1279406 九、發明說明： 【發明所屬之技術領域】 —本發明係提供一種透明笨乙烯系樹脂組成物，其係由 笨乙烯系樹脂（A)與少量之雙尿素化合物(B)所組合而成， 並且透明笨乙烯系樹脂組成物之分子量在2, 000〜20, 〇〇〇 ^，佔透明苯乙烯系樹脂組成物之16〜7重量％ ;該透明 笨乙烯系樹脂組成物之成型品之色相、翹曲性、透明性、 作為打火機的耐藥品性等物性佳。1279406 IX. Description of the Invention: [Technical Field of the Invention] The present invention provides a transparent stupid vinyl resin composition which is a combination of a stupid vinyl resin (A) and a small amount of a diurea compound (B). And the transparent stupid vinyl resin composition has a molecular weight of 2,000 to 20, 〇〇〇^, which accounts for 16 to 7% by weight of the transparent styrene resin composition; and the molded article of the transparent styrene resin composition Hue, warp, transparency, and chemical properties such as the light resistance of a lighter are good.
【先前技術】 ^透明笨乙烯系樹脂，例如丙烯腈-苯乙烯樹脂（以下衰 稱AS樹脂），因其加工成型性、物理性及機械性方面㈣ 良好的評價’尤其是賴品的良好外觀及光雜上更是; 一大特色，所以被廣泛使用在雜貨（例如打火機）、玩具' 電子、電器用品及汽車零件上。一般市售之AS樹脂，其卢 稀腈含量都在24重量％左右’然而在有耐藥品性需求之4 型品’例如打火機之外殼，前述市售之ASW脂成型品在暴 入燃料後經常產生破裂之情況，—般狀善前述問題，少 都以增加丙稀腈之含量來改善，例如日本公開特許公報耳 08-12曰7626專利，在AS樹脂製法中，其丙稀猜含量在‘ 55重量％ ’可改善财藥品性。但是隨著丙烯腈含量的增加， AS樹脂的色相變差，透明AS樹脂便帶有黃色或黃標色，特 別是在丙浠腈含量超過26重量％以上時，此—現象更為明 顯。增加丙烯腈之含量賴可改善部份耐藥品性，㈣ ^火，外殼之破_題(打火__品性)仍無法完全解 “—步來說’反而造成了⑽變差的問題。前述提 1279406 高丙_含量之AS樹脂之加工成型品時，常發生麵曲變形 之問題’本發明者雖然曾嘗試加人高級脂肪酸醯胺化合 物，例如乂亞乙基雙硬脂酿胺⑽hylene bis stearyl amide，簡稱EBA) ’但反而造成As樹脂的透明性變差，色 ，變差的不良影響。日本特許公開昭52_119654揭示一種 方香域雙尿素化合物，可做為熱可塑性樹脂之離型劑， 然而其對於丙烯腈含量在26重量％以上之AS樹脂及職 脂中特定低分子量之含量與成型品之色相、趣曲性、透明 眷性、打火機的耐藥品性等作用關係沒有任何教示。因此， 如何使AS樹脂同時具有良好的色相、麵曲性、透明性、作 為打火機外殼的耐藥品性等乃為此領域技術者極欲解決的 問題。 【發明内容】 本發明的目的在於提供—種透明苯乙料樹脂組成 物，其係由透明笨乙烯系樹脂(A)添加少量之雙尿素化合物 (B)所組合而成，並且透明笨乙烯系樹脂組成物中之分子量 在2, _〜20, _以下者，伯透明苯乙烯系樹脂組成物之 1·6〜7.0重量％，可得到具有成型品良好的色相、翹曲性、 透明性、作為打火機外殼的耐藥品性等之苯乙_樹脂組 成物。 【發明詳細說明】 本發明係在提供一種透明苯乙烯系樹脂組成物，其包 含： U) 100重量份之透明笨乙烯系樹脂(Α)，包括苯乙烯系聚 合單位62〜74重量％、腈化乙烯系聚合單位26〜38 6 l2794〇6 重量％及可共聚合單體之聚合單位〇〜40重量％ ; (2) 0· 〇〇2〜1· 〇重量份之雙尿素化合物(β)，其化學式為： R2 - NHCONH-R1-NHCONH-R3 上式化合物中，R1為二價的碳氫化合物基，R2、^分別 為碳數9〜40的脂肪族碳氳化合物基，且，Rl之二價的碳 氫化合物基包括二價的脂肪族基，特別是碳數為丨〜14的 脂肪族碳氫化合物基以及二價的芳香族碳氫化合物基；其 中，透明本乙浠系樹脂組成物之分子量在2, 〇〇〇〜20, 〇〇〇 者，佔透明苯乙烯系樹脂組成物之L 6〜7重量％，該透明 笨乙烯系樹脂組成物之成型品之色相、翹曲性、透明性、 作為打火機的耐藥品性等物性佳。 本發明之透明笨乙烯系樹脂(A)包括苯乙烯系聚合單 位62〜74重量％、腈化乙烯系聚合單位26〜38重量％及 了共t合單體之聚合單位〇〜4〇重量％所組合而成。上述 之聚合單位係前述聚合單體經聚合後形成聚合物中的一個 單位。 ^該苯乙烯系聚合單位之聚合單體具體例可為：苯乙 稀、α —曱基苯乙烯、對-第三了基苯乙烯、對-甲基苯乙烯、 鄰-曱基苯乙烯、間一甲基苯乙烯、2,4一二曱基苯乙烯、乙 基笨乙烯、α —曱基—對—甲基笨乙烯及溴苯乙烯等，其中， 以苯乙烯或α-甲基苯乙烯較佳，上述各化合物可單獨或混 j用。本發明透明苯乙稀細脂(Α)之笨乙烯彳、聚合單位 含夏為62〜74重量％，較佳為63〜72重量％，更佳為64 〜70重量％。 使用於本發明之透明笨乙烯系樹脂（Α)之腈化乙烯系 1279406 聚合單位之聚合單體具體例可為： 等，其中以丙稀腈較佳。本發明 土丙烯腈 猜化乙糊合梅乙糊脂⑷之 重量％，更佳為3G〜36重量^%，較佳為28〜37 ，所=成之社機核㈣⑼性差；若腈化乙焊系= 早位3篁為38重量％以上時，樹脂組成物之色相差。 使驗本㈣之透縣乙_樹脂⑴之可共聚合單 體之聚合單位之聚合單體具體例可為：⑽_旨系單體、 甲基丙烯酸醋系單體、單官能性馬來醯亞胺系軍體、丙烯 酸系單體(如：丙稀酸、甲基丙烯酸）、無水馬來酸、無水 甲基順丁烯—酸、無水甲基反了烯二酸、富馬酸㈤如。 acid)、衣康酸（itac〇nic add)等不飽和幾酸系化合物以 及其_化系單體(例如’富馬酸二曱§旨、衣康酸二丁醋）、 乙烯、丙烯、1-丁烯小戊烯、4_甲基_卜戊烯、氯化乙烯、 氯化^烯叉、四氟化乙烯、一氯三氟化乙烯、六氟化丙婦、 丁二烯、丙烯基胺、異丁烯基胺、醋酸乙烯、乙基乙烯基 醚、甲基乙烯基酮、三烯丙基異氰酸酯（triallyl isocyanate)等。 其中，丙烯酸酯系單體的具體例如··丙烯酸甲酯、丙 烯酸乙醋、丙烯酸異丙酯、丙烯酸正丁酯、聚乙二醇二丙 烯酸®旨等，其中，以丙烯酸正丁酯較佳。 而曱基丙烯酸酯系單體的具體例子如：甲基丙烯酸甲 酯、甲基丙烯酸乙酯、曱基丙烯酸丙酯、甲基丙烯酸丁酯、 甲基丙烯酸苯曱酯、曱基丙烯酸己酯、甲基丙烯酸環己酯、 1279406 甲基丙烯酸十二烷酯、曱基丙烯酸2-羥乙酯、曱基丙烯酸 環氧丙酯、甲基丙烯酸二曱氨基乙酯、乙撐二曱基丙烯酸 酯（ethylene dimethacrylate)、二曱基丙烯酸新戊醋 (neopentyl dimethacrylate)等，其中，以曱基丙稀酸甲 酯、甲基丙烯酸丁酯較佳。 而單官能性馬來醯亞胺系單體是指單體中只含有單一 個馬來蕴亞胺官能基’其具體例子如：馬來酿亞胺、n一曱 基馬來醯亞胺、N-異丙基馬來醯亞胺、N-丁基馬來醯亞胺、 _ N-己基馬來醢亞胺、N-辛基馬來醯亞胺、n-十二烷基馬來 酿亞胺、N-%己基馬來酿亞胺、N-苯基馬來酸亞胺（簡稱 ?^11)、.2-曱基馬來醯亞胺、1^-2,3-二曱基苯基馬來醯亞 胺、N-2, 4-二曱基苯基馬來醯亞胺、n—2, 3-二乙基苯基馬 來醯亞胺、N-2, 4-二乙基苯基馬來醯亞胺、N—2, 3—二丁基 苯基馬來醯亞胺、N-2, 4-二丁基笨基馬來醯亞胺、n—2, 6 二甲基苯基馬來醯亞胺、N-2, 3-二氯苯基馬來醯亞胺、 N-2, 4-二氣笨基馬來醯亞胺、N—2, 3—二溴苯基馬來醯亞胺 • 或1^—2,4-二溴苯基馬來醯亞胺等，其中，以N-苯基馬來醢 亞胺較佳。 本發明之透明苯乙烯系樹脂（A)之可共聚合單體之聚 合單位含置為〇〜4〇重量％，較佳為2〜4〇重量％，更佳 為3〜38重量％。 本發明之雙尿素化合物(B)係以下列化學式為代表·· R2 - NHCONH—Ri—mhCONH-R3 、上式化合物中，二價的碳氫化合物基，r2、r3分別 為碳數9〜40的脂肪族碳氫化合物基，且，^之二價的碳 9 1279406 氫化合物基包括二價的脂肪族基，特別是碳數為1〜14的 脂肪族碳氬化合物基以及二價的芳香族碳氫化合物基，其 具體例包括··亞曱基(Me仕lylene)、亞乙基（Ethylene)、 亞己基(Hexa methylene)、亞笨基(phenylene)、亞曱笨基 (Toluylene)、亞二曱笨基（Xylylene)、雙笨基亞曱基 (diphenyl methylene)等；R2、R3為碳數9〜40的脂肪族碳 氩化合物基，其具體例包括：辛烧基(capryl)、十八烧基 (stearyl)、十二烷基（lauryl)、十六烷基（cetyl)、二十 二烧基(erucyl)、十八礙烯基(oleyl)等。 本發明之雙尿素化合物(B)具體例可為：亞甲基雙十八 礙烯基尿素(Methylene bis-oleyl urea)、亞乙基雙十八 碳烯基尿素(Ethylene bis-oleyl urea)、亞二甲苯基雙十 八碳烯基尿素(Xylylene bis-oleyl urea)、亞甲笨基雙十 八碳烯基尿素（Toluylene bis-oleyl urea)、亞己基雙十 八石炭烯基尿素(Hexa methylene bis-oleyl urea)、雙苯基 亞甲基雙十八碳烯基尿素(Diphenyl methylene bis-oleyl urea);亞甲基雙順式二十二烷基尿素（Methylene bis-erucyl urea)、亞乙基雙順式二十二烧基尿素 (Ethylene bis-erucyl urea)、亞二曱苯基雙順式二十二 烧基尿素（Xylylene bis-erucyl urea)、亞甲苯基雙順式 二十二烧基尿素(Toluylene bis-erucyl urea)、亞己基雙 順式二十二院基尿素（Hexa methylene bis-erucyl urea)、 雙苯基亞甲基雙順式二十二烷基尿素(Diphenyl methylene bis-erucyl urea);亞曱基雙十八烧基尿素（Methylene bis-stearyl urea)、亞乙基雙十八烧基尿素（Ethylene 10 1279406 bis-stearyl urea)、亞二曱苯基雙十八烷基尿素(Xylylene bis-stearyl urea)、亞曱笨基雙十八烷基尿素(Toluylene bis-stearyl urea)、亞己基雙十八烷基尿素（Hexa methylene bis-stearyl urea)、雙苯基亞曱基雙十八烧基 尿素（Diphenyl methylene bis-stearyl urea)，其中，以 亞二曱苯基雙順式十八碳稀基尿素（Xylylene bis-oleyl urea)、亞曱笨基雙十八烧基尿素（Toluylene bis-stearyl urea)、亞己基雙十八烧基尿素（Hexa methylene bis-stearyl urea)、雙苯基亞甲基雙十八烷基尿素 (Diphenyl methylene bis-stearyl urea)為佳；當 R1 為二 價的脂肪族基時，透明苯乙嫦系樹脂(A)之财候性較佳。一 般市售的雙尿素化合物(B)，其商品名例如：日本化成公司[Prior Art] ^Transparent stupid vinyl resin, such as acrylonitrile-styrene resin (hereinafter referred to as AS resin), because of its processing formability, physical properties and mechanical properties (4) Good evaluation 'especially the good appearance of the product And the light is even more; a major feature, so it is widely used in groceries (such as lighters), toys 'electronics, electrical appliances and auto parts. Generally, the commercially available AS resin has a lysine content of about 24% by weight. However, in the case of a type 4 product having chemical resistance requirements such as a lighter, the aforementioned commercially available ASW fat molded article is often used after being intruded into fuel. In the case of rupture, the above problems are generally improved by increasing the content of acrylonitrile. For example, the Japanese Patent Publication No. 08-12曰7626 patent, in the AS resin method, the propylene content is in the ' 55% by weight 'can improve the chemical properties. However, as the acrylonitrile content increases, the hue of the AS resin deteriorates, and the transparent AS resin has a yellow or yellow color, especially when the acrylonitrile content exceeds 26% by weight. Increasing the content of acrylonitrile can improve some of the chemical resistance. (4) ^Fire, the broken shell of the shell (fire __ character) still can not fully solve the "-step" but caused the problem of (10) deterioration. When the above-mentioned 1279406 high-content AS resin is processed into a molded article, the problem of surface buckling often occurs. The inventors have tried to add a higher fatty acid guanamine compound, such as yttrium ethylene bis- stearylamine (10) hylene bis. Stearyl amide (EBA) 'But it causes the transparency of As resin to deteriorate, and the color and deterioration are adversely affected. Japanese Patent Laid-Open No. 52-119654 discloses a double-urea compound, which can be used as a release agent for thermoplastic resin. However, there is no suggestion regarding the relationship between the specific low molecular weight content of the AS resin and the occupational fat having an acrylonitrile content of 26% by weight or more, the hue, the flexibility, the transparency of the molded article, and the chemical resistance of the lighter. Therefore, how to make the AS resin have good hue, curvature, transparency, and chemical resistance as a lighter casing is a problem that the technicians in the field are eager to solve. The object of the present invention is to provide a transparent styrene resin composition which is composed of a transparent stupid vinyl resin (A) and a small amount of a diurea compound (B), and a transparent stupid vinyl resin. The molecular weight of the material is 2, -20, _ or less, and the content of the primary transparent styrene resin composition is 6.6 to 7.0% by weight, and a good color hue, warpage, transparency, and a lighter can be obtained. The present invention provides a transparent styrene resin composition comprising: U) 100 parts by weight of a transparent stupid vinyl resin (Α). Including styrene-based polymerization unit 62 to 74% by weight, nitrile-based ethylene polymerization unit 26 to 38 6 l2794〇6 wt%, and polymerizable unit of copolymerizable monomer 〇~40% by weight; (2) 0· 〇〇 2~1· 〇 by weight of the diurea compound (β), the chemical formula is: R2 - NHCONH-R1-NHCONH-R3 In the above compound, R1 is a divalent hydrocarbon group, and R2 and ^ are respectively carbon number. 9 to 40 aliphatic carbon oxime compound groups, and, Rl The valence hydrocarbon group includes a divalent aliphatic group, particularly an aliphatic hydrocarbon group having a carbon number of 丨14 and a divalent aromatic hydrocarbon group; wherein the transparent acetamino resin composition The molecular weight of the molded article of the transparent styrene resin composition is 6 to 7% by weight, and the color of the transparent styrene resin composition is 6 to 7 wt%. The transparent epoxy resin (A) of the present invention includes 62 to 74% by weight of a styrene-based polymerization unit and 26 to 38% by weight of a nitrile-based polymerization unit, and a total of 2 to 38% by weight of a styrene-based polymerization unit. The polymerization unit of t-monomer is 〇~4〇% by weight. The above polymerization unit is a unit in which a polymerized monomer is polymerized to form a polymer. Specific examples of the polymerizable monomer of the styrene-based polymerization unit may be: styrene, α-mercaptostyrene, p-tert-styryl, p-methylstyrene, o-nonylstyrene, M-methylstyrene, 2,4-dimercaptostyrene, ethyl stupyl ethylene, α-mercapto-p-methyl stupyl ethylene and bromostyrene, among which styrene or α-methylbenzene Ethylene is preferred, and each of the above compounds may be used singly or in combination. The styrene ethylene oxime of the transparent styrene fine condensate of the present invention has a polymerization unit of 62 to 74% by weight, preferably 63 to 72% by weight, more preferably 64 to 70% by weight. Specific examples of the polymerizable monomer of the nitrile-based vinyl 1279406 polymer unit used in the transparent vinyl resin of the present invention may be: exemplified by acrylonitrile. The weight % of the soil acrylonitrile guessing battering paste (4) is more preferably 3G~36% by weight, preferably 28~37, and the machine core (4) (9) is poor; if the nitrile is B Soldering system = When the early 3 篁 is 38% by weight or more, the color difference of the resin composition is poor. The specific example of the polymerizable monomer of the polymerizable unit of the copolymerizable monomer of the present invention (4) can be: (10) _ a monomer, a methacrylic vine monomer, a monofunctional mala Imine army, acrylic monomer (such as: acrylic acid, methacrylic acid), anhydrous maleic acid, anhydrous methyl cis-butyric acid, anhydrous methyl thiodicarboxylic acid, fumaric acid (five) . Acid), itaconic acid (itac〇nic add) and other unsaturated acid compounds and their _chemical monomers (such as 'fumaric acid diterpene, itaconic acid dibutyl vinegar), ethylene, propylene, 1 -butylene pentene, 4-methyl-p-pentene, chlorinated ethylene, chlorinated olefin, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoride, butadiene, propylene Amine, isobutyleneamine, vinyl acetate, ethyl vinyl ether, methyl vinyl ketone, triallyl isocyanate, and the like. Among them, specific examples of the acrylate monomer include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, and polyethylene glycol diacrylic acid®. Among them, n-butyl acrylate is preferred. Specific examples of the mercapto acrylate monomer are: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, phenyl methacrylate, hexyl methacrylate, Cyclohexyl methacrylate, 1279406 lauryl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dinonylaminoethyl methacrylate, ethylene dimercapto acrylate ( Ethylene dimethacrylate), neopentyl dimethacrylate, etc., of which methyl methacrylate or butyl methacrylate is preferred. The monofunctional maleimide monomer refers to a monomer containing only a single maleimide functional group. Specific examples thereof include: maleimine, n-mercaptomaleimine, N-isopropylmaleimide, N-butylmaleimide, _N-hexylmaleimide, N-octylmaleimide, n-dodecylate Imine, N-% hexylmaleimine, N-phenylmaleic acid imine (referred to as ?11), .2-mercaptomaleimine, 1^-2,3-didecyl Phenylmaleimide, N-2,4-dimercaptophenylmaleimide, n-2,3-diethylphenylmaleimide, N-2, 4-diethyl Phenyl phenyl maleimide, N-2, 3-dibutylphenyl maleimide, N-2, 4-dibutyl stupyl maleimide, n-2, 6 dimethyl Phenyl-maleimide, N-2, 3-dichlorophenylmaleimide, N-2, 4-dihydrophenylmaleimide, N-2, 3-dibromobenzene Preferably, the N-phenylmaleimide is preferably a carbamazepine or an anthracene or a bis-bromophenylmaleimide. The polymerization unit of the copolymerizable monomer of the transparent styrene resin (A) of the present invention is contained in an amount of 〇 4 to 4% by weight, preferably 2 to 4 % by weight, more preferably 3 to 38 % by weight. The bis-urea compound (B) of the present invention is represented by the following chemical formula: R2 - NHCONH-Ri-mhCONH-R3, a compound of the above formula, a divalent hydrocarbon group, and r2 and r3 are respectively a carbon number of 9 to 40. An aliphatic hydrocarbon group, and a divalent carbon 9 1279406 Hydrogen group includes a divalent aliphatic group, particularly an aliphatic carbon argon compound having a carbon number of 1 to 14 and a divalent aromatic group. Hydrocarbon group, specific examples thereof include: mercapto (ethylene), ethylene (Ethylene), hexene (phenylene), phenylene, toluylene, sub Xylylene, diphenyl methylene, etc.; R2 and R3 are aliphatic carbon argon compound groups having a carbon number of 9 to 40, and specific examples thereof include: capryl, ten Stearyl, lauryl, cetyl, erucyl, oleyl, and the like. Specific examples of the bis-urea compound (B) of the present invention may be: Methylene bis-oleyl urea, Ethylene bis-oleyl urea, Xylylene bis-oleyl urea, Toluylene bis-oleyl urea, Hexamethyl octadecyl urea (Hexa methylene) Bis-oleyl urea), Diphenyl methylene bis-oleyl urea; Methylene bis-erucyl urea, A Ethylene bis-erucyl urea, Xylylene bis-erucyl urea, and methylene bis-erucyl urea Toluylene bis-erucyl urea, Hexa methylene bis-erucyl urea, Diphenyl methylene bis-diphenyl methylene bis- Erucyl urea); Methylene bis-stearyl urea, ethylene octadecyl Uthylene (Ethylene 10 1279406 bis-stearyl urea), Xylylene bis-stearyl urea, Toluylene bis-stearyl urea, hexylene Hexa- phenyl bis-stearyl urea, diphenyl methylene bis-stearyl urea Xylylene bis-oleyl urea, Toluylene bis-stearyl urea, Hexa methylene bis-stearyl urea, Biphenyl Diphenyl methylene bis-stearyl urea is preferred; when R1 is a divalent aliphatic group, the transparent styrene resin (A) is more economical. A commercially available double urea compound (B), whose trade name is, for example, a Japanese chemical company
的 Hachreen OX、Hachreen ST、Hachreen SH、Hachreen SM 等。 本發明之雙尿素化合物（B)的製法可由胺化合物 (amine)及異氰酸酯（isocyanate)之加成反應（addition reaction)而得，上述胺化合物（amine)之具體例：十二烧 基胺（lauryl amine)、12-羥基十八烷基胺 (12-hydroxystearyl amine)、二十二烷基胺（behenyl amine)等’而異氰酸酯（isocyanate)之具體例：異氰酸甲 醋,、異氰酸丁酯、異氰酸辛酯、異氰酸十八酯、異氰酸苯 酯、亞曱基雙異氰酸酯（Methylene diisocyanate)、亞己 基雙異氰酸酯（Hexylene diisocyanate)、亞苯基雙異氰酸 酯（Phenyl ene di isocyanate)、亞二甲苯基雙異氰酸酯 (Xylylene diisocyanate)、亞甲笨基雙異氰酸酯 1279406 (Toluylene diisocyanate)等。 月透明笨乙烯系樹脂組成物中，雙尿素化合物⑻ 的h相p⑽重量份的透明笨乙烯_旨⑷的〇肩2 ·〇重=’較佳為o omu重量份，更佳為〇·嶋 二0:5重置份，當雙尿素化合物⑻添加量低於〇· 002重量 2日了’則透明笨乙烯系樹脂組成物在射出成型時易於趣曲 ^:形’且打火機的耐藥品性差(爆裂或漏氣），當雙尿素化 =⑻添加量高於丨· G重量份時，M咖苯乙烯系樹脂組 成物之射出成型品之透明度變差。 本發明之透明苯乙烯系樹脂組成物之製造方法，可藉 由批式^續式塊狀餘液聚合、魏聚合、_聚合^ 方法來7L成’其中以連續式塊狀或溶液聚合方法較佳；當 本毛明之透明苯乙烯系樹驗成物由連續式塊狀或溶液聚 5方法|Lie時’其較佳之製造方法乃將原料溶液包含·· 二2重量％之苯乙烯系單體、28〜6〇重量％之睛化乙稀系 皁體、G〜40重量％之可共聚合單體，以上合計刚重量 2 ’及相對於100重量份的全部聚合單體之溶劑〇〜⑼重 量份，連續地送人反應㈣，並㈣量之雙尿素化合物 ⑻、聚合起始劑、鏈轉㈣加人聚合反應器巾進行聚合反 應；上述所使用之溶劑可為苯、甲苯、乙苯、對二甲^、 鄰-甲苯、間二甲苯，及戊烧、辛烧、環己烧，及甲乙嗣、 丙酮、甲丁酮等。 前述聚合反應器可包括··柱狀流式聚合反應器 (P.F.R)、完全混合式聚合反應器（CSTR)或靜力混合式 (static mixing reactor)反應器之同一種或不同種類之組 1279406 合，也可併用兩種或兩種以上之反應器；例如：完全混合 式聚合反應H(CSTi〇與錄流絲合反應时⑽並用。 本發明透明笨乙烯系樹脂組成物聚合時可加入添加劑 餐與聚合，其具體例為多官能性馬來醯亞胺系化合物，例 如· N，N ―4,4 —(3,3’—二甲基二苯基曱烧）雙馬來醢亞胺 〔N，N 4,4 (3,3 -dimethyl diphenyl methane ) bismaleimide〕、N，N，-4, 4, - (3, 3,-二乙基二苯基曱烷） 雙馬來酸亞胺〔N，N，-4, 4，-（3, 3, -diethyl diphenyl • ethane) bismaleimide〕、n, N，-4, 4,-二苯基甲烷雙馬來 酿亞胺（N，N 4, 4 -diphenyl methane bismaleimide ;簡 稱BMI)，其中以N，N、4,4，—二苯基甲烧雙馬來酿亞胺較 佳，添加劑使用量為姆於⑽重量份全部聚合單體的〇 〜1重i份’較佳為〇〜〇·5重量份，更佳為〇〜〇· i重量份。 本發明透明笨乙烯系樹脂組成物聚合中添加之聚合起 始劑，其使用量為相對於100重量份全部聚合單體的〇〜 1· 〇重i份’較佳為〇· 001〜〇· 5重量份，可使用之聚合起 參 始劑之具體例可為··單官能性起始劑或者多官能性起始 劑，其中，具體之單官能性起始劑可例如：過氧化二苯甲 醯（benzoyl peroxide)、過氧化雙苯異丙基（心⑶^^ peroxide)、過氧化第三丁^t—butyl per〇xide)、第三丁 基氫過氧化物（t-butyl hydroperoxide)、氫過氧化異丙苯 (cumene hydroperoxide)、第三丁基過氧化苯甲酸酯 ((t-butyl-peroxy benzoate)、二-2-乙基己基過氧化二碳 酸酯（di-2-ethylhexyl peroxy dicarbonate)、第三丁基 過氧化異丙基碳酸酯（tert—butyl per0Xy is〇pr〇pyl 13 1279406Hachreen OX, Hachreen ST, Hachreen SH, Hachreen SM, etc. The preparation method of the bis-urea compound (B) of the present invention can be obtained by an addition reaction of an amine compound and an isocyanate, and a specific example of the above amine compound: laurylamine (lauryl) Specific examples of isocyanate, such as 12-hydroxystearyl amine, behenyl amine, etc.: isocyanate isocyanate, isocyanate Ester, octyl isocyanate, octadecyl isocyanate, phenyl isocyanate, Methylene diisocyanate, Hexylene diisocyanate, Phenyl ene di isocyanate , Xylylene diisocyanate, 1279406 (Toluylene diisocyanate), and the like. In the monthly transparent stupid vinyl resin composition, the h-phase p (10) parts by weight of the diurea compound (8) is transparent and stupid ethylene--the shoulder of the (4) 2 〇 weight = 'preferably o omu parts by weight, more preferably 〇·嶋20:5 reset parts, when the amount of double urea compound (8) is less than 〇· 002 weight 2 days, then the transparent stupid vinyl resin composition is easy to be interesting in injection molding ^: shape 'and the light resistance of the lighter is poor (Blasting or gas leakage), when the amount of addition of the double-urea = (8) is higher than the weight of the 丨·G, the transparency of the injection-molded article of the M-coffee styrene resin composition is deteriorated. The method for producing the transparent styrene resin composition of the present invention can be carried out by batch-type continuous liquid polymerization, Wei polymerization, or polymerization method, wherein 7L is formed into a continuous block or solution polymerization method. Preferably, when the transparent styrene tree test of the present hair is made from a continuous block or solution poly 5 method|Lie's preferred method of preparing the raw material solution contains 2% by weight of styrene monomer 28~6〇% by weight of the ethylated soap body, G~40% by weight of the copolymerizable monomer, the total weight of the above 2' and the solvent of the total polymerizable monomer relative to 100 parts by weight (~(9) The parts by weight are continuously sent to the reaction (4), and (4) the amount of the diurea compound (8), the polymerization initiator, and the chain transfer (4) are added to the polymerization reactor to carry out polymerization; the solvent used may be benzene, toluene or ethylbenzene. , p-dimethyl phthalate, o-toluene, m-xylene, and pentylene, octyl sulphur, cyclohexane, and methyl ethyl hydrazine, acetone, methyl ethyl ketone and the like. The foregoing polymerization reactor may comprise the same type or a different type of group 1279406 of a columnar flow polymerization reactor (PFR), a complete mixed polymerization reactor (CSTR) or a static mixing reactor. It is also possible to use two or more kinds of reactors in combination; for example, a completely mixed polymerization reaction H (CSTi〇 is used in combination with a liquid chromatography reaction (10). The transparent stupid vinyl resin composition of the present invention may be added to an additive meal during polymerization. And polymerization, a specific example thereof is a polyfunctional maleimide compound, for example, N,N-4,4-(3,3'-dimethyldiphenylfluorene) bismaleimide [ N,N 4,4 (3,3 -dimethyl diphenyl methane ) bismaleimide], N,N,-4, 4, - (3,3,-diethyldiphenylnonane) bismaleimide N,N,-4,4,-(3,3,-diethyl diphenyl • ethane) bismaleimide], n, N,-4, 4,-diphenylmethane bismaleimide (N, N 4, 4 -diphenyl methane bismaleimide; referred to as BMI), wherein N, N, 4, 4, - diphenylmethyl bromide is preferred for the imine, and the amount of the additive is (10) by weight. The 〇~1 weight i part of the monomer is preferably 〇~〇·5 parts by weight, more preferably 〇~〇·i parts by weight. The polymerization initiator added in the polymerization of the transparent styrene resin composition of the present invention The amount used is 〇~1· 〇 i i part of 100 parts by weight of all the polymerized monomers, preferably 〇· 001~〇·5 parts by weight, and a specific example of a polymerization initiator which can be used may be · a monofunctional starter or a polyfunctional starter, wherein the specific monofunctional starter can be, for example, benzoyl peroxide, diphenylisopropyl peroxide (heart (3) ^^ peroxide), peroxylated tert-butyl perxylide, t-butyl hydroperoxide, cumene hydroperoxide, tert-butyl (t-butyl-peroxy benzoate, di-2-ethylhexyl peroxy dicarbonate, tert-butyl peroxy isopropyl carbonate (tert) —butyl per0Xy is〇pr〇pyl 13 1279406
Carb〇nate，_ BPIC)、過氧化環己酮（CyC〇lheXa_ peimide) 、 2,2，_ 偶氮—雙一異丁腈 (2, 2’ -azo-bis-isobutyronitrile ;簡稱 AIBN)、匕！，—偶 氣雙-卜環己院幾腈α丨，韻—bw—cyclohexane carbonitHle) 、2,2’_ 偶氮 _ 雙 _2 甲基丁腈 (2, 2’ -azo-bis-2-methyl butyronitrile)等。其中以過氧 化一苯曱醯、過氧化雙苯異丙基、2, 2，_偶氮_雙-異丁猜較 佳。 馨 上述之多官能性起始劑之具體例可為：1，1—雙—第三丁 ^^^bite.^CU-bis-t-butyl peroxy cyclohexane > 簡稱TX-22)、1’1-雙-第三丁基過氧化_3, 3, 5_三甲基環己 烷 （1，Pbis-t—butyberoxy-S，3, 5-trimethyl cyclohexane ’簡稱τχ_29Α)等；上述聚合起始劑的添加時 機可在聚合中之第一反應器中加入，或其後續之反應器中 加入。 本I明之透明本乙烤系樹脂組成物聚合時，可添加適 • 量的鏈轉移劑，其使用量為相對100重量份全部聚合單體 勺〇 2· 〇重里伤，較佳為0· 001〜1· 〇重量份；本發明所 使用之鏈轉移劑可為單官能性鏈轉移劑或多官能性鏈轉移 ^ ’而具體之單官能性鏈轉移劑例如··硫醇(mercaptan) 類·甲基硫醇、正-丁基硫醇、環己基硫醇、正—十二院基 石瓜醇、硬脂醯基硫醇(stearyl mercaptan)、第三級十二烷 基硫醇(t-dGdeeyl mercaptan，賊TOO、正-喊硫醇、 辛基石;IL醇、弟二-辛基硫醇、第三-壬基硫醇等；多官能 性鏈轉移劑乃例如··異戊四醇四（3—巯基丙酸 14 1279406 西曰 )[pentaerythritol tetrak i s(3-mercapto propionate);簡稱petp] '異戊四醇四（2-酼基乙酸酯） [pentaerythritol tetrakis(2-mercapto ethanate)]等； 上述的鏈轉移劑添加時機可在聚合中之第一反應器中加 入，或其後續之反應器（第二反應器、第三反應器、第四反 應為）中加入。 本發明之透明苯乙烯系樹脂組成物聚合時各反應器之 反應溫度係控制在2〇〜3〇〇充，較佳為6〇〜250°C，更佳為 80 200 C ,反應器之壓力係控制在1〜i〇kg/cm2之間；且 各反應器之攪拌速度為UOOrpm，至於原料溶液滯留在反 應器内之時間—般在G. 5〜15小時，較佳為ho小時； 在樹脂聚合終了後，其單體之最後反應轉鮮約40〜70% ; 再將所得之透明苯乙烯系樹脂組成物溶融物先以預熱器加 熱，然後再以脫揮發裝置移除未反應單體及其他揮發份(脫 ，發P皆段），-般脫揮發裝置可制減壓脫氣槽，或押出脫 氣裝置脫除揮發份，之後以冷凝雜之收減回收液，並 將回收液巾之水分除去後飾作為轉溶液制；而經脫 揮發裳置脫揮之樹脂紐物經冷卻後製粒，亦可將前述炼 融物再經押出機脫揮後餘，即可得淋發明之透明苯乙 烯系樹脂組成物。上述脫揮發裝置可為：單軸或雙轴附有 脫揮口之押域，並可依需要於押出機中加人脫揮助劑， 如··水、環己烷、二氧化碳等。 本發明透明苯乙烯系樹脂組成物之雙尿素化合物⑻ 之添加位置並不限定，可例如在翻笨乙_樹脂組成物 之ω聚合反應暖加人、（ii麻反雜之轉發階段加 1279406 入(例如脫揮用之押出機）、（出）樹脂粒子再押出階段力口 入，就混合均勻性Μ，以⑴聚合反應階段加入較佳。 本發明之透明苯乙烯系樹脂組成物中，分子量在2,麵 〜2〇，_以下者，佔透明苯乙烯系樹脂組成物之1 6〜7 0 重量％的控制方法：可以為使用下述之二種或二種以上之 方法來達成，例如：⑴絲合時添加多官雛鏈轉移劑(例 如.異戊四醇四（3_雜丙咖））、（ii)雙馬來醯亞胺系之 添加劑(例如、〇，_4,4，_二笨基找雙絲醯亞胺）、（iii) 聚合時使帛第-反應！!為挪與其後續—個或—個以上之 RRR並用、（iv)在第二反應器或後續之反應器（例如：第 ^反應器、第四反應器）聚合完成之聚合物溶液，再部份回 /瓜至第-反應H巾繼續進行反應等控制方法，其卜選擇 上述至種控制方法來進行’較佳健擇三種或三種以 上的控制方法來達成。 本發明之透明苯乙烯系樹脂組成物中，Carb〇nate, _ BPIC), Cyc 〇lheXa_ peimide, 2, 2, _ azo-bis-isobutyronitrile (AIBN), 匕! ,—Odd gas double-B-cyclohexylamine nitrile α丨, rhyme—bw—cyclohexane carbonitHle), 2,2′_ azo_bis-2 methylbutyronitrile (2, 2'-azo-bis-2- Methyl butyronitrile) and the like. Among them, peroxybenzene benzoate, diphenyl isopropyl peroxide, 2, 2, _ azo-bis-isobutyl is preferred. Specific examples of the polyfunctional starter described above may be: 1,1-bis-third-buty^^^bite.^CU-bis-t-butyl peroxy cyclohexane > referred to as TX-22), 1'1 -Bis-tert-butylperoxide_3,3,5-trimethylcyclohexane (1,Pbis-t-butyberoxy-S,3,5-trimethyl cyclohexane 'abbreviated as τχ_29Α); the above polymerization initiator The timing of addition may be added to the first reactor in the polymerization, or to the subsequent reactor. When the transparent B-baked resin composition of the present invention is polymerized, an appropriate amount of a chain transfer agent may be added, and the amount of the chain transfer agent used is relatively 100 parts by weight of the total amount of the polymerized monomer. 2, 〇 heavy damage, preferably 0·001 〜1· 〇 by weight; the chain transfer agent used in the present invention may be a monofunctional chain transfer agent or a polyfunctional chain transfer, and a specific monofunctional chain transfer agent such as a mercaptan type. Methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, n-tweldium-based citrin, stearyl mercaptan, tertiary dodecyl mercaptan (t-dGdeeyl) Mercaptan, thief TOO, positive-short thiol, octyl stone; IL alcohol, di-octyl thiol, third-mercapto thiol, etc.; polyfunctional chain transfer agent is, for example, isovaleratetraol ( 3-mercaptopropionic acid 14 1279406 西曰) [pentaerythritol tetrak is (3-mercapto propionate); referred to as petp] 'pentaerythritol tetrakis (2-mercapto ethanate), etc. The above-mentioned chain transfer agent addition timing may be added to the first reactor in the polymerization, or the subsequent reactor (second The reactor, the third reactor, and the fourth reaction are added. The reaction temperature of each reactor in the polymerization of the transparent styrene resin composition of the present invention is controlled to be 2 Torr to 3 Torr, preferably 6 Torr. ~250 ° C, more preferably 80 200 C, the pressure of the reactor is controlled between 1 ~ i 〇 kg / cm 2; and the stirring speed of each reactor is UOOrpm, as the time when the raw material solution stays in the reactor - Generally, in G. 5~15 hours, preferably ho hours; after the end of the polymerization of the resin, the final reaction of the monomer is about 40~70%; and the obtained transparent styrene resin composition melt is firstly The preheater is heated, and then the unreacted monomer and other volatiles are removed by a devolatilization device (removing and sending P), and the devolatilization device can be used to make a decompression degassing tank or to remove the degassing device. Volatile, then the recovered liquid is collected by condensation, and the water of the recovered liquid towel is removed and then used as a transfer solution; and the resin which has been devolatilized by devolatilization is cooled and granulated, and the above-mentioned refining can also be carried out. After the melt is removed from the extruder, the transparent styrene tree can be invented. The defrosting device may be: a uniaxial or biaxial flank with a devolatilization, and may be added with a devolatilizer in the extruder as needed, such as water, cyclohexane, carbon dioxide. The addition position of the diurea compound (8) of the transparent styrene resin composition of the present invention is not limited, and can be, for example, added to the ω polymerization reaction of the styrene-resin composition, and (ii) 1279406 Into (for example, the extruder for devolatilization), and the resin particles are re-exited, the uniformity Μ is mixed, and (1) the polymerization step is preferably added. In the transparent styrene resin composition of the present invention, the molecular weight is 2, the surface is less than 2 Å, or less, and the control method of the transparent styrene resin composition is 16 to 70% by weight. Two or more methods are used to achieve, for example, (1) adding a multi-legged chain transfer agent (for example, pentaerythritol tetra(3), (ii) double malayan) Amine-based additives (for example, 〇, _4, 4, _ bis, bismuthimide), (iii) 帛-reaction during polymerization! For the subsequent use of one or more of the RRR, (iv) polymer solution completed in the second reactor or the subsequent reactor (for example: the second reactor, the fourth reactor), and then The control method such as the reaction/melon-to-reaction H towel continues to be reacted, and the above-mentioned control method is selected to perform the "better choice" three or more control methods. In the transparent styrene resin composition of the present invention,
〜，以下者，佔透明苯乙稀系樹脂組成物=〇: 〇重里^ ’車乂佳為2. 〇〜6. 〇重量％，更佳為2. 5〜5.5重養 % ;當透明苯乙_樹脂組成物中，分子量在2，刪〜 2〇’ 000以下者，佔透明苯乙稀系樹脂組成物之1. 6重量％ 以下，，樹脂組成物成形品之翹雜差，作為打火機外殼 ^财=品=差（爆裂或漏氣）；當透明苯乙_樹脂組成物 刀子$在2, _〜20，_以下者，佔透明苯乙稀系樹 曰、、且成物之7. 〇請以上時，樹脂域物成形品之麵曲 I，特別是作為打火機外殼的耐藥品性差。 本毛明之透明苯乙稀系樹脂組成物在不顯著損及本發 16 1279406 明樹脂組成物之效果的範圍内，可調配其他成份，此等其 他成份例如：著色劑、填充劑、難燃劑、難燃助劑（三氧化 二銻等）、光安定劑、熱安定劑、可塑劑、滑劑、離型劑、 增黏劑、帶電防止劑、氧化防止劑、導電劑等之添加劑。 上述添加劑可例如：礦物油、聚二曱基矽氧烷之有機聚矽 氧烷、位阻胺系抗氧化劑、玻璃纖維等，其可單獨使用或 混合使用；上述成份依需要可於聚合反應階段或反應完成 後添加混合；前述添加劑之使用量（基於100重量份之透明 _ 苯乙烯系樹脂組成物）一般在0〜5重量份，較佳為〇· 〇5〜2 重量份。 此外’在不顯著損及本發明樹脂之效果下，可進一步 調配其他的樹脂，而可添加的其他樹脂如：笨乙烯系甲 基）丙烯酸酯系-丙烯腈系共聚物、苯乙烯系一（甲基）丙烯酸 酉曰系共t物、本乙烯系一（曱基）丙晞酸酯系—丙烯腈系—馬來 醯亞胺系共聚物、苯乙烯系—（甲基）丙烯酸酯系—馬來醯亞 胺系共聚物、（甲基）丙烯酸酯系—馬來醯亞胺系共聚物，或 ⑩ 經二烯轉觀質（或紐改質）之前述絲物。前述添加 ^他樹脂使用量為相對於透明苯乙烯系樹脂組成物1〇〇重 量份的G〜·重量份，其可調整或提高樹驗成物的耐熱 性、剛性及流動加工性。 ”' 本毛月之透明本乙烤糸樹脂組成物的用途並無特別的 限制，其可適用於射出成型、壓縮成型、押出成型、熱成 里真空成型及中空成型所製成之成品，例如押板、成型 ΠΠ等，並可依配方調配達成高流動性、高耐熱性等需求。 本毛月之透明本乙細糸樹脂組成物之物性測定基準， 1279.406 如以下所示：~, the following, accounted for the transparent styrene resin composition = 〇: 〇 重里 ^ '车乂佳 is 2. 〇 ~ 6. 〇 weight%, more preferably 2. 5~5.5 re-raising %; when transparent benzene In the composition of the resin composition, the molecular weight is 2, and the amount of the transparent styrene resin composition is 1.6% by weight or less, and the resin composition molded article is a lighter. Shell ^ 财 = product = poor (burst or leak); when transparent styrene _ resin composition knife $ in 2, _~20, _ below, accounting for transparent styrene tree 曰, and the product of 7 When the above is applied, the surface of the resin-formed product I, in particular, is poor in chemical resistance as a lighter outer casing. The transparent styrene resin composition of the present invention can be blended with other components within a range that does not significantly impair the effect of the resin composition of the present invention, such as colorants, fillers, and flame retardants. Additives such as flame retardant additives (such as antimony trioxide), light stabilizers, thermal stabilizers, plasticizers, slip agents, release agents, tackifiers, antistatic agents, oxidation inhibitors, and conductive agents. The above additives may be, for example, mineral oil, organopolyoxyalkylene oxide, hindered amine antioxidant, glass fiber, etc., which may be used singly or in combination; the above components may be used in the polymerization reaction stage as needed. Or the mixture is added after the completion of the reaction; the amount of the above-mentioned additive (based on 100 parts by weight of the transparent styrene resin composition) is usually 0 to 5 parts by weight, preferably 5 to 2 parts by weight. Further, other resins may be further blended without significantly impairing the effect of the resin of the present invention, and other resins which may be added are, for example, a stupid vinyl methyl acrylate-acrylonitrile copolymer and a styrene one ( Methyl)acrylic acid lanthanum t-substrate, the present vinyl-based (mercapto)propionate-acrylonitrile-maleimide copolymer, styrene-(meth)acrylate- A maleic amide copolymer, a (meth) acrylate-maleimide copolymer, or a filament of 10 which is diene-transferred (or modified). The amount of the resin to be added is G to · parts by weight based on 1 part by weight of the transparent styrene resin composition, which can adjust or improve the heat resistance, rigidity and flow processability of the test article. "The use of the transparent moon bake resin composition is not particularly limited, and it can be applied to injection molding, compression molding, extrusion molding, hot forming, vacuum forming and hollow molding, for example, Plate, molding, etc., and can be formulated according to the formula to achieve high fluidity, high heat resistance, etc. The standard of physical properties of the transparent resin of this month is 1279.406 as shown below:
Ν' t—I 丨〇月乂日修(史)正替換頁 透明苯乙烯系樹脂(A)中笨乙烯系聚合單位、腈化乙烯 系聚合單位及可共聚合單體之聚合單位測定 以Nicolet公司製、型號Nexus 470之傅立葉變換紅外 線分光計（Fourier Transf0rm Infrared Spectr〇meter) 測定。 2·透明苯乙烯系樹脂組成物之分子量在2, 〇〇〇〜2〇, 〇〇〇者 之含量（基於透明苯乙烯系樹脂組成物之重量％)測定 透明苯乙烯系樹脂組成物溶於四氫呋喃之溶劑中，依據 Waters company供應至凝膠透析方法Gpc，並以聚苯乙 烯作分析標準，依以下的條件測定：Ν't-I 丨〇月乂日修 (History) is replacing the transparent styrenic resin (A) in the stupid vinyl polymerization unit, the nitrile ethylene polymerization unit and the polymerization unit of the copolymerizable monomer. The company's model, model Nexus 470, was measured by Fourier Transf0rm Infrared Spectr〇meter. 2. The molecular weight of the transparent styrene resin composition is 2, 〇〇〇 2 2 〇, and the content of the styrene resin composition (based on the weight % of the transparent styrene resin composition) is determined to be soluble in the transparent styrene resin composition. The solvent of tetrahydrofuran was supplied to the gel dialysis method Gpc according to Waters company, and was determined by the following conditions using polystyrene as an analytical standard:
管柱：KD-806M 檢出器：RI-410 , UV-486 移動相：THF(Tetrahydrofuran)(流速 1· 〇c· c/min)。 3·透明笨乙烯系樹脂組成物之透明度(Haze)測定 射出厚度3mm的圓盤，以Nippon Denshoku公司製， NDH-2000型機台，依ASTM D 1003方法測定。 4·透明本乙細糸樹脂組成物之麵曲性 將透明苯乙烯系樹脂組成物於Nigata射出機中以250 °C之射出溫度，冷卻時間25秒，模具溫度5〇t下，射 出長15cm、寬15cm、厚〇· lcm之平板，放置至室溫後， 量其翹曲高度。 〇：翹曲高度小於2mm △ •輕曲高度2mm〜3刪 X :翹曲高度大於3mm 1279406 5·透明本乙細糸樹脂組成物之色相 將透明笨乙_樹脂組成物經射出厚3mm之圓盤試片， 以目視觀察試片的黃色程度。 〇:色相澄清不帶黃色；色相佳 △:略呈黃色；色相普通 X:黃色度深；色相差 6·透明笨乙烯系樹脂組成物之打火機的耐藥品性的測定 透明笨乙烯系樹脂組成物以射出條件：射出溫度210 # C、射出壓力6bars，背壓45kg/cm2，週期I9· 6秒，得 到長X寬X壁厚為65mmx21mmxL 72mm之打火機外殼，將 打火機外殼之燃料容室中填充丁烷氣體至7〇%〜8〇% 滿，將其浸於溫度65t：的水中，測試時間為4小時，觀 察打火機外殼是否有爆裂或漏氣的情形，以50個打火 機外殼作試驗： ◎ •表爆裂或漏氣〇〜2個 〇·表爆裂或漏氣3〜5個 _ △•表爆裂或漏氣6〜8個 ·表爆裂或漏氣9個以上 【實施方式】 以下所述僅為本發明較佳可行實施例，舉凡熟習此項 技藝人仕’其依本發明精神範疇所作之修飾或等效變更， 均理應包含在本案發明申請專利範圍内。 【實施例1】 將苯乙烯單體63重量％，丙烯腈單體37重量％，及相 對苯乙烯單體及丙烯腈單體總和1〇〇重量份之乙苯1〇重量 19 1279406 份，2, 2’ -偶氮-雙-異丁腈(ΑΙΒΝ)0· 02 重量份，Ν，Ν’ -4,4’ -二苯基曱烷雙馬來醯亞胺（ΒΜΙ) 0· 1重量份，亞己基雙十 八烷基尿素(HachreenSH)O· 08重量份組成的進料溶液，用 泵浦35kg/小時之流量，連續地供給至容量40公升之第一 反應器（完全混合式聚合反應器，CSTR)中進行反應，另外， 再泵入相對於苯乙稀單體及丙烯腈單體總和1〇〇重量份之Column: KD-806M Detector: RI-410, UV-486 Mobile phase: THF (Tetrahydrofuran) (flow rate 1· 〇c· c/min). 3. Haze measurement of transparent vinyl resin composition A disk having a thickness of 3 mm was produced and measured by Nippon Denshoku Co., Ltd., NDH-2000 machine, according to ASTM D 1003. 4. The surface curvature of the transparent bismuth resin composition The transparent styrene resin composition was sprayed at a temperature of 250 ° C in a Nigata injection machine, and the cooling time was 25 seconds. The mold temperature was 5 〇t, and the injection length was 15 cm. The plate is 15 cm wide and thick and lcm. After being placed at room temperature, the warp height is measured. 〇: The warpage height is less than 2mm △ • The light height is 2mm~3. X: The warp height is greater than 3mm. 1279406 5. The color of the transparent resin composition is transparent and the styrene composition is formed by a thickness of 3mm. A test piece was taken to visually observe the yellowness of the test piece. 〇: Hue clarification without yellow color; good hue △: slightly yellow; hue ordinary X: yellow degree deep; hue difference 6 · transparent stupid vinyl resin composition of lighter resistance test of transparent stupid vinyl resin composition The injection conditions: injection temperature 210 # C, injection pressure 6 bars, back pressure 45kg/cm2, cycle I9·6 seconds, obtain a lighter shell with a length X width X wall thickness of 65mmx21mmxL 72mm, and fill the fuel chamber of the lighter housing When the alkane gas is 7〇%~8〇% full, immerse it in water with a temperature of 65t: for 4 hours. Observe the case of the lighter shell if it bursts or leaks. Test with 50 lighter shells: ◎ • Table burst or leaking 〇~2 〇·Table burst or leak 3~5 _ △• Table burst or leak 6~8·Table burst or leak 9 or more 【Embodiment】 The following is only The preferred embodiments of the present invention are intended to be included within the scope of the present invention. [Example 1] 63% by weight of styrene monomer, 37% by weight of acrylonitrile monomer, and 1 part by weight of ethyl benzene and 1 part by weight of styrene monomer and acrylonitrile monomer, 19 1279406 parts, 2 , 2'-azo-bis-isobutyronitrile (ΑΙΒΝ)0· 02 parts by weight, Ν,Ν' -4,4'-diphenylnonane bismaleimide (ΒΜΙ) 0·1 parts by weight , a feed solution of hexamethylene octadecylurea (HachreenSH) O·08 parts by weight, continuously supplied to a first reactor having a capacity of 40 liters at a flow rate of 35 kg/hour (completely mixed polymerization) The reaction is carried out in CSTR), and further, pumped in an amount of 1 part by weight based on the total of the styrene monomer and the acrylonitrile monomer.
0.3重量份的第三級十二烷基硫醇（簡稱TDM)至第一反應 器；上述第一反應器之反應溫度ll〇°C，攪拌速度i5〇rpm， 第一反應器反應完的聚合物溶液進入容量4〇公升之第二反 應器（完全混合式聚合反應器，CSTR)，第二反應器之反應 溫度115°C，攪拌速度120rpm ;第二反應器反應完的聚合 物溶液進入容量75公升之第三反應器（柱狀流式聚合反應 器，P.F. R)，第三反應器之反應溫度125°c，攪拌速度 30rpm ;第三反應器的部份聚合物溶液回流至第一反應器繼 續反應，回流量為10kg/hiS第三反應器底端之熔融樹脂測 其最後反應轉鮮在51%，料三反應n底端战融樹脂經 脫揮發設備脫縣反應的單體及糊，再麵頭押出條狀 物後，經冷卻、切粒，即可得到本發明的透明笨乙婦系樹 脂組成物，分析透明苯乙烯系樹驗成物巾，透明苯 系》(A)之笨乙烯系聚合單位之含量（重量% )、猜化 =聚合單位之含#(重量％)及可料合物之聚 H如、及姉於透明苯乙烯系樹脂⑽ 之雙尿素化合物_含量（重⑽，並且分析翻笨乙二 =樹脂組成物分子量在2, _〜2M⑼町者之含 。，並和透明本乙_樹脂組成物之透明雜㈣、趣 20 1279406 曲性、色相及製成打火機外殼的财藥品性等物性，分析及 5平價結果如表一。 【實施例2〜8】 同實施例1之透明苯乙烯系樹脂組成物的製造方法及 刼作過程，並根據表一的進料組成及聚合操作條件，依序 製得本發明透明苯乙烯系樹脂組成物的實施例2〜8，但實 施例5如表一所示為依序利用第一反應器（完全混合式聚合 反應器’CSTR)及第二反應器（柱狀流式聚合反應器，p. f. R.) 進行聚合反應；分析透明苯乙烯系樹脂組成物中，透明苯 乙烯系樹脂(A)之苯乙烯系聚合單位之含量（重量％ )、腈化 乙烯系聚合單位之含量（重量％)及可共聚合單體之聚合單 位之含量（重量％ )、及相對於透明苯乙烯系樹脂(A)l〇〇重 里伤之雙尿素化合物(B)的含量（重量份），並且分析透明笨 乙烯系樹脂組成物分子量在2, 〇〇〇〜20, 000以下者之含量 (重量％);並評價透明苯乙烯系樹脂組成物之透明度 (Haze)、翹曲性、色相及製成打火機外殼的耐藥品性等物 性’ i析及评價結果如表^ —。 【實施例9】 將苯乙烯單體63重量％，丙烯腈單體37重量％，及 相對於上述本乙細早體及丙細猜單體總和重量份之乙 笨10重量份，Ν，Ν’ -4, 4,-二笨基曱烷雙馬來醯亞胺（BMI) 〇· 05重置份、1，1—雙—第三丁基過氧化—3, 3, 5-三甲基環己 烷(ΤΧ-29Α)0·01重量份所組成的進料溶液，用泵浦35kg/ 小時之流量，連續地供給至容量4〇公升之第一反應器（完 全此合式聚合反應器，CSTR)中進行反應，另外，再泵入相 1279406 對於苯乙烯單體及丙烯腈單體總和1〇〇重量份之〇· 3重量 份的第三級十二烷基硫醇至第一反應器；上述第一反應器 之反應溫度110°c，攪拌速度i5〇rpm，第一反應器反應完 的聚合物溶液進入容量40公升之第二反應器（完全混合式 聚合反應器，CSTR)，第二反應器之反應溫度uyc，攪拌 速度120rpm，弟一反應反應完的聚合物溶液進入容量75 公升之第三反應器（柱狀流式聚合反應器，pFR)，第三反應 為之反應溫度13(TC，攪拌速度30rpm ;第三反應器之部份 聚合物溶液回流至第一反應器，回流量為1〇kg/hr;第三反 應為底端之炫融樹脂測其最後反應轉換率在Μ%，將第三反 應為底端之熔融樹脂經脫揮發設備脫揮未反應的單體及溶 劑，再經模頭押出條狀物後，經冷卻、切粒，得到透明笨 乙烯系樹脂(A)，再取上述透明苯乙烯系樹脂(A)1〇〇重量份 與亞己基雙十八烷基尿素(Hachreen SH)(B)〇 55重量份， 以附有排氣口的雙軸押出機之設定溫度19〇〜22(rc的條件 下熔融混練，可製得具顆粒(pellet)狀的本發明之透明苯 乙烯系樹脂組成物；分析透明笨乙烯系樹脂組成物中，透 明苯乙稀系樹脂（A)之苯乙烯系聚合單位之含量（重量 % )、腈化乙烯系聚合單位之含量（重量％)及可共聚合單體 之聚合單位之含量（重量％ )、及相對於透明苯乙烯系樹脂 (A)100重量份之雙尿素化合物(β)的含量（重量份），並且分 析透明苯乙烯系樹脂組成物分子量在2, 〇〇〇〜20, 〇〇〇以下 者之含量（重量❹/◦);並評價透明苯乙烯系樹脂組成物之透明 度(Haze)、翹曲性、色相及製成打火機外殼的耐藥品性等 物性，分析及評價結果如表一。 22 1279406 【比較例1】 將本乙烯單體77重量％，丙烯腈單體23重量％，及相 對於笨乙烯單體及丙烯腈單體總和100重量份之乙苯 (肪)1〇重量份，2,2’-偶氮—雙-異丁腈以1抓)〇〇25重量 份’ Ν，Ν’ -4, 4,-二苯基甲烷雙馬來醯亞胺（BMI) 0· 05重量 份’亞己基雙十八烷基尿素(HachreenSH)O· 12重量份組成 的進料溶液，用泵浦35kg/小時之流量，連續地供給至容量 40公升之第一反應器（完全混合式聚合反應器，CSTR)中進 行反應，另外，再泵入相對於苯乙烯單體及丙烯腈單體總 和100重量份之〇·3重量份的第三級十二烷基硫醇（簡稱 TDM)至第一反應器；上述第一反應器之反應溫度11〇。〇，攪 拌速度150rpm，第一反應器反應完的聚合物溶液進入容量 4〇公升之第二反應器（完全混合式聚合反應器，CSTR)，第 —反應為之反應溫度120C，授拌速度12〇rpm ;第二反應 器反應完的聚合物溶液進入容量75公升之第三反應器（柱 狀流式聚合反應器，PFR)，第三反應器之反應溫度13(rc， 攪拌速度30rpm;第三反應器底端之熔融樹脂測其最後反應 轉換率在50%，將第三反應器底端之熔融樹脂經脫揮發設備 脫揮未反應的單體及溶劑，再經模頭彳甲出條狀物後，經冷 卻、切粒，即可得到苯乙烯系樹脂組成物，分析苯乙烯系 樹脂組成物中，苯乙烯系樹脂(A)之苯乙烯系聚合單位之含 里（重量％ )、腈化乙浠系聚合單位之含量（重量％)及可共聚 合單體之聚合單位之含量（重量％ )、及相對於苯乙烯系樹 脂(A)100重量份之雙尿素化合物(B)的含量（重量份），並且 分析透明苯乙烯系樹脂組成物分子量在2, 〇〇〇〜2〇, 〇〇〇以 23 1279406 下者之含量（重量％);並評價透明苯乙烯系樹脂組成物之透 明度（Haze)、翹曲性、色相及製成打火機外殼的耐藥品性 等物性，分析及評價結果如表二。 【比較例2〜4】 同比較例1之本乙細糸樹脂組成物的製造方法及操作 過程’並根據表二的進料組成及聚合操作條件，依序製得 笨乙烯系樹脂組成物，分析笨乙烯系樹脂組成物中，苯乙 烯系樹脂(A)之苯乙烯系聚合單位之含量（重量％ )、赌化乙 烯系聚合單位之含量（重量％)及可共聚合單體之聚合單位 之含量（重量％ )、及相對於苯乙烯系樹脂(A)1〇〇重量份之 雙尿素化合物(B)的含量（重量份），並且分析透明笨乙烯系 樹脂組成物分子量在2, 000〜20, 000以下者之含量（重量 %);並評價透明苯乙浠系樹脂組成物之透明度(Haze)、鍾 曲性、色相及製成打火機外殼的耐藥品性等物性，分析及 評價結果如表二。 【比較例5】 將苯乙烯單體63重量％，丙烯腈單體37重量％，及相 對於本乙細早體及丙稀腈單體總和1QQ重量份之乙苯 (EB)10重量份，1，；[—雙-第三丁基過氧化—3, 3, 5〜三曱基環 己烧（簡稱ΤΧ-29Α)0· 01重量份，組成的進料溶液，用果浦 35kg/小時之流量，連續地供給至容量4〇公升之第一反廡 器（完全混合式聚合反應器，CSTR)中進行反應，另外，再 泵入相對於100重量份笨乙烯單體及丙烯腈單體總和1〇〇 重量份之0· 3重量份的第三級十二烷基硫醇（簡稱TDM)至 第一反應器；上述第一反應器之反應溫度11(rc，攪拌速度 24 1279406 150rpm，第一反應器反應完的聚合物溶液進入容量4〇公升 之第二反應器（完全混合式聚合反應器，CSTR)，第二反應 器之反應溫度115°C，攪拌速度120rpm ;第二反應器反應 完的聚合物溶液進入容量75公升之第三反應器（柱狀流式 聚合反應器，PFR)，第三反應器之反應溫度丨洲它，攪拌速 度30rpm;第三反應器底端之熔融樹脂測其最後反應轉換率 在53%，將第三反應器底端之熔融樹脂經脫揮發設備脫揮未 反應的單體及溶劑，再經模頭押出條狀物後，經冷卻、切 _ 粒，得到苯乙烯系樹脂(A)。將上述笨乙烯系樹脂(A)再與 亞乙基雙硬月曰醯胺（Ethylene bis stearyl amide ;簡稱 ΕΒΑ)0· 45重量份，以附有排氣口的雙轴押出機之設定溫度 190〜220°C的條件下熔融混練，可製得具顆粒(peUet)狀 的苯乙烯系樹脂組成物，分析苯乙烯系樹脂組成物中，苯 乙烯系樹脂(A)之笨乙烯系聚合單位之含量（重量％ )、腈化 乙烯系聚合單位之含量（重量及可共聚合單體之聚合單 位之含量（重量％ )、及相對於苯乙烯系樹脂(A)1〇〇重量份 • 之雙尿素化合物⑻的含量（重量份），測苯乙烯系樹脂組成 物中分子量在2, 000〜2〇, 〇〇〇以下者之含量（重量;並評 價苯乙烯_麵成物之透明度(Haze)、翹雜、色相及 製成打火機外殼的耐藥品性#物性，分析及評價結果如表 二0 【比較例6】 、同比侧5崎乙烯祕脂喊物的製造方法及操作 過，亚根據表二的進料組成及聚合操作條件製得苯乙稀 系触⑷’將上述笨乙稀系樹脂⑴再與亞己基雙十八燒 25 1279406 基尿素(Hachreen SH)1.2重量份，以附有排氣口的雙軸押 出機之設定溫度190〜220°C的條件下熔融混練，可製得笨 乙稀系樹脂組成物’分析苯乙烯系樹脂組成物中，苯乙烯 系樹脂(A)之笨乙稀系聚合單位之含量（重量％ )、腈化乙烯 系聚合單位之含量（重量％)及可共聚合單體之聚合單位之 含量（重量％ )、及相對於苯乙烯系樹脂(A)l〇〇重量份之雙 尿素化合物(B)的含量（重量份），測苯乙烯系樹脂組成物中 分子量在2, 000〜20, 000以下者之含量（重量並評價苯 乙烯系樹脂組成物之透明度(Haze)、翹曲性、色相及製成 打火機外殼的耐藥品性等物性，分析及評價結果如表二。 【比較例7】 將苯乙烯單體68重量％，丙烯腈單體32重量％，及相 對於苯乙烯單體及丙烯腈單體總和1〇〇重量份之乙苯(EB)7 重量份組成的進料溶液，用泵浦35kg/小時之流量，連續地 供給至容量40公升之第一反應器（完全混合式聚合反應 器，CSTR)中進行反應，另外，再泵入相對於笨乙烯單體及 丙烯腈單體總和100重量份之〇·3重量份的第三級十二烷 基硫醇(簡稱TDM)至反應器；上述反應器之反應溫度130 t：，攪拌速度150rpm，其最後反應轉換率在45%，聚合反 應後製得苯乙烯系樹脂組成物，分析苯乙烯系樹脂組成物 中’本乙:fep糸樹脂（A)之苯乙烯系聚合單位之含量（重量 % )、腈化乙烯系聚合單位之含量（重量。/◦)及可共聚合單體 之聚合單位之含量（重量％ )、及相對於苯乙烯系樹脂 (A)l〇〇重量份之雙尿素化合物(β)的含量（重量份），測苯乙 稀系樹脂組成物中分子量在2, 〇〇〇〜20, 000以下者之含量 26 1279406 (重量％);並評價苯乙烯系樹脂組成物之透明度(Haze)、翹 曲性、色相及製成打火機外殼的耐藥品性等物性，分析及 評價結果如表二。 由比較例1中得知，透明笨乙烯系樹脂組成物中，腈 化乙烯系聚合單位之含量太低(小於26重量％)，則樹脂組 成物製成打火機外殼的耐藥品性差；由比較例2中得知， 透明苯乙烯系樹脂組成物之分子量在2, 〇〇〇〜2〇, 〇〇〇以下 者之含量太多（大於7重量％)，則樹脂組成物之翹曲性及製 • 成打火機外殼的耐藥品性差；同樣的，由比較例3中得知， 透明苯乙烯系樹脂組成物之分子量在2, 〇〇〇〜2〇,〇〇〇以下 者之含量太少（小於1· 6重量％)，則樹脂組成物之翹曲性及 製成打火機外殼的耐藥品性差；比較例4中得知，透明苯 乙烯系樹脂組成物中不添加雙尿素化合物(B)，則樹脂組成 物之翹曲性及製成打火機外殼的耐藥品性差；比較例5中 得知’透明笨乙烯系樹脂組成物中改為添加亞乙基雙硬脂 醯月女（Ethylene bis stearyl amide)(非雙尿素化合物（B) • 類），則樹脂組成物之透明度差，色相普通且製成打火機外 成的财藥性差；由比較例6巾得知，透明苯乙烯系樹月旨 組成物中添加雙尿素化合物⑻量太多（大於1· 〇 4量份）， 則樹脂組成物之透明度變差；比較例7中得知，透明苯乙 稀系樹脂組成物中不添加雙尿素化合物⑻，則樹脂組成物 之輕曲性及製成打域外殼的_品性差。 27 1279406 SM:沭ss AN: §5雜 PNI: N-舛 ΡΕΤΡ :驷涤sgls(3-轉1^¾踝smITTDM : iw洚+卜荈胂熟眾 BMI : Ν, ΝΓ4, 4*-l·辦駟-S荈礤驷步缥跆* AIBN : 2,2·'3βιι-)4-驷 T 舔 ΤΧ-29Α : 1,τ_-脒 WT^^^/icr-f03, 5-w f 荈 *1 :^oi-s^)4+、v^^^^(Hsa methylene bislstearyl urs) *2 :^卜-^辦^^蟲^4->蘇幕1^^^(^171362:5|0^^11】 *3 "^f^l^)44-、/^w>^^(T01uylene bis-stsryl urea) *4 "难跆辦τι^)4-ι-、ν^^^^(ΜΡ^^1 methylene bis-stsryl urea)*5 :鵷Ϊ安s(Bsf篇緣零 物性 穿萆：s 聲爺辦 反應條件 1實施例編號 製成打火機外殼的耐藥品性 翹曲性 透明度（Haze) 分子量在2,000〜20,000以下者之含量（重量％) 雙尿素化合物(B)之含量(重量份） 雙尿素化合物（B)之種類 透明苯乙 烯系樹脂 (A) 1最後反應轉換率（％) 1 δ Q 鉼 H® I 鏈轉移劑(TDM) 第三反應 H(R3) 第二反應 器(R2) 第一反應 器(Rl) |可共聚合單體之聚合單位含量(重量％) | 部· cr 審 Μ® iiirtii VW 1φ 感 苯乙烯系聚合單位之含量（重量％) 1攪拌型態 .| |攪拌速度(rpm) I溫度(°c) 1 1攪拌型態 1 |攪拌速度(rpm) i |溫度(°c) 1 進料組成 fii料流量(kg/hr) S#型態 |攪拌速度(rpm) I溫度(°c) m CD 聚合起始劑 雙尿素化合 物（B) 1 ΒΜΙ | | ΡΕΤΡ 1 | ΡΜΙ 1 2 1加入位置1 1 (重量份）1 Nh 1*Φ 麥 1 (重量份） 1 種類 1 (重量份） 1 種類 1 (重量份） 1 (重量份） 1 (重量份） 1 (重量％) 1 (重量％) ◎ 〇 〇 ·〇 4^ 0.157 1 U) CD CD LTi S 2 〇 U) | P.F.R 1 f〇 Ui 「：STR 1 ο | 0.02 | AIBN 1 0.08 * p 1 1 ON U) U) Ut | CSTR i 實施例1 ◎ 〇 〇 0.54 CO 〇〇 0.24 * 1 U) 05 CO Ο o 2 〇 U) | P.F.R I 1 CSTR 1 δ 00 1 1 Γ〇·^ 1 * | 0.09 1 1 Uj ON U) U) | CSTR S 實施例2 ◎ 〇 〇 0.52 CO —α 0.471 * 1 U) σ> CO Ui U) 1 2 〇 U) | P.F.R I 1 CSTR 1 § ο 1 1 | 0.25 * 〇 Κ) • 1 U) On U) | CSTR 5 實施例3 〇 〇 〇 ρ cm GO 0.057 * 1 K) OO Ul K) 2 〇 U) | P.F.R 1 1 CSTR I δ 5 s | 0.01 | | TX-29A | | 0.03 * 1 S 1 to On UJ | CSTR i 實施例4 〇 〇 〇 CD 〇, -<l 0.083 餐 ON 00 CO o 2 | 0.15 I / | P.F.R I to Lti Κ) Ui | 0.01 ί | AIBN | 0.05 关 1 〇 ON U) | CSTR o 實施例5 ◎ 〇 〇 p> cn GO OO 1 0.24 1 U) CJ^ CO S 〇 U) 1 P.F.R 1 | CSTR I δ 5 00 1 1 | 0.12 * Κ) | 0.09 1 1 U> Os U) U) U\ | CSTR 實施例6 ◎ 〇 〇 CD CO CO 0.24 1 U) CD CO U\ o 2 〇 U) 1 P.F.R 1 U) o | CSTR I S 00 1 1 | 0.12 ώ | 0.09 1 1 Os U) U) L/i | CSTR 實施例7 ◎ 〇 〇 •o ΓΟ GO CO 0.24 1 U) CD CD Ui o - 2 〇 U) 1 P.F.R 1 | CSTR I δ 00 1 1 |. 0.12 | 0.09 1 a ON u> U) L/i | CSTR e; 實施例8 〇 〇 〇 0.63 JND OO 0.55(氺 5) * 1 U) CD CO 5 2 〇 U) | P.F.R 1 | CSTR I 1 120 1 ο 1 QQi 1 | TX-29A | 1 1 I0.05 1 1 1 u> ON U) Ln | CSTR I o 實施例9 28 1279406 *7 :&(>駟难*嶄it^OEH^XifK·象： *1 “^£>f^«+、/^^^^(Hexa methylene bis-stearyl urea) 物性 赛聲：§ 涂聆ο 反應條件 比較例編號 製成打火機外殼的耐藥品性 輕曲性 色相 透明度(Haze) 1分子量在2,000〜20,000以下者之含量（重量％) EBA之含量（重量份） 雙尿素化合物(B)之含量(重量份） 透明笨乙烯樹 脂(A) 最後反應轉換率（％) R3回流量（kg/hr) 鏈轉移劑(TDM) 第三反應器 (R3) 第二反應器 (R2) 第一反應器 (Rl) 可共聚合單體之聚合單位含量(重量％) 腈化乙烯系聚合單位之含量(重量％) [^乙烯系聚合單位之含量(重量％) 攪拌型態 攪拌速度(rpm) 溫度(°c) 攪拌型態 授拌速度(rpm) 溫度(°c) 進料組成 進料流量(kg/hr) 攪拌型態 搜拌速度(rpm) 溫度(°C) S3 聚合起始劑 雙尿素化合 物(B) BMI PETP PMI 1 CO 2 加入位置 (重量份） (重量份） (重量份）i 種類 (重量份） 種類 (重量份） (重量份） (重量份） (重量％) (重量％) X 〇 〇 CZ5 CO CO ro 0.24(^1) 1 σί 1 2 Ο P.F.R § CSTR § S 0.025 AIBN 0.12 * 0.05 t 1 K) U) U) CSTR o 比較例1 X X 〇 0.57 ·〇〇 an 0.25(*1) 1 U) ON 1 2 S P.F.R CSTR fo U\ § e; 1 1 0.12 * 1 扁 1 Uj o U) U\ CSTR E 比較例2 X X 〇 •Ο 00 ΟΊ 0.154(*1) 1 U) σ> Ό δ 肇 S ρ CSTR to LA CSTR § 0.01 TX-29A 0.08 * 〇 1 1 Uj ON U) U) CSTR i 比較例3 X X 〇 0.42 CO -<1 〇 1 U) ΟΝ \〇 L/1 U) 1 Ξ s P.F.R U) LA CSTR § § 1 I 〇 1 P I 1 U) ON Ui CSTR 比較例4 X 〇 > cn CO CO 0.45(*7) 1 1 U) OS U\ S o L〇 P.F.R CSTR § 0.01 TX-29A 1 1 1 1 1 Lk) ON Lk) Lk) L/l CSTR o 比較例5 〇 〇 〇 hp^ 〇1 oo -<l 1.2(*6) 1 U) ΟΝ ο ^J\ U) 1 Κ) U) P.F.R U) o U) CSTR § § - 1 1 1 1 P 1 1 U) so os UJ Ul CSTR 比較例6 X X 〇 0.42 CO 〇 1 »0 〇〇 ΓΟ 1 2 o U) 1 1 1 1 1 1 1 1 〇 1 1 1 1 oo ro 〇\ oo OO CSTR § 比較例7 290.3 parts by weight of a third-stage dodecyl mercaptan (abbreviated as TDM) to the first reactor; the reaction temperature of the first reactor is ll 〇 ° C, the stirring speed is i 〇 rpm, and the polymerization of the first reactor is completed. The solution enters a second reactor having a capacity of 4 liters (completely mixed polymerization reactor, CSTR), the reaction temperature of the second reactor is 115 ° C, and the stirring speed is 120 rpm; the polymer solution of the second reactor is introduced into the capacity. 75 liter third reactor (column flow polymerization reactor, PF R), third reactor reaction temperature 125 ° C, stirring speed 30 rpm; part of the third reactor polymer solution refluxed to the first reaction The reactor continues to react, and the return flow is 10kg/hiS. The molten resin at the bottom of the third reactor is measured at 51%. The reaction of the third reaction is the bottom of the reaction melt resin and the devolatilization equipment. After the strip is baked in the face and then granulated, the transparent stupid Ethylene resin composition of the present invention can be obtained, and the transparent styrene tree test towel is analyzed, and the transparent benzene system (A) is Styrene-based polymerization unit content (% by weight), guess = the content of the polymerization unit containing # (% by weight) and the poly-H of the pharmaceutically acceptable compound, such as bismuth compound (the weight (10), and the analysis of the molecular weight of the resin composition of the transparent styrene resin (10) It is contained in 2, _~2M (9), and it is transparent and transparent, and it is transparent and transparent (4), interesting 20 1279406, and the physical properties of the lighter casing, analysis and 5 parity results. [Tables 1 to 8] The manufacturing method and the manufacturing process of the transparent styrene resin composition of the first embodiment, and the present invention were sequentially prepared according to the feed composition and polymerization operation conditions of Table 1. Examples 2 to 8 of the transparent styrene resin composition, but Example 5 shows the first reactor (completely mixed polymerization reactor 'CSTR) and the second reactor (column flow) as shown in Table 1 Polymerization reactor, pf R.) Polymerization reaction; analysis of transparent styrene resin composition, content of styrene polymer unit (% by weight) of transparent styrene resin (A), nitrile ethylene polymerization unit Content (% by weight) and copolymerizable single The content (% by weight) of the polymerization unit of the body, and the content (parts by weight) of the diurea compound (B) which is heavily viscous with respect to the transparent styrene resin (A), and analysis of the transparent stupid vinyl resin composition The content of the molecular weight of 2, 〇〇〇~20,000 or less (% by weight); and the transparency (Haze), warpage, hue, and chemical resistance of the outer casing of the lighter made of the transparent styrene resin composition were evaluated. The physical property analysis and evaluation results are shown in Table 1. [Example 9] 63% by weight of styrene monomer, 37% by weight of acrylonitrile monomer, and the above-mentioned monomer 10 parts by weight of total weight, Ν, Ν' -4, 4,-di-p-decyl bis-maleimide (BMI) 〇 · 05 reset parts, 1,1 - double - third A feed solution consisting of 0. 01 parts by weight of oxidized-3,3,5-trimethylcyclohexane (ΤΧ-29Α) was continuously supplied to a capacity of 4 liters by a pump at a flow rate of 35 kg/hour. The first reactor (completely this combined polymerization reactor, CSTR) is reacted, and in addition, pumped into the phase 1279406 for styrene monomer and C 1 part by weight of the nitrile monomer and 3 parts by weight of the third stage dodecyl mercaptan to the first reactor; the reaction temperature of the first reactor is 110 ° C, the stirring speed is i5 rpm, the first The reactor-reacted polymer solution enters a second reactor having a capacity of 40 liters (completely mixed polymerization reactor, CSTR), the reaction temperature of the second reactor is uyc, the stirring speed is 120 rpm, and the polymer after the reaction is completed. The solution enters a third reactor having a capacity of 75 liters (column flow polymerization reactor, pFR), and the third reaction is a reaction temperature of 13 (TC, a stirring speed of 30 rpm; a portion of the polymer solution of the third reactor is refluxed to the first In a reactor, the reflux flow rate is 1 〇kg/hr; the third reaction is the bottom end of the blush resin, and the final reaction conversion rate is Μ%, and the third reaction is the bottom end of the molten resin devolatilized by the devolatilization device. After reacting the monomer and the solvent, the strip is extruded through a die, and then cooled and pelletized to obtain a transparent stupid vinyl resin (A), and then the transparent styrene resin (A) is used in an amount of 1 part by weight. Hexamethylene octadecyl urea (Hachreen SH) (B) 〇 55 weight The transparent styrene resin composition of the present invention having a pellet shape can be obtained by melt-kneading at a set temperature of 19 〇 22 to 22 (with rc) with a vent opening; In the styrene-based resin composition, the content (% by weight) of the styrene-based polymerization unit of the transparent styrene-based resin (A), the content (% by weight) of the nitrile-based ethylene-based polymerization unit, and the polymerization of the copolymerizable monomer The content (% by weight) of the unit, and the content (parts by weight) of the diurea compound (β) per 100 parts by weight of the transparent styrene resin (A), and the molecular weight of the transparent styrene resin composition is 2, 〇 〇〇~20, 〇〇〇 the content of the following (weight ❹ / ◦); and evaluate the transparency (Haze), warpage, hue, and chemical properties of the lighter casing made of the transparent styrene resin composition The results of the analysis and evaluation are shown in Table 1. 22 1279406 [Comparative Example 1] 77% by weight of the present ethylene monomer, 23% by weight of the acrylonitrile monomer, and 1 part by weight of ethylbenzene (fat) based on 100 parts by weight of the total of the stupid ethylene monomer and the acrylonitrile monomer. , 2,2'-azo-bis-isobutyronitrile with 1 grab) 〇〇 25 parts by weight 'Ν,Ν' -4, 4,-diphenylmethane bismaleimide (BMI) 0· 05 A feed solution of parts by weight of 'hexamethylene octadecyl urea (Hachreen SH) O·12 parts by weight, continuously supplied to a first reactor having a capacity of 40 liters at a flow rate of 35 kg/hour (fully mixed) The reaction is carried out in a polymerization reactor, CSTR), and further, 3 parts by weight of a third-order dodecyl mercaptan (abbreviated as TDM) is added in an amount of 100 parts by weight based on the total of the styrene monomer and the acrylonitrile monomer. To the first reactor; the reaction temperature of the first reactor described above is 11 Torr. 〇, stirring speed 150rpm, the polymer solution reacted in the first reactor enters the second reactor with a capacity of 4 liters (completely mixed polymerization reactor, CSTR), the reaction temperature is 120C, and the mixing speed is 12 〇 rpm ; the second reactor reacted polymer solution into a third reactor with a capacity of 75 liters (column flow polymerization reactor, PFR), the third reactor reaction temperature 13 (rc, stirring speed 30 rpm; The molten resin at the bottom of the three reactors is measured at a final reaction conversion rate of 50%, and the molten resin at the bottom end of the third reactor is devolatilized by the devolatilization device to unreacted monomers and solvents, and then the die is released through the die. After cooling, the styrene resin composition is obtained by cooling and dicing, and the styrene resin composition (A) is contained in the styrene resin composition (A). The content (% by weight) of the nitrile acetonitrile polymerization unit and the content (% by weight) of the polymerization unit of the copolymerizable monomer, and the diurea compound (B) based on 100 parts by weight of the styrene resin (A) Content (parts by weight) and analysis The molecular weight of the styrene-based resin composition is 2, 〇〇〇 2 2 〇, and the content (% by weight) of 23 1279406; and the transparency (Haze) and warpage of the transparent styrene resin composition are evaluated. Physical properties such as properties, color, and chemical resistance of the outer casing of the lighter were as follows. The results of the analysis and evaluation are shown in Table 2. [Comparative Examples 2 to 4] The manufacturing method and operation procedure of the present fine resin composition of Comparative Example 1 According to the feed composition and the polymerization operation conditions of Table 2, a stupid vinyl resin composition was sequentially obtained, and the content of the styrene-based polymerization unit of the styrene resin (A) in the stupid vinyl resin composition was analyzed (% by weight). And the content (% by weight) of the polymerization unit of the copolymerizable monomer and the content of the polymerization unit of the copolymerizable monomer (% by weight), and the diuretic compound (1 part by weight relative to the styrene resin (A)) B) content (parts by weight), and analysis of the content (% by weight) of the molecular weight of the transparent stupid vinyl resin composition of from 2,000 to 20,000 or less; and evaluation of transparency of the transparent styrene resin composition (Haze) ), bell curvature, hue and Physical properties such as chemical resistance of the outer casing of the lighter were measured, and the results of analysis and evaluation are shown in Table 2. [Comparative Example 5] 63% by weight of styrene monomer, 37% by weight of acrylonitrile monomer, and relative to the prior art A total of acrylonitrile monomer and 1QQ parts by weight of ethylbenzene (EB) 10 parts by weight, 1,; [-bis-tertiary butyl peroxy-3, 3, 5~ tridecylcyclohexane (referred to as ΤΧ-29Α) 0. 01 parts by weight, the composition of the feed solution was continuously supplied to a first reactor of a capacity of 4 liters (completely mixed polymerization reactor, CSTR) at a flow rate of 35 kg/hour of fruit pu. Further, the third stage of dodecyl mercaptan (abbreviated as TDM) is added to the first reactor in an amount of 1 part by weight based on 100 parts by weight of the total of 100 parts by weight of the stupid ethylene monomer and the acrylonitrile monomer. The reaction temperature of the first reactor is 11 (rc, stirring speed 24 1279406 150 rpm, and the polymer solution reacted in the first reactor enters a second reactor (completely mixed polymerization reactor, CSTR) having a capacity of 4 liters. The reaction temperature of the second reactor is 115 ° C, the stirring speed is 120 rpm; the polymerization of the second reactor is completed. The solution enters a third reactor with a capacity of 75 liters (column flow polymerization reactor, PFR), the reaction temperature of the third reactor is at a temperature of 30 rpm, and the molten resin at the bottom of the third reactor is measured. Finally, the conversion rate of the reaction is 53%. The molten resin at the bottom of the third reactor is devolatilized from the unreacted monomer and solvent through the devolatilization apparatus, and then the strip is extruded through the die, and then cooled and cut into pellets to obtain Styrene resin (A). The above-mentioned stupid vinyl resin (A) is further combined with ethylene 45% by weight of Ethylene bis stearylamide (abbreviated as ΕΒΑ), and the set temperature of the biaxial extruder with the vent is 190. The styrene resin composition having a granule (peUet) shape can be obtained by melt-kneading at a temperature of -220 ° C, and the styrene-based resin composition is analyzed as a stupid ethylene-based polymerization unit of the styrene-based resin (A). Content (% by weight), content of the nitrileated ethylene-based polymerization unit (weight and content of the polymerizable unit of the copolymerizable monomer (% by weight), and the amount of the styrene-based resin (A) 1 part by weight The content (parts by weight) of the urea compound (8), the molecular weight of the styrene resin composition in the range of 2,000 to 2 Torr, the content of the following (weight; and the transparency of the styrene _ surface product (Haze) The product quality, analysis and evaluation results are shown in Table 2 0 [Comparative Example 6], the manufacturing method and operation of the 5-year-old vinyl sulphate sharks on the side of the year, The feed composition and polymerization operating conditions of the second method Touch (4)' to add the above-mentioned stupid ethylene resin (1) to 1.2 parts by weight of hexylene octadecene 25 1279406-based urea (Hachreen SH) to a set temperature of 190 to 220 ° with a vented biaxial extruder The melt-kneading under the condition of C can produce a stupid ethylene resin composition' analysis of the styrene resin composition, the content (% by weight) of the stupid ethylene polymerization unit of the styrene resin (A), and the nitrileization. The content (% by weight) of the ethylene-based polymerization unit and the content (% by weight) of the polymerization unit of the copolymerizable monomer, and the content of the diurea compound (B) per part by weight of the styrene-based resin (A) (parts by weight), the content of the styrene resin composition having a molecular weight of 2,000 to 20,000 or less (weight and evaluation of transparency (Haze), warpage, hue, and preparation of the styrene resin composition Physical properties such as chemical resistance of the lighter casing, analysis and evaluation results are shown in Table 2. [Comparative Example 7] 68% by weight of styrene monomer, 32% by weight of acrylonitrile monomer, and styrene monomer and acrylonitrile single Total and 1 part by weight of ethylbenzene (EB) 7 weight The composition of the feed solution was continuously supplied to a first reactor (full-mix polymerization reactor, CSTR) having a capacity of 40 liters by a pump at a flow rate of 35 kg/hour, and further, pumped in parallel with stupid ethylene. 100 parts by weight of the monomer and acrylonitrile monomer and 3 parts by weight of the third stage dodecyl mercaptan (TDM for short) to the reactor; the reaction temperature of the above reactor is 130 t:, the stirring speed is 150 rpm, Finally, the reaction conversion rate was 45%, and a styrene resin composition was obtained after the polymerization reaction, and the content (% by weight) of the styrene-based polymerization unit of the present B:fep糸 resin (A) in the styrene resin composition was analyzed. The content of the nitrile ethylene-based polymerization unit (weight. /◦) and the content (% by weight) of the polymerization unit of the copolymerizable monomer, and the content (parts by weight) of the diurea compound (β) relative to the styrene resin (A) In the ethylene resin composition, the molecular weight is 2, 〇〇〇~20,000 or less, and the content is 26,1279,406 (% by weight); and the transparency (Haze), warpage, hue, and system of the styrene resin composition are evaluated. Physical properties such as chemical resistance of the lighter casing, and analysis and evaluation results are shown in Table 2. In Comparative Example 1, it was found that the content of the nitrile ethylene-based polymerization unit was too low (less than 26% by weight) in the transparent vinyl resin composition, and the resin composition was poor in chemical resistance of the outer casing of the lighter; 2, it is known that the molecular weight of the transparent styrene resin composition is 2, 〇〇〇 2 2 〇, and the content of the following is too large (more than 7% by weight), the warpage property of the resin composition and the system • The chemical resistance of the outer casing of the lighter is poor; similarly, as seen in Comparative Example 3, the molecular weight of the transparent styrene resin composition is 2, 〇〇〇~2〇, and the content of the 〇〇〇 is less (less than 1·6 wt%), the warpage property of the resin composition and the chemical resistance of the outer casing of the lighter were poor; in Comparative Example 4, it was found that the diuret compound (B) was not added to the transparent styrene resin composition. The warpage of the resin composition and the chemical resistance of the outer casing of the lighter were poor; in Comparative Example 5, it was found that the "transparent stupid vinyl resin composition" was replaced with Ethylene bis stearyl amide. (non-biurea compound (B) • class) The resin composition has poor transparency, and the hue is ordinary and the property of the lighter is poor. The amount of the double urea compound (8) added to the composition of the transparent styrene tree is too large (more than 1) 〇4 parts by weight), the transparency of the resin composition was deteriorated; in Comparative Example 7, it was found that the softness of the resin composition was not obtained by adding the double urea compound (8) to the transparent styrene resin composition. The _ character of the shell is poor. 27 1279406 SM:沭ss AN: §5 Miscellaneous PNI: N-舛ΡΕΤΡ: 驷 s sgls (3-turn 1^3⁄4踝smITTDM: iw洚+ Buddhism BMI: Ν, ΝΓ4, 4*-l·驷-S荈礤驷步缥跆* AIBN : 2,2·'3βιι-)4-驷T 舔ΤΧ-29Α : 1,τ_-脒WT^^^/icr-f03, 5-wf 荈*1 :^oi-s^)4+, v^^^^(Hsa methylene bislstearyl urs) *2 :^卜-^办^^虫^4->Su curtain 1^^^(^171362:5|0 ^^11] *3 "^f^l^)44-, /^w>^^(T01uylene bis-stsryl urea) *4 "Difficult to do τι^)4-ι-, ν^^^^ (ΜΡ^^1 methylene bis-stsryl urea)*5 : 鹓Ϊ安s (Bsf 缘零物性穿萆: s 声 爷 办 reaction condition 1 example number made of lighter shell chemical resistance warp transparency ( Haze) Content of molecular weight of 2,000 to 20,000 or less (% by weight) Content of diurea compound (B) (parts by weight) Type of double urea compound (B) Transparent styrene resin (A) 1 Final reaction conversion ratio (% 1 δ Q 鉼H® I chain transfer agent (TDM) third reaction H(R3) second reactor (R2) first reactor (Rl) | polymerization unit content of copolymerizable monomer (% by weight) | Department · cr Review® iiirti i VW 1φ styrene-based polymerization unit content (% by weight) 1 Stirring type.| | Stirring speed (rpm) I Temperature (°c) 1 1 Stirring type 1 | Stirring speed (rpm) i | Temperature (° c) 1 Feed composition fii material flow rate (kg/hr) S# type | stirring speed (rpm) I temperature (°c) m CD polymerization initiator double urea compound (B) 1 ΒΜΙ | | ΡΕΤΡ 1 | ΡΜΙ 1 2 1 Add position 1 1 (parts by weight) 1 Nh 1*Φ Wheat 1 (parts by weight) 1 Type 1 (parts by weight) 1 Type 1 (parts by weight) 1 (parts by weight) 1 (parts by weight) 1 (% by weight) 1 (% by weight) ◎ 〇〇·〇4^ 0.157 1 U) CD CD LTi S 2 〇U) | PFR 1 f〇Ui ":STR 1 ο | 0.02 | AIBN 1 0.08 * p 1 1 ON U) U Ut | CSTR i Example 1 ◎ 〇〇0.54 CO 〇〇0.24 * 1 U) 05 CO Ο o 2 〇U) | PFR I 1 CSTR 1 δ 00 1 1 Γ〇·^ 1 * | 0.09 1 1 Uj ON U) U) | CSTR S Example 2 ◎ 〇〇 0.52 CO — α 0.471 * 1 U) σ > CO Ui U) 1 2 〇U) | PFR I 1 CSTR 1 § ο 1 1 | 0.25 * 〇Κ) • 1 U) On U) | CSTR 5 Example 3 〇〇〇ρ cm GO 0.057 * 1 K) OO Ul K) 2 〇 U) | PFR 1 1 CSTR I δ 5 s | 0.01 | | TX-29A | | 0.03 * 1 S 1 to On UJ | CSTR i Example 4 〇〇〇CD 〇, -<l 0.083 Meal ON 00 CO o 2 | 0.15 I / | PFR I to Lti Κ) Ui | 0.01 ί | AIBN | 0.05 Off 1 〇 ON U) | CSTR o Example 5 ◎ 〇〇p> cn GO OO 1 0.24 1 U) CJ^ CO S 〇 U) 1 PFR 1 | CSTR I δ 5 00 1 1 | 0.12 * Κ) | 0.09 1 1 U> Os U) U) U\ | CSTR Example 6 ◎ 〇〇CD CO CO 0.24 1 U) CD CO U\ o 2 〇U) 1 PFR 1 U) o | CSTR IS 00 1 1 | 0.12 ώ | 0.09 1 1 Os U) U) L/i | CSTR Example 7 ◎ 〇〇•o ΓΟ GO CO 0.24 1 U) CD CD Ui o - 2 〇U) 1 PFR 1 | CSTR I δ 00 1 1 |. 0.12 | 0.09 1 a ON u> U) L/i | CSTR e; Example 8 〇〇〇0.63 JND OO 0.55 (氺5 * 1 U) CD CO 5 2 〇U) | PFR 1 | CSTR I 1 120 1 ο 1 QQi 1 | TX-29A | 1 1 I0.05 1 1 1 u> ON U) Ln | CSTR I o Example 9 28 1279406 *7 :&(>驷难*崭it^OEH^XifK·象: *1 “^£>f^«+, /^^^^(Hexa methylene bis-stearyl urea) physical game sound: § 涂听ο Reaction conditions Comparison example No. Chemical resistance of the lighter casing is made of light-colored hue transparency (Haze) 1 Content of molecular weight of 2,000-20,000 or less (% by weight) EBA content (parts by weight) Biuret compound ( B) Content (parts by weight) Transparent Stupid Vinyl Resin (A) Final Reaction Conversion Rate (%) R3 Return Flow (kg/hr) Chain Transfer Agent (TDM) Third Reactor (R3) Second Reactor (R2) First reactor (Rl) Polymerizable unit content of copolymerizable monomer (% by weight) Content of nitrile ethylene-based polymerization unit (% by weight) [^ Content of ethylene-based polymerization unit (% by weight) Stirring type stirring speed ( Rpm) Temperature (°c) Stirring type Mixing speed (rpm) Temperature (°c) Feed composition Feed flow rate (kg/hr) Stirring type mixing speed (rpm) Temperature (°C) S3 Polymerization start Agent diurea compound (B) BMI PETP PMI 1 CO 2 Add position (parts by weight) (parts by weight) (parts by weight) i Species (parts by weight) Species (parts by weight) (parts by weight) (parts by weight) (% by weight) (% by weight) X 〇〇CZ5 CO CO ro 0.24(^1) 1 σί 1 2 Ο PFR § CSTR § S 0.025 AIB N 0.12 * 0.05 t 1 K) U) U) CSTR o Comparative Example 1 XX 〇0.57 ·〇〇an 0.25(*1) 1 U) ON 1 2 S PFR CSTR fo U\ § e; 1 1 0.12 * 1 Flat 1 Uj o U) U\ CSTR E Comparative Example 2 XX 〇•Ο 00 ΟΊ 0.154(*1) 1 U) σ> Ό δ 肇S ρ CSTR to LA CSTR § 0.01 TX-29A 0.08 * 〇1 1 Uj ON U U) CSTR i Comparative Example 3 XX 〇0.42 CO -<1 〇1 U) ΟΝ \〇L/1 U) 1 Ξ s PFR U) LA CSTR § § 1 I 〇1 PI 1 U) ON Ui CSTR Comparison Example 4 X 〇> cn CO CO 0.45(*7) 1 1 U) OS U\ S o L〇PFR CSTR § 0.01 TX-29A 1 1 1 1 1 Lk) ON Lk) Lk) L/l CSTR o Comparison Example 5 〇〇〇hp^ 〇1 oo -<l 1.2(*6) 1 U) ΟΝ ο ^J\ U) 1 Κ) U) PFR U) o U) CSTR § § - 1 1 1 1 P 1 1 U) so os UJ Ul CSTR Comparative Example 6 XX 〇0.42 CO 〇1 »0 〇〇ΓΟ 1 2 o U) 1 1 1 1 1 1 1 1 〇1 1 1 1 oo ro 〇\ oo OO CSTR § Comparative example 7 29