxycyclohexyl) propane, “Pertetra A” manufactured by NOF Corporation was used. This raw material solution was continuously supplied to the first reactor at a rate of 13.5 kg per hour. The capacity of each reactor was 39 liters for the first reactor, 39 liters for the second reactor, and 16 liters for the third reactor. The reaction temperature of each reactor is 120 ° C in the first reactor, 125 ° C in the second reactor, 125 ° C in the third reactor, with a temperature gradient along the flow direction, 135 ° C in the middle part, and at the outlet part. The temperature was adjusted to 140 ° C. Subsequently, the solution containing the polymer continuously taken out from the third reactor was introduced into a vacuum devolatilization tank with a preheater constituted of two stages in series, and after separating unreacted styrene and ethylbenzene, a strand shape After being extruded and cooled, it was cut into pellets. The temperature of the first stage preheater is set to 200 ° C., the pressure of the vacuum devolatilization tank is set to 6.65 × 10 4 Pa, the temperature of the second stage preheater is set to 250 ° C., and vacuum degassing is performed. The pressure in the volatilization tank was 665 Pa.
Ｓｔ−ＭＡ（８％）：スチレン−メタクリル酸共重合体（メタクリル酸単位８質量％）
原料溶液としてスチレン７６．１質量％、エチルベンゼン１５．５質量％、メタクリル酸５．９質量％、オクタノール２．５質量％の混合溶液を作製し、スチレンとメタクリル酸の合計量に対して１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン（日本油脂（株）製「パーヘキサＣ」）を質量基準で３００ｐｐｍ混合して原料溶液とし、この原料溶液を毎時１２．６ｋｇの割合で第１反応器へ連続的に供給し、反応温度を第１反応器で１２４℃、第２反応器で１３８℃、第３反応器では、流れの方向に沿って温度勾配をつけ、中間部分で１２０℃、出口部分で１３８℃となるよう調整し、２段目の予熱器の温度を２３５℃に設定した以外は、メタクリル酸単位１質量％品と同様とした。
St-MA (8%): Styrene-methacrylic acid copolymer (methacrylic acid unit 8% by mass)
As a raw material solution, a mixed solution of 76.1% by mass of styrene, 15.5% by mass of ethylbenzene, 5.9% by mass of methacrylic acid, and 2.5% by mass of octanol was prepared. 300 ppm of 1-bis (t-butylperoxy) cyclohexane (Nippon Yushi Co., Ltd. “Perhexa C”) was mixed to make a raw material solution, and this raw material solution was made into the first reactor at a rate of 12.6 kg / hour. The reaction temperature is 124 ° C. in the first reactor, 138 ° C. in the second reactor, and in the third reactor, a temperature gradient is created along the direction of flow, and 120 ° C. in the middle part, the outlet The temperature was adjusted to 138 ° C. in part, and the temperature of the second stage preheater was set to 235 ° C., and was the same as the 1% by mass product of methacrylic acid unit.
Ｓｔ−ＭＡ（１０％）：スチレン−メタクリル酸共重合体（メタクリル酸単位１０質量％）
原料溶液としてスチレン７４．１質量％、エチルベンゼン１５．５質量％、メタクリル酸７．９質量％、オクタノール２．５質量％の混合溶液を作製し、スチレンとメタクリル酸の合計量に対して１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン（日本油脂（株）製「パーヘキサＣ」）を質量基準で２５０ｐｐｍ混合して原料溶液とし、この原料溶液を毎時１２．０ｋｇの割合で第１反応器へ連続的に供給し、反応温度を第１反応器で１２４℃、第２反応器で１３８℃、第３反応器では、流れの方向に沿って温度勾配をつけ、中間部分で１２０℃、出口部分で１３８℃となるよう調整し、２段目の予熱器の温度を２２０℃に設定した以外は、メタクリル酸単位１質量％品と同様とした。
St-MA (10%): Styrene-methacrylic acid copolymer (methacrylic acid unit 10% by mass)
As a raw material solution, a mixed solution of 74.1% by mass of styrene, 15.5% by mass of ethylbenzene, 7.9% by mass of methacrylic acid, and 2.5% by mass of octanol was prepared. 1-bis (t-butylperoxy) cyclohexane (“Perhexa C” manufactured by Nippon Oil & Fats Co., Ltd.) was mixed at 250 ppm on a mass basis to form a raw material solution, and this raw material solution was mixed with the first reactor at a rate of 12.0 kg / hour. The reaction temperature is 124 ° C. in the first reactor, 138 ° C. in the second reactor, and in the third reactor, a temperature gradient is created along the direction of flow, and 120 ° C. in the middle part, the outlet The temperature was adjusted to 138 ° C. in the portion, and the temperature of the second stage preheater was set to 220 ° C. The same as the 1% by mass product of methacrylic acid unit.
〔フィラー成分〕
エスベンＮＺ：（株）ホージュン製 ベンジルジメチルステアリルアンモニウム塩にて処理したベントナイト
エスベンＮＸ：（株）ホージュン製 ジメチルステアリルアンモニウム塩にて処理したベントナイト
エスベンＥ：（株）ホージュン製 トリメチルステアリルアンモニウム塩にて処理したベントナイト
ベンゲルＡ：（株）ホージュン製 ベントナイト（未処理）
タルク：富士タルク工業（株）製 ＫＰタルク
ＧＦ：旭硝子（株）製 ガラス繊維 グレード：ＣＳ０３ＭＡＦＴ１６４Ｇ、平均長：１３μｍ
４Ｃ１８Ｂ−Ｔｓ：トピー工業（株）製 合成マイカ
４Ｃ２２−Ｔｓ：トピー工業（株）製 合成マイカ
４ＣＤ−Ｔｓ：トピー工業（株）製 合成マイカ
(Filler component)
Sven NZ: Bentonite treated with benzyldimethylstearylammonium salt manufactured by Hojun Co., Ltd. Sven NX: Bentonite treated with dimethylstearylammonium salt manufactured by Hojun Co., Ltd. Bentonite Bengel A: Bentonite (untreated) manufactured by Hojun Co., Ltd.
Talc: manufactured by Fuji Talc Industrial Co., Ltd. KP Talc GF: manufactured by Asahi Glass Co., Ltd. Glass fiber Grade: CS03MAFT164G, average length: 13 μm
4C18B-Ts: Topy Industries, Ltd. synthetic mica 4C22-Ts: Topy Industries, Ltd. synthetic mica 4CD-Ts: Topy Industries, Ltd. synthetic mica
〔分散剤成分〕
Ｚｎ−Ｓｔ：日本油脂（株）製 ステアリン酸亜鉛
Ｃａ−Ｓｔ：日本油脂（株）製 ステアリン酸カルシウム
Ｍｇ−Ｓｔ：日本油脂（株）製 ステアリン酸マグネシウム
Ｐｂ−Ｓｔ：堺化学工業（株）製 ステアリン酸鉛
Ｂａ−Ｌａ：堺化学工業（株）製 ラウリン酸バリウム
ＥＢＳ：日本油脂（株）製 エチレンビスステアリルアミド
Ｓｔ：日本油脂（株）製 ステアリン酸
Ｚｎ−ＢＡ：堺化学工業（株）製 ｐ−ｔ−ブチル−安息香酸亜鉛
(Dispersant component)
Zn-St: manufactured by Nippon Oil & Fat Co., Ltd. Zinc stearate Ca-St: manufactured by Nippon Oil & Fat Co., Ltd. calcium stearate Mg-St: manufactured by Nippon Oil & Fats Co., Ltd. Magnesium stearate Pb-St: manufactured by Sakai Chemical Industry Co., Ltd. Lead acid Ba-La: Sakai Chemical Industry Co., Ltd. Barium Laurate EBS: Nippon Oil & Fat Co., Ltd. Ethylenebisstearylamide St: Nippon Oil & Fat Co., Ltd. Stearic acid Zn-BA: Sakai Chemical Industry Co., Ltd. p -T-butyl-zinc benzoate
〔評価〕
各例における物性の測定は、以下の方法に従って測定した。
[Evaluation]
The physical properties in each example were measured according to the following method.
（１）ヘーズ値（％）
ＪＩＳ Ｋ ７１３６（１９９４年）に準拠して、日本電色工業（株）製ＮＤＨ２００濁度計にて測定した。
(1) Haze value (%)
Based on JIS K 7136 (1994), it measured with the NDH200 turbidimeter by Nippon Denshoku Industries Co., Ltd.
（２）曲げ弾性率（ＭＰａ）
ＪＩＳ Ｋ ７２０３（１９９４年）に準拠して、（株）東洋精機製ベントグラフにて測定した。
(2) Flexural modulus (MPa)
In accordance with JIS K 7203 (1994), the measurement was performed with a bent graph manufactured by Toyo Seiki Co., Ltd.
（３）比重（ｇ／ｃｍ3）
ＪＩＳ Ｋ ７１１２（１９９９年）に準拠して、ミラージュ貿易製ＥＤ−１２０Ｔ電子比重計にて測定した。
(3) Specific gravity (g / cm 3 )
Based on JIS K 7112 (1999), it measured with the ED-120T electronic hydrometer made from Mirage Trading.
（４）透明性
ヘーズ値が１０％以下を「○」、１０％を超える場合を「×」とした。
(4) Transparency A haze value of 10% or less was rated as “◯”, and a value exceeding 10% was defined as “x”.
（実施例１）
樹脂成分としてスチレン−メタクリル酸共重合体（東洋スチレン（株）製 メタクリル酸４質量％）１００質量部に、フィラー成分としてベンジルジメチルステアリルアンモニウム塩にて処理したベントナイト（ホージュン（株）製「エスベンＮＺ」）を２質量部、分散剤成分としてステアリン酸亜鉛（日本油脂（株）製）３質量部を配合し、タンブラーミキサーでプレブレンドした後、シリンダー温度１７０℃に設定した池貝鉄鋼（株）製二軸押出機「ＰＣＭ−３０」（スクリュー径Φ３０ｍｍ、Ｌ／Ｄ＝４１．３）で溶融混練してポリスチレン系樹脂組成物を得た。二軸押出機の運転条件は下記の通りである。
（１）シリンダー設定温度：１５０℃（搬送部位）〜１７０℃（混練り〜計量部位）
（２）スクリュー回転数：４５０ｒｐｍ
（３）吐出量：１０ｋｇ／ｈ
（４）樹脂温度：１５０〜１７０℃
Example 1
Bentonite ("Esven NZ" manufactured by Hojun Co., Ltd.) treated with 100 parts by mass of styrene-methacrylic acid copolymer (4% by mass of methacrylic acid manufactured by Toyo Styrene Co., Ltd.) as a resin component and benzyldimethylstearyl ammonium salt as a filler component 2) parts by weight, 3 parts by weight of zinc stearate (manufactured by Nippon Oil & Fats Co., Ltd.) as a dispersant component, pre-blended with a tumbler mixer, and then made by Ikekai Steel Co., Ltd., set at a cylinder temperature of 170 ° C. It was melt-kneaded with a twin screw extruder “PCM-30” (screw diameter Φ30 mm, L / D = 41.3) to obtain a polystyrene resin composition. The operating conditions of the twin screw extruder are as follows.
(1) Cylinder set temperature: 150 ° C. (conveying part) to 170 ° C. (kneading to measuring part)
(2) Screw rotation speed: 450rpm
(3) Discharge rate: 10 kg / h
(4) Resin temperature: 150-170 ° C
得られたポリスチレン系樹脂組成物をペレタイズした後、７０℃で４時間熱風乾燥し、シリンダー温度２１０℃、金型温度４０℃で射出成形を行い、試験片を作製し、物性測定に供した。ヘーズ測定用試験片には、１、２、３ｍｍ３段プレートを作製し、１ｍｍ箇所の部位にて、測定を実施した。測定結果を表１に示した。 After pelletizing the obtained polystyrene-based resin composition, it was dried with hot air at 70 ° C. for 4 hours, injection molded at a cylinder temperature of 210 ° C. and a mold temperature of 40 ° C., a test piece was prepared, and subjected to physical property measurement. As test pieces for haze measurement, 1, 2, 3 mm three-stage plates were prepared, and measurement was carried out at a site of 1 mm. The measurement results are shown in Table 1.
（実施例２〜１１，比較例１〜２１）
樹脂成分、フィラー成分、分散剤成分をそれぞれ表１〜３に示す組成に変更する以外は実施例１と同様にしてポリスチレン系樹脂組成物を得、物性を評価した。結果を表１〜３に示す。
(Examples 2-11, Comparative Examples 1-21)
A polystyrene resin composition was obtained in the same manner as in Example 1 except that the resin component, filler component, and dispersant component were changed to the compositions shown in Tables 1 to 3, and the physical properties were evaluated. The results are shown in Tables 1-3.
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| JP2004244510A (en) * | 2003-02-13 | 2004-09-02 | Sekisui Chem Co Ltd | Resin composition, resin sheet, wiring board and coating agent |
| JP2006089683A (en) * | 2004-09-27 | 2006-04-06 | Nippon Steel Chem Co Ltd | Flame retardant resin composition |
| JP2008274097A (en) * | 2007-04-27 | 2008-11-13 | Sumitomo Electric Ind Ltd | Ionomer resin composition and heat shrinkable tube using the same |
| JP2010090339A (en) * | 2008-10-10 | 2010-04-22 | Ps Japan Corp | Flame-retardant resin composition and molded article |
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| JP2004244510A (en) * | 2003-02-13 | 2004-09-02 | Sekisui Chem Co Ltd | Resin composition, resin sheet, wiring board and coating agent |
| JP2006089683A (en) * | 2004-09-27 | 2006-04-06 | Nippon Steel Chem Co Ltd | Flame retardant resin composition |
| JP2008274097A (en) * | 2007-04-27 | 2008-11-13 | Sumitomo Electric Ind Ltd | Ionomer resin composition and heat shrinkable tube using the same |
| JP2010090339A (en) * | 2008-10-10 | 2010-04-22 | Ps Japan Corp | Flame-retardant resin composition and molded article |
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