TW202222969A - Transparent thermoplastic resin composition, production method therefor, and molded article thereof - Google Patents

Abstract

This transparent thermoplastic resin composition comprises: a graft copolymer (A) which is obtained by graft-copolymerizing a monomer mixture (a) containing at least an aromatic vinyl-based monomer (a1) and a (meth)acrylic acid ester-based monomer (a2) in the presence of a rubbery polymer (r); a vinyl-based copolymer (B) which is obtained by copolymerizing a monomer mixture (b) containing at least an aromatic vinyl-based monomer (b1), a (meth)acrylic acid ester-based monomer (b2), and a vinyl cyanide-based monomer (b3); the ester wax (C) below; and the organic acid monoester (D) below. The ester wax (C) is at least one ester wax which is selected from the group consisting of glycerin fatty acid esters (c1) and a fatty acid ester (c2) obtained from the group consisting of a C12-C30 linear saturated monocarboxylic acid and at least one alcohol selected from among a C14-C30 linear saturated monohydric alcohol and a C2-C30 polyhydric alcohol such as dihydric to hexahydric alcohols. The organic acid monoester (D) is an organic acid monoester obtained from a dicarboxylic anhydride and a C14-C30 linear saturated monohydric alcohol. Provided are: a transparent thermoplastic resin composition having excellent impact resistance and fluidity while maintaining high transparency and favorable color tone; and a molded article thereof.

Description

透明熱可塑性樹脂組成物、其製造方法及成形品Transparent thermoplastic resin composition, method for producing the same, and molded article

本發明係關於透明熱可塑性樹脂組成物、其製造方法及成形品。The present invention relates to a transparent thermoplastic resin composition, a method for producing the same, and a molded article.

於二烯系橡膠等橡膠質聚合體中含有使苯乙烯、α-甲基苯乙烯等芳香族乙烯化合物、丙烯腈、甲基丙烯腈等氰化乙烯化合物、甲基丙烯酸甲酯、丙烯酸甲酯等不飽和羧酸烷基酯化合物進行共聚合的接枝共聚合體而成的透明ABS(Acrylonitrile Butadiene Styrene，丙烯腈-丁二烯-苯乙烯)樹脂，係因透明性、耐衝擊性、剛性等機械強度均衡、以流動性為起因之成形加工性及成本效率等均優異，故被廣泛利用於家電製品、通訊關聯機器、一般雜貨及醫療用機器等用途。Aromatic vinyl compounds such as styrene and α-methyl styrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methyl methacrylate, and methyl acrylate are contained in rubbery polymers such as diene rubber. Transparent ABS (Acrylonitrile Butadiene Styrene, Acrylonitrile-Butadiene-Styrene) resin, which is a graft copolymer obtained by copolymerizing an unsaturated carboxylic acid alkyl ester compound, is characterized by transparency, impact resistance, rigidity, etc. It is widely used in home appliances, communication-related equipment, general miscellaneous goods, and medical equipment because of its balanced mechanical strength, excellent formability due to fluidity, and cost efficiency.

含有蓖麻子硬化油之樹脂組成物已提案有以下文獻。例如，專利文獻1提案一種熱可塑性樹脂組成物，係含有下述者之橡膠改質苯乙烯系樹脂組成物：(I)苯乙烯-(甲基)丙烯酸酯系共聚合體之連續相60~80質量%，其係苯乙烯系單體、(甲基)丙烯酸酯系單體、及視需要所使用之可與此等單體共聚合之乙烯系單體的共聚合體；(II)於橡膠狀彈性體接枝了苯乙烯-(甲基)丙烯酸酯系共聚合體的接枝共聚合體之分散相40~20質量%，該苯乙烯-(甲基)丙烯酸酯系共聚合體係苯乙烯系單體、(甲基)丙烯酸酯系單體、及視需要所使用之可與此等單體共聚合之乙烯系單體的共聚合體；分散相之體積平均粒徑為0.3~0.6μm；規定連續相之重量平均分子量(Mw)、(甲基)丙烯酸酯系單體單位、苯乙烯系單體單位之間的特定計算式中所使用值的特定範圍；且相對於該樹脂組成物100質量份，含有有機聚矽氧烷0.005~0.05質量份；又，相對於上述橡膠改質苯乙烯系樹脂組成物100質量份，含有酯系滑劑0.1~2.5質量份；酯系滑劑為硬化蓖麻子油。The following documents have been proposed for resin compositions containing castor bean hardened oil. For example, Patent Document 1 proposes a thermoplastic resin composition comprising a rubber-modified styrene-based resin composition comprising (I) a continuous phase of styrene-(meth)acrylate-based copolymer 60 to 80 % by mass, which is a copolymer of styrene-based monomers, (meth)acrylate-based monomers, and optionally used vinyl-based monomers that can be copolymerized with these monomers; (II) in rubbery The dispersed phase of the graft copolymer in which the styrene-(meth)acrylate-based copolymer is grafted to the elastomer is 40 to 20% by mass, and the styrene-(meth)acrylate-based copolymer system is a styrene-based monomer. , (meth)acrylate-based monomers, and copolymers of vinyl-based monomers that can be copolymerized with these monomers as needed; the volume average particle size of the dispersed phase is 0.3~0.6 μm; the continuous phase is specified The specific range of the values used in the specific calculation formula between the weight-average molecular weight (Mw), (meth)acrylate-based monomer unit, and styrene-based monomer unit; and relative to 100 parts by mass of the resin composition, It contains 0.005 to 0.05 parts by mass of organopolysiloxane; and, with respect to 100 parts by mass of the rubber-modified styrene resin composition, 0.1 to 2.5 parts by mass of an ester-based lubricant; the ester-based lubricant is hardened castor oil .

另一方面，含有脂肪酸酯之樹脂組成物已提案有以下文獻。例如，專利文獻2提案一種使流動性提升之橡膠強化苯乙烯系樹脂組成物，其目的在於改善透明性良好之橡膠強化苯乙烯系樹脂之成形加工時的流動性，於含有多元醇脂肪酸酯作為流動性提升劑的苯乙烯系樹脂中，其特徵在於，苯乙烯系樹脂為透明性良好之橡膠強化苯乙烯系樹脂，多元醇脂肪酸酯為聚氧乙烯脂肪酸酯，且含有此聚氧乙烯多元醇脂肪酸酯0.1~3重量份。例如，專利文獻3提案一種透明熱可塑性樹脂組成物，作為獲得不損及具有透明性之橡膠強化苯乙烯系樹脂之透明性與耐衝擊性，除了耐傷性及表面硬度以外，表面平滑性亦優越的透明橡膠強化苯乙烯系熱可塑性樹脂組成物的手段，該熱可塑性樹脂組成物係相對於含有橡膠質聚合體(a)及不飽和羧酸烷基酯系單體(d)之接枝共聚合體(A)、與含有不飽和羧酸烷基酯系單體(d)之乙烯系共聚合體(B)之合計100重量份，調配屬於碳數12~32之高級脂肪酸與碳數12~32之高級醇之酯化物的高級脂肪酸酯(C)1~5重量份而成，其特徵在於，相對於(A)與(B)之合計量，橡膠質聚合體(a)之調配量為2.5~11.5重量%之範圍。例如，專利文獻4提案一種擠出成形用透明熱可塑性樹脂組成物，作為獲得擠出成形性、模具轉印性及物性均衡優越之擠出成形用透明熱可塑性樹脂組成物的手段，該樹脂組成物係含有藉由橡膠質聚合體所強化之橡膠強化苯乙烯系共聚合體(I)，且(A)該樹脂組成物中，含有丙酮可溶性樹脂成分，該丙酮可溶性樹脂成分係由含有芳香族乙烯系單體(a1)5~70重量%、不飽和羧酸烷基酯系單體(a2)30~95重量%、氰化乙烯系單體(a3)0~50重量%及可與此等共聚合之其他單體(a4)0~50重量%的單體組成所製造；(B)上述丙酮可溶性樹脂成分之甲基乙基酮中之還原黏度為0.30~2.00dl/g；(C)相對於上述橡膠強化苯乙烯系共聚合體(I)100重量份，含有融點為60~90℃之脂肪酸酯系蠟(II)0.05~5重量份；(D)根據ISO-1133，以220℃、98N所測定之熔融流動速率為15g/10min以下。On the other hand, the following documents have been proposed for resin compositions containing fatty acid esters. For example, Patent Document 2 proposes a rubber-reinforced styrene-based resin composition with improved fluidity for the purpose of improving the fluidity during molding of a rubber-reinforced styrene-based resin with good transparency. The styrene-based resin as a fluidity enhancer is characterized in that the styrene-based resin is a rubber-reinforced styrene-based resin with good transparency, the polyol fatty acid ester is a polyoxyethylene fatty acid ester, and the polyoxyethylene fatty acid ester is contained in the styrene-based resin. 0.1 to 3 parts by weight of ethylene polyol fatty acid ester. For example, Patent Document 3 proposes a transparent thermoplastic resin composition which is excellent in surface smoothness in addition to scratch resistance and surface hardness in order to obtain transparency and impact resistance of a rubber-reinforced styrene-based resin that does not impair transparency. A transparent rubber-reinforced styrene-based thermoplastic resin composition based on graft copolymerization of a rubbery polymer (a) and an unsaturated carboxylate-based monomer (d) A total of 100 parts by weight of the combination (A) and the ethylene-based copolymer (B) containing the unsaturated carboxylic acid alkyl ester-based monomer (d), and the higher fatty acids belonging to the carbon number of 12 to 32 and the carbon number of 12 to 32 are prepared. It is characterized in that, with respect to the total amount of (A) and (B), the compounding amount of the rubbery polymer (a) is The range of 2.5 to 11.5% by weight. For example, Patent Document 4 proposes a transparent thermoplastic resin composition for extrusion molding as a means of obtaining a transparent thermoplastic resin composition for extrusion molding having excellent extrusion moldability, die transferability and well-balanced physical properties. The system contains a rubber-reinforced styrene copolymer (I) reinforced by a rubbery polymer, and (A) the resin composition contains an acetone-soluble resin component, the acetone-soluble resin component is composed of an aromatic vinyl System monomer (a1) 5~70% by weight, unsaturated carboxylate alkyl ester monomer (a2) 30~95% by weight, vinyl cyanide monomer (a3) 0~50% by weight and can be combined with these Other monomers to be copolymerized (a4) are manufactured with a monomer composition of 0 to 50% by weight; (B) the reduced viscosity in the methyl ethyl ketone of the acetone-soluble resin component is 0.30 to 2.00 dl/g; (C) With respect to 100 parts by weight of the above-mentioned rubber-reinforced styrene-based copolymer (I), 0.05 to 5 parts by weight of fatty acid ester wax (II) having a melting point of 60 to 90° C.; (D) according to ISO-1133, with 220 The melt flow rate measured at ℃ and 98N is 15g/10min or less.

再者，含有蓖麻子硬化油與脂肪酸酯之樹脂組成物已提案有以下文獻。例如，專利文獻5中，作為減低成形時之牽絲、且透明性亦優越之環狀烯烴系熱可塑性樹脂組成物，係由酯A與酯B所構成、且酯A與酯B之質量比為20：80~80：20的環狀烯烴系熱可塑性樹脂用滑劑。提案了一種酯，係由酯A：蓖麻子硬化油、酯B：價數4~12之脂肪族多元醇與碳數12~30之直鏈飽和脂肪酸所得，羥基價為25mgKOH/g以下。例如，專利文獻6中，透明熱可塑性樹脂組成物係含有下述者而成：於橡膠質聚合體(r)存在下，使至少含有芳香族乙烯系單體(a1)及(甲基)丙烯酸酯系單體(a2)之單體混合物(a)進行接枝共聚合而得的接枝共聚合體(A)；使至少含有芳香族乙烯系單體(b1)、(甲基)丙烯酸酯系單體(b2)及氰化乙烯系單體(b3)之單體混合物(b)進行共聚合而成的乙烯系共聚合體(B)；下述酯蠟(C)；及下述酯蠟(D)。酯蠟(C)：蓖麻子硬化油，酯蠟(D)：提案了由碳數12~30之直鏈飽和單羧酸，與選自由碳數14~30之直鏈飽和單元醇及碳數2~30之2~6價之多元醇所構成群之至少一種醇所構成的脂肪酸酯。 [先前技術文獻] [專利文獻] Furthermore, the following documents have been proposed for resin compositions containing castor bean hardened oil and fatty acid ester. For example, in Patent Document 5, as a cyclic olefin-based thermoplastic resin composition with reduced stringing during molding and excellent transparency, the composition is composed of ester A and ester B, and the mass ratio of ester A and ester B is It is a 20:80~80:20 lubricant for cyclic olefin-based thermoplastic resins. An ester is proposed, which is obtained from ester A: castor bean hardened oil, ester B: aliphatic polyol with a valence of 4-12 and a straight-chain saturated fatty acid with a carbon number of 12-30, and the hydroxyl value is 25 mgKOH/g or less. For example, in Patent Document 6, the transparent thermoplastic resin composition contains at least an aromatic vinyl-based monomer (a1) and (meth)acrylic acid in the presence of a rubbery polymer (r). A graft copolymer (A) obtained by graft-copolymerizing a monomer mixture (a) of an ester-based monomer (a2); containing at least an aromatic vinyl-based monomer (b1), a (meth)acrylate-based A vinyl-based copolymer (B) obtained by copolymerizing a monomer mixture (b) of a monomer (b2) and a vinyl cyanide-based monomer (b3); the following ester wax (C); and the following ester wax ( D). Ester wax (C): Castor bean hardened oil, Ester wax (D): A linear saturated monocarboxylic acid having 12 to 30 carbon atoms, a linear saturated unit alcohol having 14 to 30 carbon atoms and an alcohol having a carbon number of 14 to 30 are proposed. Fatty acid ester composed of at least one alcohol of the group composed of 2 to 30 polyols with 2 to 6 valences. [Prior Art Literature] [Patent Literature]

專利文獻1：國際專利公開第2003/102076號 專利文獻2：日本專利特開2004-182874號公報 專利文獻3：日本專利特開2007-154034號公報 專利文獻4：日本專利特開2005-281514號公報 專利文獻5：日本專利特開2014-189734號公報 專利文獻6：日本專利特開2020-139054號公報 Patent Document 1: International Patent Publication No. 2003/102076 Patent Document 2: Japanese Patent Laid-Open No. 2004-182874 Patent Document 3: Japanese Patent Laid-Open No. 2007-154034 Patent Document 4: Japanese Patent Laid-Open No. 2005-281514 Patent Document 5: Japanese Patent Laid-Open No. 2014-189734 Patent Document 6: Japanese Patent Laid-Open No. 2020-139054

(發明所欲解決之問題)(The problem that the invention intends to solve)

然而，習知之熱可塑性樹脂組成物無法以高水準具備透明性、耐衝擊性、流動性，而要求進一步改良。However, conventional thermoplastic resin compositions cannot have high levels of transparency, impact resistance, and fluidity, and further improvements are required.

本發明之課題在於解決上述習知技術中之問題點，目的在於提供兼具透明性、耐衝擊性、流動性，亦即於維持特別高度之透明性、良好之色調之下，兼具優越之耐衝擊性及流動性的透明熱可塑性樹脂組成物及其成形品。 (解決問題之技術手段) The object of the present invention is to solve the problems of the above-mentioned conventional techniques, and the object is to provide a product that has both transparency, impact resistance, and fluidity, that is, while maintaining a particularly high degree of transparency and a good color tone. A transparent thermoplastic resin composition with impact resistance and fluidity, and a molded product thereof. (Technical means to solve problems)

為了解決上述課題，本發明之透明熱可塑性樹脂組成物係具有下述構成。亦即， 一種透明熱可塑性樹脂組成物，係含有下述者而成：於橡膠質聚合體(r)存在下，使至少含有芳香族乙烯系單體(a1)及(甲基)丙烯酸酯系單體(a2)之單體混合物(a)進行接枝共聚合而得的接枝共聚合體(A)；使至少含有芳香族乙烯系單體(b1)、(甲基)丙烯酸酯系單體(b2)及氰化乙烯系單體(b3)之單體混合物(b)進行共聚合而成的乙烯系共聚合體(B)；下述酯蠟(C)；及下述有機酸單酯(D)。 In order to solve the above-mentioned problems, the transparent thermoplastic resin composition of the present invention has the following structure. that is, A transparent thermoplastic resin composition comprising at least an aromatic vinyl-based monomer (a1) and a (meth)acrylate-based monomer ( The graft copolymer (A) obtained by the graft copolymerization of the monomer mixture (a) of a2); it contains at least an aromatic vinyl monomer (b1) and a (meth)acrylate monomer (b2) A vinyl-based copolymer (B) obtained by copolymerizing a monomer mixture (b) of a vinyl cyanide-based monomer (b3); the following ester wax (C); and the following organic acid monoester (D).

酯蠟(C)：選自由甘油脂肪酸酯類(c1)及脂肪酸酯(c2)所構成群之至少一種酯蠟；該脂肪酸酯(c2)係由碳數12~30之直鏈飽和單羧酸、與選自由碳數14~30之直鏈飽和單元醇及碳數2~30之2~6價之多元醇所構成群之至少一種醇所得； 有機酸單酯(D)：由二羧酸酐、與碳數14~30之直鏈飽和單元醇所得之有機酸單酯。 本發明之透明熱可塑性樹脂組成物之製造方法係具有下述構成。亦即， 一種透明熱可塑性樹脂組成物之製造方法，係調配：於橡膠質聚合體(r)存在下，使至少含有芳香族乙烯系單體(a1)及(甲基)丙烯酸酯系單體(a2)之單體混合物(a)進行接枝共聚合而得的接枝共聚合體(A)；使至少含有芳香族乙烯系單體(b1)、(甲基)丙烯酸酯系單體(b2)及氰化乙烯系單體(b3)之單體混合物(b)進行共聚合而成的乙烯系共聚合體(B)；下述酯蠟(C)；及下述有機酸單酯(D)，並進行熔融混練。 Ester wax (C): at least one ester wax selected from the group consisting of glycerol fatty acid esters (c1) and fatty acid esters (c2); the fatty acid ester (c2) is composed of a straight-chain saturated monolayer having 12 to 30 carbon atoms. Carboxylic acid, and at least one alcohol selected from the group consisting of straight-chain saturated unit alcohols with 14-30 carbon atoms and 2-6 valent polyols with 2-30 carbon atoms; Organic acid monoester (D): an organic acid monoester obtained from dicarboxylic acid anhydride and a straight-chain saturated unit alcohol having 14 to 30 carbon atoms. The manufacturing method of the transparent thermoplastic resin composition of this invention has the following structure. that is, A method for producing a transparent thermoplastic resin composition, comprising: in the presence of a rubbery polymer (r), at least an aromatic vinyl-based monomer (a1) and a (meth)acrylate-based monomer (a2) are prepared. The graft copolymer (A) obtained by graft copolymerizing the monomer mixture (a); at least containing aromatic vinyl monomer (b1), (meth)acrylate monomer (b2) and cyanide The vinyl-based copolymer (B) obtained by copolymerizing the monomer mixture (b) of the vinyl-based monomer (b3); the following ester wax (C); and the following organic acid monoester (D), and the Melt kneading.

酯蠟(C)：選自由甘油脂肪酸酯類(c1)及脂肪酸酯(c2)所構成群之至少一種酯蠟；該脂肪酸酯(c2)係由碳數12~30之直鏈飽和單羧酸、與選自由碳數14~30之直鏈飽和單元醇及碳數2~30之2~6價之多元醇所構成群之至少一種醇所得； 有機酸單酯(D)：由二羧酸酐、與碳數14~30之直鏈飽和單元醇所得之有機酸單酯。 本發明之成形品係具有下述構成。亦即， 一種成形品，係將上述透明熱可塑性樹脂組成物進行成形而成。 Ester wax (C): at least one ester wax selected from the group consisting of glycerol fatty acid esters (c1) and fatty acid esters (c2); the fatty acid ester (c2) is composed of a straight-chain saturated monolayer having 12 to 30 carbon atoms. Carboxylic acid, and at least one alcohol selected from the group consisting of straight-chain saturated unit alcohols with 14-30 carbon atoms and 2-6 valent polyols with 2-30 carbon atoms; Organic acid monoester (D): an organic acid monoester obtained from dicarboxylic acid anhydride and a straight-chain saturated unit alcohol having 14 to 30 carbon atoms. The molded product of the present invention has the following constitution. that is, A molded article obtained by molding the above-mentioned transparent thermoplastic resin composition.

本發明之透明熱可塑性樹脂組成物，較佳係相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，上述酯蠟(C)之含量為0.4~2質量份。In the transparent thermoplastic resin composition of the present invention, the content of the ester wax (C) is preferably 0.4 to 2 parts by mass relative to 100 parts by mass in total of the graft copolymer (A) and the vinyl copolymer (B). .

本發明之透明熱可塑性樹脂組成物，較佳係相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，上述有機酸單酯(D)之含量為0.1~2質量份。In the transparent thermoplastic resin composition of the present invention, the content of the organic acid monoester (D) is preferably 0.1 to 2 parts by mass based on 100 parts by mass in total of the graft copolymer (A) and the vinyl copolymer (B). parts by mass.

本發明之透明熱可塑性樹脂組成物，較佳係上述有機酸單酯(D)為順丁烯二酸單酯。In the transparent thermoplastic resin composition of the present invention, the organic acid monoester (D) is preferably maleic acid monoester.

本發明之透明熱可塑性樹脂組成物，較佳係上述酯蠟(C)為蓖麻子硬化油。 (對照先前技術之功效) In the transparent thermoplastic resin composition of the present invention, it is preferable that the above-mentioned ester wax (C) is castor bean hardened oil. (Compared to the efficacy of the prior art)

藉由本發明，可獲得於維持特別高度之透明性、良好之色調之下，具備優越之耐衝擊性，進而亦兼具優越之流動性的透明熱可塑性樹脂組成物。According to the present invention, a transparent thermoplastic resin composition having excellent impact resistance and excellent fluidity can be obtained while maintaining a particularly high degree of transparency and a good color tone.

以下詳述本發明，但此等為表示較佳實施形態之一例，本發明並不限定於此等內容。The present invention will be described in detail below, but these are examples of preferred embodiments, and the present invention is not limited to these contents.

尚且，本說明書中，所謂「(甲基)丙烯酸」係指丙烯酸或甲基丙烯酸。In addition, in this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid.

本發明之透明熱可塑性樹脂組成物，係含有後述接枝共聚合體(A)、乙烯系共聚合體(B)及特定之酯蠟(C)及特定之有機酸單酯(D)而成。藉由含有接枝共聚合體(A)，可提升透明熱可塑性樹脂組成物之成形性，並提升成形品之耐衝擊性、透明性、色調。又，藉由含有乙烯系共聚合體(B)，可提升透明熱可塑性樹脂組成物之流動性，並提升成形品之透明性、色調。而且，藉由含有特定之酯蠟，則不致使成形品之透明性、色調降低，進一步提升成形品之耐衝擊性，同時提升透明熱可塑性樹脂組成物之流動性而可獲得良好之成形性。再者，藉由含有特定之有機酸單酯，則不致使成形品之透明性、色調降低，更加提升透明熱可塑性樹脂組成物之流動性，進而可獲得良好之成形性。The transparent thermoplastic resin composition of the present invention contains a graft copolymer (A), a vinyl copolymer (B), a specific ester wax (C), and a specific organic acid monoester (D) described later. By containing the graft copolymer (A), the moldability of the transparent thermoplastic resin composition can be improved, and the impact resistance, transparency, and color tone of the molded article can be improved. In addition, by containing the vinyl copolymer (B), the fluidity of the transparent thermoplastic resin composition can be improved, and the transparency and color tone of the molded article can be improved. In addition, by containing a specific ester wax, the transparency and color tone of the molded article are not lowered, the impact resistance of the molded article is further improved, and the fluidity of the transparent thermoplastic resin composition is improved to obtain good moldability. Furthermore, by containing a specific organic acid monoester, the transparency and color tone of the molded product are not lowered, and the fluidity of the transparent thermoplastic resin composition is further improved, thereby obtaining good moldability.

(接枝共聚合體(A)) 構成本發明之透明熱可塑性樹脂組成物的接枝共聚合體(A)，係於橡膠質聚合體(r)存在下，使至少含有芳香族乙烯系單體(a1)及(甲基)丙烯酸酯系單體(a2)之單體混合物(a)進行接枝共聚合而得者。單體混合物(a)亦可進一步含有可與上述(a1)及上述(a2)共聚合之其他單體(a3)。 (graft copolymer (A)) The graft copolymer (A) constituting the transparent thermoplastic resin composition of the present invention contains at least an aromatic vinyl monomer (a1) and a (meth)acrylate in the presence of the rubbery polymer (r). It is obtained by graft copolymerization of monomer mixture (a) of monomer (a2). The monomer mixture (a) may further contain other monomer (a3) which can be copolymerized with the above-mentioned (a1) and the above-mentioned (a2).

作為橡膠質聚合體(r)，可舉例如聚丁二烯、聚(丁二烯-苯乙烯)(SBR)、聚(丁二烯-丙烯腈)(NBR)、聚(丁二烯-丙烯酸丁酯)、聚(丁二烯-甲基丙烯酸甲酯)、聚(丙烯酸丁酯-甲基丙烯酸甲酯)、聚(丁二烯-丙烯酸乙酯)、天然橡膠等。此等可單獨使用1種、亦可使用2種以上。其中，由更加提升樹脂組成物之耐衝擊性、透明性、色調的觀點而言，較佳為聚丁二烯、SBR、NBR、天然橡膠，更佳為聚丁二烯。Examples of the rubbery polymer (r) include polybutadiene, poly(butadiene-styrene) (SBR), poly(butadiene-acrylonitrile) (NBR), poly(butadiene-acrylic acid) butyl), poly(butadiene-methyl methacrylate), poly(butyl acrylate-methyl methacrylate), poly(butadiene-ethyl acrylate), natural rubber, etc. These may be used individually by 1 type, and may use 2 or more types. Among them, from the viewpoint of further improving the impact resistance, transparency, and color tone of the resin composition, polybutadiene, SBR, NBR, and natural rubber are preferred, and polybutadiene is more preferred.

橡膠質聚合體(r)之質量平均粒徑較佳為0.15μm以上且0.4μm以下、更佳為0.20μm以上且0.35μm以下、又更佳為0.25μm以上且0.35μm以下。藉由將橡膠質聚合體(r)之質量平均粒徑設為0.15μm以上，可更加提升成形品之耐衝擊性。另一方面，藉由將橡膠質聚合體(r)之質量平均粒徑設為0.4μm以下，可更加提升成形品之透明性、色調。The mass average particle diameter of the rubbery polymer (r) is preferably 0.15 μm or more and 0.4 μm or less, more preferably 0.20 μm or more and 0.35 μm or less, and still more preferably 0.25 μm or more and 0.35 μm or less. By setting the mass average particle diameter of the rubbery polymer (r) to be 0.15 μm or more, the impact resistance of the molded product can be further improved. On the other hand, by setting the mass average particle diameter of the rubbery polymer (r) to be 0.4 μm or less, the transparency and color tone of the molded article can be further improved.

橡膠質聚合體(r)之質量平均粒徑係將橡膠質聚合體(r)之乳膠以水媒體稀釋、分散，藉由雷射散射繞射法粒度分佈測定裝置(例如「LS 13 320」(Beckman Coulter股份有限公司))測定粒徑分佈，由該粒徑分佈可算出。The mass average particle size of the rubbery polymer (r) is obtained by diluting and dispersing the latex of the rubbery polymer (r) with a water medium, and measuring the particle size distribution by a laser scattering diffraction method (such as "LS 13 320" ( Beckman Coulter Co., Ltd.)) measures the particle size distribution, and can calculate from the particle size distribution.

相對於構成接枝共聚合體(A)之橡膠質聚合體(r)及後述單體混合物(a)之總量，橡膠質聚合體(r)之含量較佳為20質量%以上且80質量%以下。若橡膠質聚合體(r)之含量為20質量%以上，可更加提升成形品之耐衝擊性及色調、透明性。橡膠質聚合體(r)之含量更佳為35質量%以上。另一方面，若橡膠質聚合體(r)之含量為80質量%以下，可更加提升透明熱可塑性樹脂組成物之流動性、成形品之耐衝擊性。橡膠質聚合體(r)之含量更佳為60質量%以下。The content of the rubbery polymer (r) is preferably 20% by mass or more and 80% by mass relative to the total amount of the rubbery polymer (r) constituting the graft copolymer (A) and the monomer mixture (a) described later. the following. If the content of the rubbery polymer (r) is 20 mass % or more, the impact resistance, color tone, and transparency of the molded article can be further improved. The content of the rubbery polymer (r) is more preferably 35% by mass or more. On the other hand, when the content of the rubbery polymer (r) is 80 mass % or less, the fluidity of the transparent thermoplastic resin composition and the impact resistance of the molded article can be further improved. The content of the rubbery polymer (r) is more preferably 60 mass % or less.

作為單體混合物(a)中之芳香族乙烯系單體(a1)，可舉例如苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、間甲基苯乙烯、鄰甲基苯乙烯、乙烯基甲苯、第三丁基苯乙烯等苯乙烯系單體等。此等可單獨使用1種、亦可含有2種以上。此等之中，由更加提升透明熱可塑性樹脂組成物之流動性及成形品之透明性、剛性的觀點而言，較佳為苯乙烯。As the aromatic vinyl-based monomer (a1) in the monomer mixture (a), for example, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, Styrenic monomers such as vinyl toluene and tertiary butyl styrene, etc. These may be used individually by 1 type, and may contain 2 or more types. Among these, from the viewpoint of further enhancing the fluidity of the transparent thermoplastic resin composition and the transparency and rigidity of the molded article, styrene is preferred.

單體混合物(a)中之芳香族乙烯系單體(a1)的含量，係由更加提升透明熱可塑性樹脂組成物之流動性及成形品之透明性、剛性的觀點而言，於單體混合物(a)之合計100質量%中，較佳為5質量%以上、更佳為10質量%以上、又更佳為20質量%以上。另一方面，單體混合物(a)中之芳香族乙烯系單體(a1)的含量，係由提升成形品之耐衝擊性及透明性的觀點而言，較佳為40質量%以下、更佳為35質量%以下、又更佳為30質量%以下。The content of the aromatic vinyl-based monomer (a1) in the monomer mixture (a) is higher than the monomer mixture from the viewpoint of further improving the fluidity of the transparent thermoplastic resin composition and the transparency and rigidity of the molded product. In the total 100 mass % of (a), 5 mass % or more is preferable, 10 mass % or more is more preferable, and 20 mass % or more is more preferable. On the other hand, the content of the aromatic vinyl monomer (a1) in the monomer mixture (a) is preferably 40 mass % or less, from the viewpoint of improving the impact resistance and transparency of the molded product. Preferably it is 35 mass % or less, More preferably, it is 30 mass % or less.

作為單體混合物(a)中之(甲基)丙烯酸酯系單體(a2)，較佳為例如碳數1~6之醇與丙烯酸或甲基丙烯酸之酯。碳數1~6之醇與丙烯酸或甲基丙烯酸之酯亦可進一步具有羥基或鹵基等取代基。作為碳數1~6之醇與丙烯酸或甲基丙烯酸之酯，可舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸氯甲酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸2,3,4,5,6-五羥基己酯、(甲基)丙烯酸2,3,4,5-四羥基戊酯等。此等可單獨使用1種、亦可含有2種以上。此等之中，由提升成形品之透明性的觀點而言，較佳為(甲基)丙烯酸甲酯。As the (meth)acrylate-based monomer (a2) in the monomer mixture (a), for example, esters of alcohols having 1 to 6 carbon atoms and acrylic acid or methacrylic acid are preferable. The ester of the alcohol having 1 to 6 carbon atoms and acrylic acid or methacrylic acid may further have a substituent such as a hydroxyl group or a halogen group. Examples of esters of alcohols having 1 to 6 carbon atoms and acrylic acid or methacrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. n-Butyl, 3-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, chloromethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate , 2,3,4,5,6-pentahydroxyhexyl (meth)acrylate, 2,3,4,5-tetrahydroxypentyl (meth)acrylate, etc. These may be used individually by 1 type, and may contain 2 or more types. Among these, from the viewpoint of improving the transparency of the molded product, methyl (meth)acrylate is preferred.

單體混合物(a)中之(甲基)丙烯酸酯系單體(a2)的含量，由提升成形品之透明性的觀點而言，於單體混合物(a)之合計100質量%中，較佳為30質量%以上、更佳為50質量%以上、又更佳為70質量%以上。另一方面，單體混合物(a)中之(甲基)丙烯酸酯系單體(a2)的含量，由提升成形品之透明性的觀點而言，於單體混合物(a)之合計100質量%中，較佳為85質量%以下、更佳為80質量%以下、又更佳為75質量%以下。The content of the (meth)acrylate-based monomer (a2) in the monomer mixture (a) is higher than the total 100 mass % of the monomer mixture (a) from the viewpoint of improving transparency of the molded article Preferably it is 30 mass % or more, More preferably, it is 50 mass % or more, More preferably, it is 70 mass % or more. On the other hand, the content of the (meth)acrylate-based monomer (a2) in the monomer mixture (a) is 100 mass in total of the monomer mixture (a) from the viewpoint of improving the transparency of the molded article. In %, preferably 85 mass % or less, more preferably 80 mass % or less, and still more preferably 75 mass % or less.

又，可與此等共聚合之其他單體(a3)係上述芳香族乙烯系單體(a1)、(甲基)丙烯酸酯系單體(a2)以外的乙烯系單體，只要為未損及本發明效果者則無特別限制。In addition, other monomers (a3) that can be copolymerized with these are vinyl-based monomers other than the above-mentioned aromatic vinyl-based monomer (a1) and (meth)acrylate-based monomer (a2), as long as they are not damaged and the effects of the present invention are not particularly limited.

作為其他單體(a3)，具體而言，可舉例如氰化乙烯系單體、不飽和脂肪酸、丙烯醯胺系單體、順丁烯二醯亞胺系單體等。此等可單獨使用1種、亦可含有2種以上。As another monomer (a3), a vinyl cyanide-type monomer, an unsaturated fatty acid, an acrylamide-type monomer, a maleimide-type monomer etc. are mentioned specifically,. These may be used individually by 1 type, and may contain 2 or more types.

作為氰化乙烯系單體，可舉例如丙烯腈、甲基丙烯腈、乙基丙烯腈等。此等可單獨使用1種、亦可含有2種以上。此等之中，由更加提升成形品之耐衝擊性的觀點而言，較佳為丙烯腈。As a vinyl cyanide type monomer, acrylonitrile, methacrylonitrile, ethacrylonitrile, etc. are mentioned, for example. These may be used individually by 1 type, and may contain 2 or more types. Among these, acrylonitrile is preferred from the viewpoint of further improving the impact resistance of the molded product.

作為不飽和脂肪酸，可舉例如衣康酸、順丁烯二酸、反丁烯二酸、丁烯酸、丙烯酸、甲基丙烯酸等。As an unsaturated fatty acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, acrylic acid, methacrylic acid, etc. are mentioned, for example.

作為丙烯醯胺系單體，可舉例如丙烯醯胺、甲基丙烯醯胺、N-甲基丙烯醯胺等。As acrylamide-type monomer, acrylamide, methacrylamide, N-methacrylamide, etc. are mentioned, for example.

作為順丁烯二醯亞胺系單體，可舉例如N-甲基順丁烯二醯亞胺、N-乙基順丁烯二醯亞胺、N-異丙基順丁烯二醯亞胺、N-丁基順丁烯二醯亞胺、N-己基順丁烯二醯亞胺、N-辛基順丁烯二醯亞胺、N-十二烷基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺等。Examples of the maleimide-based monomer include N-methylmaleimide, N-ethylmaleimide, and N-isopropylmaleimide. Amine, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-ring Hexylmaleimide, N-phenylmaleimide, etc.

單體混合物(a)中之其他單體(a3)的含量，係由提升成形品之耐衝擊性的觀點而言，較佳為2質量%以上。另一方面，由提升成形品之色調的觀點而言，較佳為50質量%以下、更佳為20質量%以下、又更佳為5質量%以下。The content of the other monomer (a3) in the monomer mixture (a) is preferably 2 mass % or more from the viewpoint of improving the impact resistance of the molded product. On the other hand, from the viewpoint of improving the color tone of the molded product, it is preferably 50% by mass or less, more preferably 20% by mass or less, and still more preferably 5% by mass or less.

接枝共聚合體(A)之接枝率並無特別限制，由提升成形品之耐衝擊性的觀點而言，較佳為10%以上且100%以下。The graft ratio of the graft copolymer (A) is not particularly limited, but is preferably 10% or more and 100% or less from the viewpoint of improving the impact resistance of the molded product.

於此，接枝共聚合體(A)之接枝率可藉以下方法求得。首先，對接枝共聚合體(A)約1g(m：樣本質量)添加丙酮80ml，於70℃熱水浴中回流3小時，將此溶液以8,000rpm(10,000G)離心40分鐘後，過濾不溶份，得到丙酮不溶份。將所得丙酮不溶份以80℃減壓乾燥5小時，測定其質量(n)，由下式算出接枝率。於此，X為接枝共聚合體(A)之橡膠質聚合體含有率(%)。Here, the graft ratio of the graft copolymer (A) can be obtained by the following method. First, 80 ml of acetone was added to about 1 g (m: sample mass) of the graft copolymer (A), and the solution was refluxed in a hot water bath at 70°C for 3 hours. parts to obtain acetone-insoluble parts. The obtained acetone-insoluble fraction was dried under reduced pressure at 80° C. for 5 hours, the mass (n) was measured, and the graft ratio was calculated from the following formula. Here, X is the rubbery polymer content (%) of the graft copolymer (A).

接枝率(%)={[(n)-((m)×X/100)]/[(m)×X/100]}×100。Grafting ratio (%)={[(n)-((m)×X/100)]/[(m)×X/100]}×100.

本發明中，接枝共聚合體(A)之製造方法係由可將橡膠質聚合體(r)之質量平均粒徑輕易控制於所需範圍、或可藉由聚合時之除熱輕易控制聚合穩定性而言，較佳為乳化聚合法。In the present invention, the method for producing the graft copolymer (A) is that the mass average particle size of the rubbery polymer (r) can be easily controlled within a desired range, or the polymerization stability can be easily controlled by removing heat during polymerization. In terms of properties, the emulsion polymerization method is preferred.

藉由乳化聚合法製造接枝共聚合體(A)時，橡膠質聚合體(r)與單體混合物(a)之填裝方法並無特別限定。例如，可於初期一次填裝此等全部，亦可為了調整共聚合體組成之分佈，連續地填裝單體混合物(a)之一部分、或分割單體混合物(a)之一部分或全部而填裝。於此，所謂連續地填裝單體混合物(a)之一部分，係指於初期填裝單體混合物(a)之一部分，並經時性地連續填裝剩餘部分。又，所謂分割單體混合物(a)之一部分或全部而填裝，係指將單體混合物(a)之一部分或全部於初期填裝後之時點進行填裝。When the graft copolymer (A) is produced by the emulsion polymerization method, the packing method of the rubbery polymer (r) and the monomer mixture (a) is not particularly limited. For example, all of these may be charged at one time at the initial stage, or a part of the monomer mixture (a) may be continuously charged, or a part or all of the monomer mixture (a) may be charged continuously in order to adjust the distribution of the copolymer composition. . Here, the term "continuously charging a part of the monomer mixture (a)" means that a part of the monomer mixture (a) is charged at the initial stage, and the remaining part is continuously charged over time. In addition, charging by dividing a part or the whole of the monomer mixture (a) means charging a part or the whole of the monomer mixture (a) at a point after the initial charging.

藉由乳化聚合法製造接枝共聚合體(A)時，亦可添加各種界面活性劑作為乳化劑。作為各種界面活性劑，特佳係使用羧酸鹽型、硫酸酯鹽型、磺酸鹽型等陰離子系界面活性劑。此等可單獨使用1種、亦可組合2種以上。又，於此所謂鹽，可舉例如鈉鹽、鋰鹽、鉀鹽等鹼金屬鹽、銨鹽等。When producing the graft copolymer (A) by the emulsion polymerization method, various surfactants may be added as an emulsifier. As various surfactants, anionic surfactants such as carboxylate-type, sulfate-ester-type, and sulfonate-type surfactants are particularly preferably used. These may be used individually by 1 type, and may combine 2 or more types. Moreover, as a salt here, alkali metal salts, such as a sodium salt, a lithium salt, a potassium salt, an ammonium salt, etc. are mentioned, for example.

作為羧酸鹽型之乳化劑，可舉例如辛酸鹽、癸酸鹽、月桂酸鹽、肉荳蔻酸鹽、軟脂酸鹽、硬脂酸鹽、油酸鹽、亞麻油酸鹽、次亞麻油酸鹽、松脂酸鹽、二十二酸鹽、二烷基磺基琥珀酸鹽等。Examples of carboxylate-type emulsifiers include caprylate, caprate, laurate, myristate, palmitate, stearate, oleate, linoleate, and linseed oil. acid salt, rosinate, behenate, dialkylsulfosuccinate, etc.

作為硫酸酯鹽型之乳化劑，可舉例如蓖麻子油硫酸酯鹽、月桂醇硫酸酯鹽、聚氧乙烯月桂基硫酸鹽、聚氧乙烯烷基醚硫酸鹽、聚氧乙烯烷基苯基醚硫酸鹽等。Examples of sulfate-type emulsifiers include castor oil sulfate, lauryl sulfate, polyoxyethylene lauryl sulfate, polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkyl phenyl ether. Sulfate etc.

作為磺酸鹽型之乳化劑，可舉例如十二烷基苯磺酸鹽、烷基萘磺酸鹽、烷基二苯基醚二磺酸鹽、萘磺酸鹽縮合物等。As a sulfonate type emulsifier, a dodecylbenzenesulfonate, an alkylnaphthalenesulfonate, an alkyldiphenyl ether disulfonate, a naphthalenesulfonate condensate, etc. are mentioned, for example.

於藉由乳化聚合法製造接枝共聚合體(A)時，視需要亦可添加起始劑。作為起始劑，可舉例如過氧化物、偶氮系化合物、水溶性之過硫酸鉀等。此等可單獨使用1種、亦可組合2種以上。When producing the graft copolymer (A) by an emulsion polymerization method, an initiator may be added as needed. As a starting agent, a peroxide, an azo compound, a water-soluble potassium persulfate etc. are mentioned, for example. These may be used individually by 1 type, and may combine 2 or more types.

作為過氧化物，可舉例如過氧化苯甲醯、異丙苯過氧化氫、過氧化二異丙苯、二異丙基苯過氧化氫、第三丁基過氧化氫、過氧乙酸第三丁酯、過氧苯甲酸第三丁酯、碳酸第三丁基異丙酯、過氧化二第三丁基、過氧辛酸第三丁酯、1,1-雙(第三丁基過氧基)3,3,5-三甲基環己烷、1,1-雙(第三丁基過氧基)環己烷、第三丁基過氧基-2-乙基己酸酯等。其中，特佳係使用異丙苯過氧化氫、1,1-雙(第三丁基過氧基)3,3,5-三甲基環己烷、1,1-雙(第三丁基過氧基)環己烷。As the peroxide, for example, benzyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, peracetic acid tertiary Butyl ester, tert-butyl peroxybenzoate, tert-butyl isopropyl carbonate, di-tert-butyl peroxide, tert-butyl peroxyoctanoate, 1,1-bis(tert-butylperoxy ) 3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butylperoxy-2-ethylhexanoate, and the like. Among them, the particularly preferred ones use cumene hydroperoxide, 1,1-bis(tert-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy) peroxy) cyclohexane.

作為偶氮系化合物，可舉例如偶氮雙異丁腈、偶氮雙(2,4-二甲基)戊腈、2-苯基偶氮-2,4-二甲基-4-甲氧基戊腈、2-氰基-2-丙基偶氮甲醯胺、1,1’-偶氮雙環己烷-1-甲腈、偶氮雙(4-甲氧基-2,4-二甲基)戊腈、2,2’-偶氮雙異丁酸二甲基酯、1-第三丁基偶氮-2-氰基丁烷、2-第三丁基偶氮-2-氰基-4-甲氧基-4-甲基戊烷等。其中，特佳係使用1,1’-偶氮雙環己烷-1-甲腈、偶氮雙異丁腈。As the azo compound, for example, azobisisobutyronitrile, azobis(2,4-dimethyl)valeronitrile, 2-phenylazo-2,4-dimethyl-4-methoxy valeronitrile, 2-cyano-2-propylazocarbamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis(4-methoxy-2,4-di Methyl)valeronitrile, dimethyl 2,2'-azobisisobutyrate, 1-tert-butylazo-2-cyanobutane, 2-tert-butylazo-2-cyano base-4-methoxy-4-methylpentane, etc. Among them, 1,1'-azobiscyclohexane-1-carbonitrile and azobisisobutyronitrile are particularly preferred.

用於製造接枝共聚合體(A)所使用之起始劑的添加量並無特別限制，由接枝共聚合體(A)之生產性的觀點而言，相對於橡膠質聚合體(r)與單體混合物(a)之合計100質量份，較佳為0.1質量份以上且0.5質量份以下。The addition amount of the initiator used for producing the graft copolymer (A) is not particularly limited, but from the viewpoint of the productivity of the graft copolymer (A), the amount of the starting agent relative to the rubbery polymer (r) and The total of 100 parts by mass of the monomer mixture (a) is preferably 0.1 part by mass or more and 0.5 part by mass or less.

藉由乳化聚合法製造接枝共聚合體(A)時，亦可使用鏈轉移劑。藉由使用鏈轉移劑，可將接枝共聚合體(A)之接枝率容易調整為所需範圍。作為鏈轉移劑，可舉例如正辛基硫醇、第三(十二烷基)硫醇、正十二烷基硫醇、正十四烷基硫醇、正十八烷基硫醇等硫醇；萜品油烯等萜等。此等可單獨使用1種、亦可組合2種以上。其中，較佳係使用正辛基硫醇、第三(十二烷基)硫醇。When producing the graft copolymer (A) by an emulsion polymerization method, a chain transfer agent can also be used. By using a chain transfer agent, the graft ratio of the graft copolymer (A) can be easily adjusted to a desired range. Examples of the chain transfer agent include sulfur such as n-octyl mercaptan, tertiary (dodecyl) mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, and n-octadecyl mercaptan. Alcohols; terpenes such as terpinolene, etc. These may be used individually by 1 type, and may combine 2 or more types. Among them, n-octyl mercaptan and tertiary (dodecyl) mercaptan are preferably used.

用於製造接枝共聚合體(A)所使用之鏈轉移劑的添加量並無特別限制，由容易控制接枝共聚合體(A)之接枝率的觀點而言，相對於橡膠質聚合體(r)與單體混合物(a)之合計100質量份，較佳為0.2質量份以上且0.7質量份以下。下限更佳為0.4質量份以上，上限更佳為0.6質量份以下。The addition amount of the chain transfer agent used for the production of the graft copolymer (A) is not particularly limited, but from the viewpoint of easy control of the graft ratio of the graft copolymer (A), the amount of the chain transfer agent relative to the rubbery polymer ( r) The total amount of the monomer mixture (a) is 100 parts by mass, preferably 0.2 parts by mass or more and 0.7 parts by mass or less. The lower limit is more preferably 0.4 part by mass or more, and the upper limit is more preferably 0.6 part by mass or less.

藉由乳化聚合製造接枝共聚合體(A)時，聚合溫度並無特別限制，由乳化穩定性的觀點而言，較佳為40~70℃。When producing the graft copolymer (A) by emulsion polymerization, the polymerization temperature is not particularly limited, but from the viewpoint of emulsion stability, it is preferably 40 to 70°C.

藉由乳化聚合法製造接枝共聚合體(A)時，一般係對接枝共聚合體乳膠添加凝固劑，回收接枝共聚合體(A)。作為凝固劑，較佳係使用酸或水溶性鹽。When the graft copolymer (A) is produced by the emulsion polymerization method, a coagulant is generally added to the graft copolymer latex, and the graft copolymer (A) is recovered. As the coagulant, an acid or a water-soluble salt is preferably used.

作為酸，可舉例如硫酸、鹽酸、磷酸、醋酸等。作為水溶性鹽，可舉例如氯化鈣、氯化鎂、氯化鋇、氯化鋁、硫酸鎂、硫酸鋁、硫酸鋁銨、硫酸鋁鉀、硫酸鋁鈉等。此等可單獨使用1種、亦可組合2種以上。由提升成形品之色調的觀點而言，較佳係於熱可塑性樹脂組成物中不殘存乳化劑，且較佳係使用鹼脂肪酸鹽作為乳化劑進行酸凝固。此時，較佳係接著藉由例如氫氧化鈉等鹼進行中和，去除乳化劑。As an acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, etc. are mentioned, for example. As a water-soluble salt, calcium chloride, magnesium chloride, barium chloride, aluminum chloride, magnesium sulfate, aluminum sulfate, aluminum ammonium sulfate, aluminum potassium sulfate, aluminum sodium sulfate, etc. are mentioned, for example. These may be used individually by 1 type, and may combine 2 or more types. From the viewpoint of improving the color tone of the molded product, it is preferable that the emulsifier does not remain in the thermoplastic resin composition, and it is preferable to perform acid coagulation using an alkali fatty acid salt as the emulsifier. In this case, the emulsifier is preferably removed by neutralization with an alkali such as sodium hydroxide next.

(乙烯系共聚合體(B)) 構成本發明之透明熱可塑性樹脂組成物的乙烯系共聚合體(B)，係使至少含有芳香族乙烯系單體(b1)、(甲基)丙烯酸酯系單體(b2)及氰化乙烯系單體(b3)之單體混合物(b)進行共聚合而得者。單體混合物(b)亦可進一步含有可與上述(b1)~(b3)共聚合之其他單體(b4)。 (Ethylene-based copolymer (B)) The vinyl-based copolymer (B) constituting the transparent thermoplastic resin composition of the present invention contains at least an aromatic vinyl-based monomer (b1), a (meth)acrylate-based monomer (b2), and a vinyl cyanide-based monomer It is obtained by copolymerizing the monomer mixture (b) of the monomer (b3). The monomer mixture (b) may further contain other monomer (b4) which can be copolymerized with the above-mentioned (b1) to (b3).

作為芳香族乙烯系單體(b1)，可舉例如作為芳香族乙烯系單體(a1)所例示者，較佳為苯乙烯。As the aromatic vinyl-based monomer (b1), for example, those exemplified as the aromatic vinyl-based monomer (a1) may be mentioned, and styrene is preferable.

單體混合物(b)中之芳香族乙烯系單體(b1)的含量，由可更加提升透明熱可塑性樹脂組成物之流動性及成形品之透明性、剛性的觀點而言，於單體混合物(b)之合計100質量%中，較佳為5質量%以上、更佳為10質量%以上、又更佳為20質量%以上。另一方面，單體混合物(b)中之芳香族乙烯系單體(b1)的含量係由提升成形品之耐衝擊性及透明性的觀點而言，較佳為40質量%以下、更佳為30質量%以下、又更佳為25質量%以下。The content of the aromatic vinyl-based monomer (b1) in the monomer mixture (b) can further improve the fluidity of the transparent thermoplastic resin composition and the transparency and rigidity of the molded article. In the total 100 mass % of (b), 5 mass % or more is preferable, 10 mass % or more is more preferable, and 20 mass % or more is more preferable. On the other hand, the content of the aromatic vinyl monomer (b1) in the monomer mixture (b) is preferably 40 mass % or less, more preferably from the viewpoint of improving the impact resistance and transparency of the molded article. It is 30 mass % or less, More preferably, it is 25 mass % or less.

作為(甲基)丙烯酸酯系單體(b2)，可舉例如作為(甲基)丙烯酸酯系單體(a2)所例示者，較佳為(甲基)丙烯酸甲酯。As a (meth)acrylate type monomer (b2), what was illustrated as a (meth)acrylate type monomer (a2) is mentioned, for example, Methyl (meth)acrylate is preferable.

單體混合物(b)中之(甲基)丙烯酸酯系單體(b2)的含量，由可提升成形品之透明性的觀點而言，於單體混合物(b)之合計100質量%中，較佳為30質量%以上、更佳為50質量%以上、又更佳為60質量%以上。另一方面，單體混合物(b)中之(甲基)丙烯酸酯系單體(b2)的含量係由更加提升成形品之透明性的觀點而言，較佳為85質量%以下、更佳為80質量%以下、又更佳為75質量%以下。The content of the (meth)acrylate-based monomer (b2) in the monomer mixture (b) is, from the viewpoint of improving the transparency of the molded article, in the total 100 mass % of the monomer mixture (b), Preferably it is 30 mass % or more, More preferably, it is 50 mass % or more, More preferably, it is 60 mass % or more. On the other hand, the content of the (meth)acrylate-based monomer (b2) in the monomer mixture (b) is preferably 85% by mass or less, more preferably from the viewpoint of further improving the transparency of the molded product It is 80 mass % or less, More preferably, it is 75 mass % or less.

作為氰化乙烯系單體(b3)，可舉例如丙烯腈、甲基丙烯腈、乙基丙烯腈等。此等可單獨使用1種、亦可含有2種以上。此等之中，由更加提升成形品之耐衝擊性的觀點而言，較佳為丙烯腈。As a vinyl cyanide type monomer (b3), acrylonitrile, methacrylonitrile, ethacrylonitrile, etc. are mentioned, for example. These may be used individually by 1 type, and may contain 2 or more types. Among these, acrylonitrile is preferred from the viewpoint of further improving the impact resistance of the molded product.

單體混合物(b)中之氰化乙烯系單體(b3)的含量，係由更加提升成形品之耐衝擊性的觀點而言，於單體混合物(b)之合計100質量%中，較佳為2質量%以上、更佳為3質量%以上。另一方面，單體混合物(b)中之氰化乙烯系單體(b3)的含量係由提升成形品之色調的觀點而言，較佳為50質量%以下、更佳為20質量%以下、又更佳為10質量%以下、最佳為5質量%以下。The content of the vinyl cyanide-based monomer (b3) in the monomer mixture (b) is more than Preferably it is 2 mass % or more, More preferably, it is 3 mass % or more. On the other hand, the content of the vinyl cyanide-based monomer (b3) in the monomer mixture (b) is preferably 50 mass % or less, more preferably 20 mass % or less, from the viewpoint of improving the color tone of the molded product , and more preferably 10 mass % or less, and most preferably 5 mass % or less.

又，可與此等共聚合之其他單體(b4)，係上述芳香族乙烯系單體(b1)、(甲基)丙烯酸酯系單體(b2)、氰化乙烯系單體(b3)以外之乙烯系單體，只要為不損及本發明效果者則無特別限制。Further, other monomers (b4) that can be copolymerized with these are the above-mentioned aromatic vinyl monomers (b1), (meth)acrylate-based monomers (b2), and vinyl cyanide-based monomers (b3) Other vinyl-based monomers are not particularly limited as long as they do not impair the effects of the present invention.

作為其他單體(b4)，具體而言，可舉例如不飽和脂肪酸、丙烯醯胺系單體、順丁烯二醯亞胺系單體等。此等可單獨使用1種、亦可含有2種以上。Specific examples of the other monomer (b4) include unsaturated fatty acids, acrylamide-based monomers, maleimide-based monomers, and the like. These may be used individually by 1 type, and may contain 2 or more types.

作為不飽和脂肪酸，可舉例如衣康酸、順丁烯二酸、反丁烯二酸、丁烯酸、丙烯酸、甲基丙烯酸等。As an unsaturated fatty acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, acrylic acid, methacrylic acid, etc. are mentioned, for example.

作為丙烯醯胺系單體，可舉例如丙烯醯胺、甲基丙烯醯胺、N-甲基丙烯醯胺等。As acrylamide-type monomer, acrylamide, methacrylamide, N-methacrylamide, etc. are mentioned, for example.

作為順丁烯二醯亞胺系單體，可舉例如N-甲基順丁烯二醯亞胺、N-乙基順丁烯二醯亞胺、N-異丙基順丁烯二醯亞胺、N-丁基順丁烯二醯亞胺、N-己基順丁烯二醯亞胺、N-辛基順丁烯二醯亞胺、N-十二烷基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺等。Examples of the maleimide-based monomer include N-methylmaleimide, N-ethylmaleimide, and N-isopropylmaleimide. Amine, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-ring Hexylmaleimide, N-phenylmaleimide, etc.

單體混合物(b)中之其他單體(b4)的含量，係由提升透明熱可塑性樹脂組成物之流動性、成形品之耐衝擊性、透明性及色調的觀點而言，較佳為20質量%以下、更佳為10質量%以下。The content of the other monomers (b4) in the monomer mixture (b) is preferably 20 from the viewpoint of improving the fluidity of the transparent thermoplastic resin composition, impact resistance, transparency and color tone of the molded product. % by mass or less, more preferably 10% by mass or less.

本發明中，乙烯系共聚合體(B)之製造方法並無特別限制，由提升所得透明熱可塑性樹脂組成物之流動性、成形品之透明性及色調的觀點而言，較佳係使用連續塊狀聚合法或連續溶液聚合法。尤其是藉由使用連續塊狀聚合法或連續溶液聚合法，可使乙烯系共聚合體(B)之分子量分佈狹窄，故提升流動性。In the present invention, the method for producing the ethylene-based copolymer (B) is not particularly limited, but from the viewpoint of improving the fluidity of the obtained transparent thermoplastic resin composition, the transparency of the molded article, and the color tone, a continuous block is preferably used. state-of-the-art polymerization or continuous solution polymerization. In particular, by using the continuous block polymerization method or the continuous solution polymerization method, the molecular weight distribution of the ethylene-based copolymer (B) can be narrowed, thereby improving the fluidity.

作為藉由連續塊狀聚合法或連續溶液聚合法製造乙烯系共聚合體(B)之方法，可採用習知公知之任意方法，可舉例如於聚合槽中使單體混合物(b)進行聚合後，進行脫單體(脫溶媒、揮發)之方法。As a method for producing the vinyl copolymer (B) by a continuous block polymerization method or a continuous solution polymerization method, any conventionally known method can be adopted, and for example, after polymerizing the monomer mixture (b) in a polymerization tank, for example, , carry out the method of removing monomer (removing solvent, volatilization).

作為聚合槽，可使用例如具有槳翼、渦輪葉片、螺旋翼、布魯馬金式(Brumargin)葉片、多層葉片、錨式葉片、柵漿式(Maxblend)葉片、雙螺旋葉片(double-helical)等攪拌葉片的混合式聚合槽；或者各種塔式反應器等。又，亦可將多管反應器、揉捏式反應器及雙軸擠出機等使用作為聚合反應器(例如參照高分子製造程序之評估10「耐衝擊性聚苯乙烯之評估」高分子學會、1989年1月26日發行等)。As the polymerization tank, for example, a propeller blade, a turbine blade, a propeller blade, a Brumargin blade, a multi-layer blade, an anchor blade, a Maxblend blade, or a double-helical blade can be used. Mixed polymerization tanks such as stirring blades; or various tower reactors, etc. In addition, a multi-tube reactor, a kneading reactor, and a twin-screw extruder can also be used as a polymerization reactor (for example, refer to Evaluation of Polymer Manufacturing Procedures 10 "Evaluation of Impact-Resistant Polystyrene" by the Society of Polymer Science and Technology. , issued on January 26, 1989, etc.).

此等聚合槽或聚合反應器可使用2座(2槽)以上，視需要亦可組合2種以上之聚合槽或聚合反應器。由減小乙烯系共聚合體(B)之分散度的觀點而言，聚合槽或聚合反應器較佳係2座(2槽)以下，更佳係單槽式的完全混合型聚合槽。As these polymerization tanks or polymerization reactors, two or more (two tanks) may be used, and if necessary, two or more polymerization tanks or polymerization reactors may be combined. From the viewpoint of reducing the degree of dispersion of the ethylene-based copolymer (B), the number of polymerization tanks or polymerization reactors is preferably two or less (two tanks), and more preferably a single tank type complete mixing type polymerization tank.

於此等聚合槽或聚合反應器中進行聚合所得的反應混合物，通常接著供於脫單體步驟，去除單體及溶媒等其他揮發成分。作為脫單體之方法，可舉例如：利用具排氣的單軸或雙軸擠出機，於加熱下、常壓或減壓下，從排氣孔去除揮發成分的方法；利用滾筒中內建有離心型等板翅式加熱器的蒸發器去除揮發成分的方法；利用離心型等薄膜蒸發器去除揮發成分的方法；使用多管式熱交換器施行預熱、發泡，對真空槽施行閃化而去除揮發成分的方法等。此等之中，特佳係使用藉由具排氣的單軸或雙軸擠出機去除揮發成分的方法。The reaction mixture obtained by carrying out the polymerization in these polymerization tanks or polymerization reactors is usually subsequently subjected to a de-monomerization step to remove other volatile components such as monomers and solvents. As a method for removing monomers, for example: a method of removing volatile components from a vent hole under heating, normal pressure or reduced pressure using a single-screw or twin-screw extruder with vent; A method for removing volatile components from an evaporator equipped with a centrifugal type plate-fin heater; a method for removing volatile components using a centrifugal type and other thin-film evaporators; preheating and foaming using a multi-tube heat exchanger, and a vacuum tank A method of removing volatile components by flashing, etc. Among them, the method of removing volatile components by a single-screw or double-screw extruder with venting is particularly preferred.

製造乙烯系共聚合體(B)時，視需要亦可使用起始劑或鏈轉移劑。作為起始劑及鏈轉移劑，可舉例如於接枝共聚合體(A)之製造方法中所例示之起始劑及鏈轉移劑。起始劑亦可使用氧化還原系統。When producing the ethylene-based copolymer (B), an initiator or a chain transfer agent may be used as necessary. As an initiator and a chain transfer agent, the initiator and chain transfer agent illustrated by the manufacturing method of a graft copolymer (A) are mentioned, for example. Redox systems can also be used as initiators.

用於製造乙烯系共聚合體(B)所使用之起始劑的添加量並無特別的限制，由提高乙烯系共聚合體(B)之聚合率的觀點而言，相對於單體混合物(b)之合計100質量份，較佳係0.01~0.03質量份。The addition amount of the initiator used for producing the vinyl-based copolymer (B) is not particularly limited, but from the viewpoint of increasing the polymerization rate of the vinyl-based copolymer (B), the amount relative to the monomer mixture (b) The total of 100 parts by mass is preferably 0.01 to 0.03 parts by mass.

用於製造乙烯系共聚合體(B)所使用之鏈轉移劑的添加量並無特別的限制，由提升乙烯系共聚合體(B)之流動性的觀點而言，相對於單體混合物(b)之合計100質量份，較佳為0.10~0.30質量份。The addition amount of the chain transfer agent used for producing the vinyl-based copolymer (B) is not particularly limited, but from the viewpoint of improving the fluidity of the vinyl-based copolymer (B), it is relatively The total of 100 parts by mass is preferably 0.10 to 0.30 parts by mass.

於藉由連續塊狀聚合法或連續溶液聚合法製造乙烯系共聚合體(B)的情況，聚合溫度並無特別的限制，由乙烯系共聚合體(B)之生產性的觀點而言，較佳係120~140℃。In the case of producing the ethylene-based copolymer (B) by a continuous bulk polymerization method or a continuous solution polymerization method, the polymerization temperature is not particularly limited, but is preferred from the viewpoint of the productivity of the ethylene-based copolymer (B). Department of 120 ~ 140 ℃.

於藉由連續溶液聚合法製造乙烯系共聚合體(B)的情況，溶媒量係由生產性的觀點而言，於聚合溶液中較佳係30質量%以下、更佳係20質量%以下。作為溶媒，由聚合穩定性的觀點而言，較佳係使用乙苯或甲基乙基酮、更佳係使用乙苯。When producing an ethylene-based copolymer (B) by a continuous solution polymerization method, the solvent amount is preferably 30 mass % or less, more preferably 20 mass % or less in the polymerization solution from the viewpoint of productivity. As the solvent, from the viewpoint of polymerization stability, ethylbenzene or methyl ethyl ketone is preferably used, and ethylbenzene is more preferably used.

本發明之透明熱可塑性樹脂組成物中，相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，較佳係接枝共聚合體(A)為10質量份以上且60質量份以下、及乙烯系共聚合體(B)為40質量份以上~90質量份以下。藉由設為接枝共聚合體(A)之含量10質量份以上、乙烯系共聚合體(B)之含量90質量份以下，可更加提升成形品之耐衝擊性。相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，更佳係含有接枝共聚合體(A)20質量份以上、乙烯系共聚合體(B)80質量份以下。另一方面，藉由設為接枝共聚合體(A)之含量60質量份以下、乙烯系共聚合體(B)之含量40質量份以上，提升透明熱可塑性樹脂組成物之流動性，亦有提升透明性、色調之情形。相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，更佳係含有接枝共聚合體(A)50質量份以下、乙烯系共聚合體(B)50質量份以上。In the transparent thermoplastic resin composition of the present invention, it is preferable that the graft copolymer (A) is 10 parts by mass or more with respect to 100 parts by mass in total of the graft copolymer (A) and the vinyl copolymer (B). 60 parts by mass or less, and the ethylene-based copolymer (B) is 40 parts by mass or more and 90 parts by mass or less. By setting the content of the graft copolymer (A) to 10 parts by mass or more and the content of the ethylene-based copolymer (B) to be 90 parts by mass or less, the impact resistance of the molded article can be further improved. It is more preferable to contain 20 parts by mass or more of the graft copolymer (A) and 80 parts by mass or less of the ethylene-based copolymer (B) with respect to 100 parts by mass of the total of the graft copolymer (A) and the ethylene-based copolymer (B). . On the other hand, by setting the content of the graft copolymer (A) to 60 parts by mass or less and the content of the vinyl copolymer (B) to be 40 parts by mass or more, the fluidity of the transparent thermoplastic resin composition is improved, and the Transparency, color tone. It is more preferable to contain 50 parts by mass or less of the graft copolymer (A) and 50 parts by mass or more of the ethylene-based copolymer (B) with respect to 100 parts by mass of the total of the graft copolymer (A) and the ethylene-based copolymer (B). .

本發明之透明熱可塑性樹脂組成物係除了接枝共聚合體(A)及乙烯系共聚合體(B)以外，進一步含有酯蠟(C)及有機酸單酯(D)。酯蠟(C)係選自由甘油脂肪酸酯類(c1)及脂肪酸酯(c2)所構成群之至少一種；該脂肪酸酯(c2)係由碳數12~30之直鏈飽和單羧酸、與選自由碳數14~30之直鏈飽和單元醇及碳數2~30之2~6價之多元醇所構成群之至少一種醇所得。有機酸單酯(D)係由二羧酸酐、與碳數14~30之直鏈飽和單元醇所得之有機酸單酯。The transparent thermoplastic resin composition of the present invention further contains an ester wax (C) and an organic acid monoester (D) in addition to the graft copolymer (A) and the vinyl copolymer (B). The ester wax (C) is at least one selected from the group consisting of glycerol fatty acid esters (c1) and fatty acid esters (c2); the fatty acid ester (c2) is a linear saturated monocarboxylic acid having 12 to 30 carbon atoms , and at least one alcohol selected from the group consisting of straight-chain saturated unit alcohols having 14 to 30 carbon atoms and polyhydric alcohols having 2 to 30 carbon atoms. The organic acid monoester (D) is an organic acid monoester obtained from a dicarboxylic acid anhydride and a straight-chain saturated unit alcohol having 14 to 30 carbon atoms.

於酯蠟(C)中使用甘油脂肪酸酯類(c1)時，較佳係脂肪酸之烷基部分之碳數為C ₁₁(月桂酸)~C ₂₈(二十八酸)之單脂肪酸酯、二脂肪酸酯及三脂肪酸酯之任一者，更佳係C ₁₇(硬脂酸)~C ₂₁(二十二酸)之單脂肪酸酯、二脂肪酸酯及三脂肪酸酯之任一者。又更佳係C ₁₇(硬脂酸)~C ₂₁(二十二酸)之單脂肪酸酯、二脂肪酸酯及三脂肪酸酯之任一者。又，烷基部分亦可含有羥基。此等不僅在抑制所得成形品放置於高溫下時之滲出等方面特別有效，而且於高溫下長期間使用時亦使成形體不致發生起霧等。若表示此等之具體例，則為甘油單硬脂酸酯、甘油三硬脂酸酯、甘油二硬脂酸酯、甘油單二十二酸酯、甘油二(二十二酸)酯、甘油三(二十二酸)酯、甘油-12-羥基單硬脂酸酯等。由可抑制成形品之透明性惡化的觀點而言，較佳係於構造中具有屬於極性基之羥基，為甘油單硬脂酸酯、甘油單硬脂酸酯、甘油單二十二酸酯、甘油二(二十二酸)酯、甘油-12-羥基單硬脂酸酯。又，作為甘油脂肪酸酯類(c1)，較佳係使用蓖麻子硬化油。該蓖麻子硬化油係藉由將蓖麻子油進行氫化而得。蓖麻子硬化油係由以12-羥基硬脂酸為主成分之混合脂肪酸、與甘油所構成的酯。此等亦可使用2種以上。 When using glycerol fatty acid esters (c1) in the ester wax (C), the carbon number of the alkyl part of the fatty acid is preferably a mono-fatty acid ester whose carbon number is C ₁₁ (lauric acid) to C ₂₈ (docosanoic acid), Any one of di-fatty acid ester and tri-fatty acid ester, more preferably any of mono-fatty acid ester, di-fatty acid ester and tri-fatty acid ester of C ₁₇ (stearic acid) to C ₂₁ (behenic acid) one. Still more preferable is any one of mono-fatty acid ester, di-fatty acid ester and tri-fatty acid ester of C ₁₇ (stearic acid) to C ₂₁ (behenic acid). In addition, the alkyl moiety may contain a hydroxyl group. These are not only particularly effective in suppressing exudation and the like of the obtained molded product when it is left at a high temperature, but also prevent the molded product from fogging and the like when it is used at a high temperature for a long period of time. Specific examples of these are glycerol monostearate, glycerol tristearate, glycerol distearate, glycerol monobehenate, glycerol di(behenate), glycerin Tris(docosanoic acid) ester, glycerol-12-hydroxy monostearate, etc. From the viewpoint of suppressing the deterioration of transparency of the molded product, it is preferable to have a hydroxyl group belonging to a polar group in the structure, and it is preferably glycerol monostearate, glycerol monostearate, glycerol monobehenate, Glyceryl di (behenate), glycerol-12-hydroxy monostearate. Moreover, it is preferable to use castor bean hardened oil as glycerol fatty acid ester (c1). The castor bean hardened oil is obtained by hydrogenating castor bean oil. Castor bean hardened oil is an ester composed of a mixed fatty acid containing 12-hydroxystearic acid as the main component, and glycerin. Two or more of these may be used.

作為酯蠟(C)，於使用屬於甘油脂肪酸酯類(c1)之蓖麻子硬化油時，並無特別限制，由提升透明熱可塑性樹脂組成物之色調的觀點而言，蓖麻子硬化油之碘價較佳為5以下、更佳為3以下。若碘價為5以下，可抑制因加工時之熱劣化所造成的變色。As the ester wax (C), when castor bean hardened oil belonging to the glycerol fatty acid esters (c1) is used, there is no particular limitation. From the viewpoint of enhancing the color tone of the transparent thermoplastic resin composition, iodine of castor bean hardened oil is used. The price is preferably 5 or less, more preferably 3 or less. When the iodine value is 5 or less, discoloration due to thermal deterioration during processing can be suppressed.

作為酯蠟(C)，於使用由碳數12~30之直鏈飽和單羧酸、與選自由碳數14~30之直鏈飽和單元醇及碳數2~30之2~6價之多元醇所構成群之至少一種醇所得的脂肪酸酯(c2)時，脂肪酸酯(c2)係由羧酸(c2-1)與醇(c2-2)所得之酯化合物。此羧酸(c2-1)係碳數12~30之直鏈飽和單羧酸，醇(c2-2)係選自由碳數14~30之直鏈飽和單元醇及碳數2~30之2~6價之多元醇所構成群之至少一種醇。As the ester wax (C), a linear saturated monocarboxylic acid having a carbon number of 12 to 30, a linear saturated unit alcohol having a carbon number of 14 to 30, and a polyvalent polyvalent alcohol having a valence of 2 to 6 having a carbon number of 2 to 30 are used. In the case of fatty acid ester (c2) obtained from at least one alcohol in the alcohol group, the fatty acid ester (c2) is an ester compound obtained from carboxylic acid (c2-1) and alcohol (c2-2). The carboxylic acid (c2-1) is a linear saturated monocarboxylic acid with a carbon number of 12-30, and the alcohol (c2-2) is selected from a linear saturated unit alcohol with a carbon number of 14-30 and a carbon number of 2-30. At least one alcohol in the group of ~6-valent polyols.

直鏈飽和單羧酸為碳數12~30，較佳碳數為18~22。在碳數未滿12時，由於融點低，故於透明熱可塑性樹脂組成物之成形時污染成形品表面，或使透明熱可塑性樹脂組成物之耐衝擊性及耐熱性降低。另一方面，碳數為31以上之直鏈飽和羧酸係難以依工業製品之形式取得，或有使成形品之透明性降低之虞。The straight-chain saturated monocarboxylic acid has 12-30 carbon atoms, preferably 18-22 carbon atoms. When the number of carbon atoms is less than 12, since the melting point is low, the surface of the molded product is contaminated during molding of the transparent thermoplastic resin composition, or the impact resistance and heat resistance of the transparent thermoplastic resin composition are lowered. On the other hand, it is difficult to obtain a linear saturated carboxylic acid having a carbon number of 31 or more in the form of an industrial product, or there is a possibility that the transparency of the molded product may be lowered.

作為碳數12~30之直鏈飽和單羧酸，可舉例如月桂酸、肉荳蔻酸、軟脂酸、硬脂酸、花生酸、二十二酸、二十六酸、二十八酸、三十酸等。此等亦可使用2種以上。Examples of linear saturated monocarboxylic acids having 12 to 30 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, behenic acid, behenic acid, Thirty acid, etc. Two or more of these may be used.

作為上述直鏈飽和單元醇，可舉例如肉荳蔻醇、鯨蠟醇、硬脂醇、花生醇、二十二醇、二十四醇、二十六醇、二十八醇、三十醇等。此等亦可使用2種以上。Examples of the above-mentioned straight-chain saturated unit alcohol include myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, behenyl alcohol, behenyl alcohol, stearyl alcohol, triacosyl alcohol, and the like . Two or more of these may be used.

上述2~6價之多元醇中，作為二元醇，可舉例如乙二醇、丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、1,12-十二烷二醇、1,14-十四烷二醇、1,16-十六烷二醇、1,18-十八烷二醇、1,20-二十烷二醇、1,30-三十烷二醇、二乙二醇、二丙二醇、2,2,4-三甲基-1,3-戊二醇、新戊二醇、1,4-環己烷二甲醇、螺甘油、1,4-苯二醇、雙酚A、氫化雙酚A等。作為三元醇，可舉例如1,2,4-丁三醇、1,2,5-戊三醇、2-甲基-1,2,4-丁三醇、甘油、2-甲基丙三醇、三羥甲基乙烷、三羥乙基乙烷、三羥甲基丙烷、1,3,5-三羥甲基苯等。作為四元醇，可舉例如1,2,3,6-己烷四醇、季戊四醇等，作為五元醇，可舉例如葡萄糖等，作為六元醇，可舉例如二季戊四醇等。此等可使用2種以上。Among the above-mentioned divalent to hexavalent polyhydric alcohols, examples of dihydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol Alcohol, 1,20-Eicosanediol, 1,30-Triacontanediol, Diethylene glycol, Dipropylene glycol, 2,2,4-Trimethyl-1,3-pentanediol, Neopentyl Diol, 1,4-cyclohexanedimethanol, spiroglycerol, 1,4-benzenediol, bisphenol A, hydrogenated bisphenol A, etc. Examples of trihydric alcohols include 1,2,4-butanetriol, 1,2,5-pentanetriol, 2-methyl-1,2,4-butanetriol, glycerin, and 2-methylpropane. Triol, trimethylolethane, trimethylolethane, trimethylolpropane, 1,3,5-trimethylolbenzene, etc. As a tetrahydric alcohol, 1,2,3,6- hexanetetraol, pentaerythritol etc. are mentioned, for example, Glucose etc. are mentioned as a pentahydric alcohol, for example, dipentaerythritol etc. are mentioned as a hexahydric alcohol, for example. Two or more of these can be used.

於使用由以上所示單羧酸及多元醇所得酯蠟(C)時，由提升含有此之透明熱可塑性樹脂組成物之耐衝擊性及耐熱性的觀點而言，較佳係由碳數14~24之直鏈飽和單元醇或碳數2~12之2價以上之多元醇、與碳數12~30之直鏈飽和羧酸所得的脂肪酸酯；更佳係由碳數14~24之直鏈飽和單元醇或碳數2~12之2價以上之多元醇、與碳數12~24之直鏈飽和羧酸所得的脂肪酸酯；又更佳係屬於四元醇之季戊四醇或屬於六元醇之二季戊四醇、與碳數12~22之直鏈飽和羧酸所得的脂肪酸酯。脂肪酸酯亦可殘存部分未反應之羥基。具體而言，為季戊四醇二硬脂酸酯、季戊四醇三硬脂酸酯、季戊四醇四硬脂酸酯、季戊四醇二(二十二酸)酯、季戊四醇三(二十二酸)酯、季戊四醇四(二十二酸)酯。由可抑制成形品之透明性惡化的觀點而言，較佳係於構造中具有屬於極性基之羥基，為季戊四醇二硬脂酸酯、季戊四醇三硬脂酸酯、季戊四醇二(二十二酸)酯、季戊四醇三(二十二酸)酯。此等亦可使用2種以上。When using the ester wax (C) obtained from the monocarboxylic acid and polyhydric alcohol shown above, from the viewpoint of improving the impact resistance and heat resistance of the transparent thermoplastic resin composition containing it, it is preferable to use the ester wax (C) having 14 carbon atoms. A straight-chain saturated unit alcohol of ~24 or a polyhydric alcohol with a carbon number of 2-12 or more, and a fatty acid ester of a straight-chain saturated carboxylic acid with a carbon number of 12-30; Straight-chain saturated unit alcohols or polyhydric alcohols with 2-12 carbon atoms or more than 2 valences, and fatty acid esters obtained from straight-chain saturated carboxylic acids with 12-24 carbon atoms; more preferably, pentaerythritol belonging to tetrahydric alcohols or pentaerythritol belonging to hexavalent alcohols A fatty acid ester obtained from dipentaerythritol, which is a polyhydric alcohol, and a straight-chain saturated carboxylic acid with a carbon number of 12 to 22. The fatty acid ester may also have some unreacted hydroxyl groups remaining. Specifically, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, pentaerythritol bis(docosanoate), pentaerythritol tris(docosanoate), pentaerythritol tetra(didodecanoate) dodecanoic acid) ester. From the viewpoint of suppressing the deterioration of transparency of the molded product, it is preferable to have a hydroxyl group belonging to a polar group in the structure, and it is preferably pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol bis(docosanoic acid) ester, pentaerythritol tris(docosanoic acid) ester. Two or more of these may be used.

又，於使用由單羧酸及多元醇所得之酯蠟(C)時的酸價，較佳為15mgKOH/g以下。酸價更佳為10mgKOH/g以下、又更佳為8mgKOH/g以下、特佳為1.0mgKOH/g以下。酸價若為15mgKOH/g以下，則酯蠟(C)之耐熱性高，可抑制屬於低分子成分之未反應殘存脂肪酸之氣化。又，酸價係根據JOCS(日本油化學會)2.3.1所測定之值。Moreover, when using the ester wax (C) obtained from a monocarboxylic acid and a polyhydric alcohol, the acid value is preferably 15 mgKOH/g or less. The acid value is more preferably 10 mgKOH/g or less, more preferably 8 mgKOH/g or less, and particularly preferably 1.0 mgKOH/g or less. When the acid value is 15 mgKOH/g or less, the heat resistance of the ester wax (C) is high, and the vaporization of the unreacted residual fatty acid which is a low molecular weight component can be suppressed. In addition, the acid value is a value measured according to JOCS (Japan Oil Chemical Society) 2.3.1.

於使用本發明之由單羧酸及多元醇所得酯蠟(C)時，酯蠟(C)之合成係進行酯化反應(縮合反應)。反應係於觸媒存在下或不存在下，通常依120~240℃之溫度進行。藉由此種酯化反應，可獲得酯化粗製生成物。When the ester wax (C) obtained from a monocarboxylic acid and a polyhydric alcohol of the present invention is used, the synthesis of the ester wax (C) proceeds with an esterification reaction (condensation reaction). The reaction is carried out in the presence or absence of a catalyst, usually at a temperature of 120-240°C. Through such an esterification reaction, a crude esterified product can be obtained.

接著，將該酯化粗製生成物中剩餘之羧酸(c2-1)，藉由使用了鹼水溶液之脫酸而去除。脫酸時所使用之鹼水溶液，可舉例如氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉等之鹼金屬鹽，碳酸銨等銨鹽等之水溶液。通常使用5~20質量%濃度之鹼水溶液。鹼之量係相對於使羧酸與醇反應所得之酯化粗製生成物之酸價，以1~2倍當量為宜。Next, the carboxylic acid (c2-1) remaining in the crude product of esterification was removed by deacidification using an aqueous alkali solution. The alkaline aqueous solution used in the deacidification includes, for example, an aqueous solution of an alkali metal salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate, and an aqueous solution of an ammonium salt such as ammonium carbonate. Usually, an alkaline aqueous solution with a concentration of 5 to 20% by mass is used. The amount of the base is preferably 1 to 2 times equivalent to the acid value of the crude esterification product obtained by reacting carboxylic acid and alcohol.

如此由單羧酸及多元醇所得之酯蠟(C)，係酸價成為既定範圍。The acid value of the ester wax (C) obtained from a monocarboxylic acid and a polyhydric alcohol in this way is within a predetermined range.

本發明之酯蠟，可藉由在對上述羧酸(c2-1)與醇(c2-2)之酯化反應所得之酯化粗製生成物以鹼水溶液進行脫酸時，添加特定有機溶劑而簡便地獲得。此有機溶劑為烴溶劑。藉由使用此等特定有機溶劑，於水洗時，可獲得更良好的分層狀態。The ester wax of the present invention can be obtained by adding a specific organic solvent when deacidifying the crude esterified product obtained by the esterification reaction of the carboxylic acid (c2-1) and the alcohol (c2-2) with an aqueous alkali solution. easily obtained. This organic solvent is a hydrocarbon solvent. By using these specific organic solvents, when washing with water, a better layered state can be obtained.

作為上述烴溶劑，可舉例如甲苯、二甲苯、環己烷及正庚烷等。於使用烴溶劑時，該溶劑之添加量係相對於酯化粗製生成物100質量份，較佳為5質量份以上且100質量份以下。藉由將烴溶劑之添加量設為5質量份以上，則分層狀態良好。又，藉由設為100質量份以下，可依短時間進行溶媒去除步驟，可提升生產性。As said hydrocarbon solvent, toluene, xylene, cyclohexane, n-heptane, etc. are mentioned, for example. When a hydrocarbon solvent is used, the addition amount of the solvent is preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the crude esterification product. By setting the addition amount of the hydrocarbon solvent to 5 parts by mass or more, the layered state is favorable. Moreover, by setting it as 100 mass parts or less, a solvent removal process can be performed in a short time, and productivity can be improved.

除了上述烴溶劑以外，藉由相對於酯化粗製生成物100質量份，將碳數1~3之醇(分離用醇)依3質量份以上且30質量份以下、較佳為依5質量份以上且30質量份以下之比例添加，可使分層狀態更加良好。作為此種分離用醇，可舉例如甲醇、乙醇、正丙醇、異丙醇等。In addition to the above-mentioned hydrocarbon solvent, with respect to 100 parts by mass of the crude esterification product, the alcohol having 1 to 3 carbon atoms (separation alcohol) is 3 parts by mass or more and 30 parts by mass or less, preferably 5 parts by mass. Adding in a ratio of more than 30 parts by mass or less can make the layered state more favorable. As such an alcohol for separation, methanol, ethanol, n-propanol, isopropanol, etc. are mentioned, for example.

脫酸係將上述酯化粗製生成物、烴溶劑及鹼水溶液、進而視需要之分離用醇(與烴溶劑併用)混合，將存在於酯化粗製生成物中之酸藉由鹼進行中和而進行。通常，藉由將此等充分混合而進行脫酸。脫酸係保持於較酯化粗製生成物之融解溫度高的溫度而進行。通常較佳為50℃以上且100℃以下、更佳為70℃以上且90℃以下。於上述較佳溫度下，無發生分層不良或乳化之虞，另一方面，亦無酯發生水解之虞。The deacidification system mixes the above-mentioned crude esterification product, a hydrocarbon solvent, an aqueous alkali solution, and optionally an alcohol for separation (used in combination with a hydrocarbon solvent), and neutralizes the acid present in the crude esterification product with an alkali. conduct. Usually, deacidification is carried out by mixing these thoroughly. The deacidification is carried out by maintaining the temperature higher than the melting temperature of the crude esterification product. Usually, it is preferably 50°C or higher and 100°C or lower, more preferably 70°C or higher and 90°C or lower. At the above-mentioned preferred temperature, there is no risk of poor delamination or emulsification, and on the other hand, there is no risk of hydrolysis of the ester.

由於藉由上述脫酸使含有酯之油層(酯層)與鹼水層分離，故去除此鹼水層。接著，對酯層使用溫水或熱水(50~100℃)進行水洗。水洗係重複進行至水洗廢水成為幾乎中性(例如pH為7或小於7之程度)為止。上述烴溶劑、及視需要所使用之分離用醇等溶劑，可藉由重複進行脫酸後之水洗而由酯層去除。進而於水洗後，於減壓條件下可完全去除酯中殘存之溶劑。如此可獲得目標之蠟酯。Since the oil layer (ester layer) containing the ester was separated from the alkaline aqueous layer by the above deacidification, the alkaline aqueous layer was removed. Next, the ester layer is washed with warm water or hot water (50 to 100° C.). The water washing is repeated until the water washing wastewater becomes almost neutral (for example, the pH is 7 or less). The above-mentioned hydrocarbon solvent and a solvent such as an alcohol for separation used as needed can be removed from the ester layer by repeating the water washing after deacidification. Furthermore, after washing with water, the residual solvent in the ester can be completely removed under reduced pressure. In this way, the target wax ester can be obtained.

若採用以上方法，則脫酸時不致發生分層不良或乳化，可依高產率製造高品質之酯蠟(C)。如此所得之酯蠟(C)係低揮發性物質、原料醇、原料羧酸等之含量少，顯示高耐熱特性。因此，可有效地使用於透明熱可塑性樹脂。If the above method is adopted, poor delamination or emulsification will not occur during deacidification, and high-quality ester wax (C) can be produced in high yield. The ester wax (C) thus obtained has a low content of low-volatile substances, raw material alcohol, raw material carboxylic acid, etc., and exhibits high heat resistance characteristics. Therefore, it can be effectively used for transparent thermoplastic resins.

本發明所使用之有機酸單酯(D)，係由二羧酸酐(d-1)與醇(d-2)所得的酯化合物。此醇(d-2)為碳數14~30之直鏈飽和單元醇(d-2)。The organic acid monoester (D) used in the present invention is an ester compound obtained from a dicarboxylic acid anhydride (d-1) and an alcohol (d-2). The alcohol (d-2) is a straight-chain saturated unit alcohol (d-2) having 14 to 30 carbon atoms.

作為二羧酸酐(d-1)，可舉例如順丁烯二酸酐、琥珀酸酐、酞酸酐等。其中，由與醇(d-2)間之反應性的觀點而言，較佳為順丁烯二酸酐。此等可使用2種以上。As dicarboxylic anhydride (d-1), maleic anhydride, succinic anhydride, phthalic anhydride, etc. are mentioned, for example. Among them, from the viewpoint of reactivity with the alcohol (d-2), maleic anhydride is preferred. Two or more of these can be used.

作為上述直鏈飽和單元醇(d-2)，可舉例如肉荳蔻醇、鯨蠟醇、硬脂醇、花生醇、二十二醇、二十四醇、二十六醇、二十八醇、三十醇等。此等可使用2種以上。Examples of the straight-chain saturated unit alcohol (d-2) include myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, behenyl alcohol, behenyl alcohol, and stearyl alcohol. , Triacontol, etc. Two or more of these can be used.

由以上所示二羧酸酐(d-1)及醇(d-2)所得之本發明所使用的有機酸單酯(D)，係由提升含有此之透明熱可塑性樹脂組成物之耐衝擊性及耐熱性的觀點而言，較佳為由二羧酸酐、與碳數12~24之直鏈飽和單元醇所得的有機酸單酯；更佳為由順丁烯二酸酐與碳數14~22之直鏈飽和單元醇所得的脂肪酸酯；特佳為順丁烯二酸單硬脂酸酯、順丁烯二酸單二十二酸酯。此等可使用2種以上。又，本發明之有機酸單酯(D)亦可依20質量%以下之比例含有在使碳數14~24之直鏈飽和單元醇、與二羧酸酐進行酯化反應時、依副反應物之形式所生成的有機酸二酯。The organic acid monoester (D) used in the present invention obtained from the dicarboxylic anhydride (d-1) and the alcohol (d-2) shown above is used to improve the impact resistance of the transparent thermoplastic resin composition containing it. From the viewpoint of heat resistance, it is preferably an organic acid monoester obtained from a dicarboxylic acid anhydride and a straight-chain saturated unit alcohol having 12 to 24 carbon atoms; The fatty acid ester obtained from the straight-chain saturated unit alcohol; particularly preferred are maleic acid monostearate and maleic acid monobehenate. Two or more of these can be used. In addition, the organic acid monoester (D) of the present invention may be contained at a ratio of 20% by mass or less. When a linear saturated unit alcohol having 14 to 24 carbon atoms is esterified with a dicarboxylic acid anhydride, a side reactant may be added. The organic acid diester formed in the form of.

本發明之有機酸單酯(D)的合成、及構造的特定，可藉由日本專利特開平5-70525號公報、特開2001-220365號公報、特開2002-265417號公報、特開2007-197364號公報記載之公知合成法、分析法獲得。The synthesis of the organic acid monoester (D) of the present invention and the identification of the structure can be carried out by Japanese Patent Laid-Open No. 5-70525, Japanese Patent Laid-Open No. 2001-220365, Japanese Patent Laid-Open No. 2002-265417, and Japanese Patent Laid-Open No. 2007 - Obtained by known synthesis and analysis methods described in Gazette 197364.

酯蠟(C)由於在構造中於烷基部分不具有屬於極性基之羥基，或由於在構造中雖具有屬於極性基之羥基但烷基部分之分子量高、顯示親性油，故於透明熱可塑性樹脂組成物中偏存於橡膠質聚合體(r)周邊，使橡膠質聚合體(r)周邊之彈性係數下降，緩和橡膠相與基質相間所發生的急遽彈性係數差，可緩和界面的應力集中。又，藉由偏存於橡膠質聚合體(r)周邊而使橡膠質聚合體(r)對於衝擊的滑性提升，可提高橡膠質聚合體(r)之衝擊性吸收能力。其結果，不致使成形品之透明性、色調顯著降低，可提升成形品之耐衝擊性。又，對透明熱可塑性樹脂組成物之流動性提升顯示一定效果。由可抑制成形品之透明性惡化的觀點而言，更佳係於構造中具有屬於極性基之羥基者。Since the ester wax (C) does not have a hydroxyl group belonging to a polar group in the alkyl part in the structure, or has a hydroxyl group belonging to a polar group in the structure, the molecular weight of the alkyl part is high and shows an affinity oil, so it is transparent heat. The plastic resin composition partially exists around the rubber polymer (r), which reduces the elastic coefficient around the rubber polymer (r), relieves the abrupt difference in elastic coefficient between the rubber phase and the matrix phase, and relieves the interface stress. concentrated. In addition, by being unevenly distributed around the rubbery polymer (r), the slidability of the rubbery polymer (r) to impact is improved, and the impact absorption capacity of the rubbery polymer (r) can be improved. As a result, the impact resistance of the molded product can be improved without significantly reducing the transparency and color tone of the molded product. In addition, it exhibits a certain effect on the improvement of the fluidity of the transparent thermoplastic resin composition. From the viewpoint of suppressing the deterioration of the transparency of the molded product, it is more preferable to have a hydroxyl group which is a polar group in the structure.

另一方面，有機酸單酯(D)由於具有屬於極性基之羧酸基，故可於透明熱可塑性樹脂組成物對基質相之分散性佳、保持成形品之透明性、色調之下，較單獨使用酯蠟(C)的情況，更加提升透明熱可塑性樹脂組成物之流動性。On the other hand, since the organic acid monoester (D) has a carboxylic acid group which is a polar group, it can be better in dispersibility of the transparent thermoplastic resin composition to the matrix phase, while maintaining the transparency and color tone of the molded article. When the ester wax (C) is used alone, the fluidity of the transparent thermoplastic resin composition is further improved.

本發明之透明熱可塑性樹脂組成物係相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，較佳為含有酯蠟(C)0.4質量份以上且2.0質量份以下。相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，藉由將酯蠟(C)之含量設為0.4質量份以上，可更加提升成形品之耐衝擊性。另一方面，藉由設為2.0質量份以下，由成形時之氣體發生量少、外觀提升的觀點而言為較佳。酯蠟(C)之含量係相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，更佳為0.5質量份以上。另一方面，酯蠟(C)之含量更佳為1.5質量份以下。The transparent thermoplastic resin composition of the present invention preferably contains at least 0.4 parts by mass and 2.0 parts by mass of the ester wax (C) with respect to 100 parts by mass in total of the graft copolymer (A) and the vinyl copolymer (B). the following. By setting the content of the ester wax (C) to 0.4 parts by mass or more relative to 100 parts by mass in total of the graft copolymer (A) and the ethylene-based copolymer (B), the impact resistance of the molded product can be further improved. On the other hand, by setting it as 2.0 mass parts or less, it is preferable from a viewpoint that the gas generation amount at the time of shaping|molding is small and an external appearance improves. The content of the ester wax (C) is more preferably 0.5 parts by mass or more with respect to 100 parts by mass in total of the graft copolymer (A) and the ethylene-based copolymer (B). On the other hand, the content of the ester wax (C) is more preferably 1.5 parts by mass or less.

本發明之透明熱可塑性樹脂組成物係相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，較佳為含有有機酸單酯(D)0.1質量份以上且2.0質量份以下。相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，藉由將有機酸單酯(D)之含量設為0.1質量份以上，可更加提升透明熱可塑性樹脂組成物之流動性。另一方面，藉由設為2.0質量份以下，由成形時之氣體發生量少、外觀提升的觀點而言為較佳。有機酸單酯(D)之含量係相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，更佳為0.4質量份以上、又更佳為0.6質量份以上。另一方面，有機酸單酯(D)之含量更佳為1.5質量份以下、又更佳為1.0質量份以下。The transparent thermoplastic resin composition of the present invention preferably contains 0.1 part by mass or more and 2.0 part by mass of the organic acid monoester (D) with respect to 100 parts by mass in total of the graft copolymer (A) and the vinyl copolymer (B). parts by mass or less. By setting the content of the organic acid monoester (D) to 0.1 part by mass or more with respect to 100 parts by mass in total of the graft copolymer (A) and the vinyl copolymer (B), the transparent thermoplastic resin composition can be further improved fluidity of things. On the other hand, by setting it as 2.0 mass parts or less, it is preferable from a viewpoint that the gas generation amount at the time of shaping|molding is small and an external appearance improves. The content of the organic acid monoester (D) is more preferably 0.4 parts by mass or more, and more preferably 0.6 parts by mass or more with respect to 100 parts by mass in total of the graft copolymer (A) and the vinyl copolymer (B). On the other hand, the content of the organic acid monoester (D) is more preferably 1.5 parts by mass or less, and still more preferably 1.0 parts by mass or less.

酯蠟(C)及有機酸單酯(D)可分別個別地添加，亦可作為預先調製之混合物再添加。又，亦可添加：將酯蠟(C)與有機酸單酯(D)依融點以上之溫度進行加熱熔融而均勻混合，其後，使其冷卻固化，進行粉碎或造粒者。The ester wax (C) and the organic acid monoester (D) may be added individually, or may be added as a preliminarily prepared mixture. Moreover, you may add what heat-melts the ester wax (C) and the organic acid monoester (D) at the temperature higher than a melting point, and mixes uniformly, and then it cools and solidifies, and grind|pulverizes or granulates.

本發明之透明熱可塑性樹脂組成物之「透明」，係指對方板成形品(縱50mm、橫40mm、厚4mm)使用東洋精機(股)製直讀式霧度計，所測定之方板成形品之總光線穿透率為80%以上者。較佳為85%以上者。The "transparency" of the transparent thermoplastic resin composition of the present invention refers to the square plate formed by using a direct-reading haze meter manufactured by Toyo Seiki Co., Ltd. for a square plate formed product (length 50 mm, width 40 mm, thickness 4 mm). The total light transmittance of the product is more than 80%. Preferably it is 85% or more.

本發明之透明熱可塑性樹脂組成物中，進一步視需要，在不損及本發明目的之範圍內，亦可調配玻璃纖維、玻璃粉、玻璃珠、玻璃片、礬土、氧化鋁纖維、碳纖維、石墨纖維、不鏽鋼纖維、晶鬚、鈦酸鉀纖維、矽灰石、石綿、硬質黏土、煅燒黏土、滑石、高嶺土、雲母、碳酸鈣、碳酸鎂、氧化鋁及礦物等無機填充材；受阻酚系、含硫化合物系或含磷有機化合物系等抗氧化劑；酚系、丙烯酸酯系等熱穩定劑；苯并***系、二苯基酮系或水楊酸酯系等紫外線吸收劑；受阻胺系光穩定劑；高級脂肪酸、酸酯、酸醯胺系或高級醇等滑劑及可塑劑；二十八酸及其鹽、其酯、其半酯、硬脂醇、硬脂醯胺及乙烯蠟、矽氧烷化合物等脫模劑；各種難燃劑；難燃助劑；亞磷酸鹽、次磷酸鹽等抗著色劑；磷酸、磷酸一鈉、順丁烯二酸酐、琥珀酸酐等中和劑；核劑；胺系、磺酸系、聚醚系等抗靜電劑；碳黑、顏料、染料等著色劑等。In the transparent thermoplastic resin composition of the present invention, glass fibers, glass powder, glass beads, glass flakes, alumina, alumina fibers, carbon fibers, Inorganic fillers such as graphite fibers, stainless steel fibers, whiskers, potassium titanate fibers, wollastonite, asbestos, hard clay, calcined clay, talc, kaolin, mica, calcium carbonate, magnesium carbonate, alumina and minerals; hindered phenolic , antioxidants such as sulfur-containing compounds or phosphorus-containing organic compounds; thermal stabilizers such as phenols and acrylates; UV absorbers such as benzotriazoles, benzophenones or salicylates; hindered amines Light stabilizers; lubricants and plasticizers such as higher fatty acids, acid esters, acid amides or higher alcohols; octadecanoic acid and its salts, its esters, its half-esters, stearyl alcohol, stearylamine and ethylene Mold release agents such as waxes and siloxane compounds; various flame retardants; flame retardant additives; anti-colorants such as phosphite and hypophosphite; neutralization of phosphoric acid, monosodium phosphate, maleic anhydride, succinic anhydride, etc. Nucleating agents; amine, sulfonic acid, polyether and other antistatic agents; carbon black, pigments, dyes and other colorants.

本發明之透明熱可塑性樹脂組成物，可獲得屬於流動性指標之熔融流動速率(220℃、98N)為20g/10min以上、較佳為22g/10min以上，屬於耐衝擊性指標之夏比衝擊值為9kJ/m ²以上、較佳為10kJ/m ²以上，屬於透明性指標之總光線穿透率為80%以上、較佳為84%以上的透明熱可塑性樹脂組成物。 The transparent thermoplastic resin composition of the present invention can obtain a melt flow rate (220°C, 98N), which is an index of fluidity, of 20 g/10min or more, preferably 22 g/10min or more, and a Charpy impact value, which is an index of impact resistance. A transparent thermoplastic resin composition having a total light transmittance of 9 kJ/m ² or more, preferably 10 kJ/m ² or more, and a transparency index of 80% or more, preferably 84% or more.

(透明熱可塑性樹脂組成物之製造方法) 其次，針對本發明之透明熱可塑性樹脂組成物的製造方法進行說明。本發明之透明熱可塑性樹脂組成物，係例如藉由調配上述接枝共聚合體(A)、乙烯系共聚合體(B)、酯蠟(C)、有機酸單酯(D)及視需要之其他成分，並進行熔融混練而可獲得。更佳係將乙烯系共聚合體(B)進行連續塊狀聚合，進而連續地將接枝共聚合體(A)、酯蠟(C)、有機酸單酯(D)、視需要之其他成分進行熔融混練之方法。藉由由乙烯系共聚合體(B)之製造起、連續地進行屬於最終物之透明熱可塑性樹脂組成物之製造，可減低熱履歷，使透明熱可塑性樹脂組成物之色調良好。 (Manufacturing method of transparent thermoplastic resin composition) Next, the manufacturing method of the transparent thermoplastic resin composition of this invention is demonstrated. The transparent thermoplastic resin composition of the present invention is prepared, for example, by formulating the above-mentioned graft copolymer (A), vinyl copolymer (B), ester wax (C), organic acid monoester (D) and others as needed. components, and melt-kneading can be obtained. More preferably, the ethylene-based copolymer (B) is continuously mass-polymerized, and the graft copolymer (A), ester wax (C), organic acid monoester (D), and other components as needed are continuously melted. The method of mixing. By continuously producing the final transparent thermoplastic resin composition from the production of the vinyl copolymer (B), the thermal history can be reduced and the color tone of the transparent thermoplastic resin composition can be improved.

圖1表示本發明所適合使用之透明熱可塑性樹脂組成物之製造裝置之一實施態樣的概略圖。圖1所示透明熱可塑性樹脂組成物之製造裝置，係具備用於製造乙烯系共聚合體(B)的反應槽1、用於將所得乙烯系共聚合體(B)加熱至既定溫度的預熱機2、及雙軸擠出機型脫單體機3，並分別連結著。再者，依對雙軸擠出機型脫單體機3進行側進料之方式，連接著用於供給接枝共聚合體(A)、酯蠟(C)及有機酸單酯(D)的雙軸擠出機型進料器5。反應槽1係具有攪拌機(螺帶葉片)7，雙軸擠出機型脫單體機3係具有用於去除未反應之單體等揮發成分的排氣口8。FIG. 1 is a schematic view showing an embodiment of an apparatus for producing a transparent thermoplastic resin composition suitable for use in the present invention. The apparatus for producing a transparent thermoplastic resin composition shown in FIG. 1 includes a reaction tank 1 for producing an ethylene-based copolymer (B), and a preheater for heating the obtained ethylene-based copolymer (B) to a predetermined temperature 2, and the double-shaft extruder type de-monomer 3, and are connected separately. Furthermore, in a manner of side feeding the twin-screw extruder type de-monomerizer 3, a feeder for supplying the graft copolymer (A), ester wax (C) and organic acid monoester (D) is connected. Biaxial extruder type feeder 5. The reaction tank 1 has a stirrer (ribbon blade) 7, and the twin-screw extruder type de-monomer 3 has an exhaust port 8 for removing volatile components such as unreacted monomers.

由反應槽1連續地供給之反應生成物(乙烯系共聚合體(B))，係藉由預熱機2加熱至既定溫度，接著供給至雙軸擠出機型脫單體機3。雙軸擠出機型脫單體機3中，一般而言，係依150~280℃左右之溫度，於常壓或減壓下，從排氣口8將未反應單體等揮發成分排除至系統外。此揮發成分之去除，一般而言，係進行至揮發成分成為既定量、例如10質量%以下、更佳為5質量%以下為止。又，所去除之揮發成分較佳係再次供給至反應槽1。The reaction product (ethylene-based copolymer (B)) continuously supplied from the reaction tank 1 is heated to a predetermined temperature by the preheater 2 and then supplied to the twin-screw extruder type de-monomer 3 . In the twin-screw extruder type de-monomer 3, generally speaking, volatile components such as unreacted monomers are removed from the exhaust port 8 under normal pressure or reduced pressure at a temperature of about 150 to 280°C. outside the system. The removal of this volatile component is generally performed until the volatile component becomes a predetermined amount, for example, 10 mass % or less, more preferably 5 mass % or less. In addition, the removed volatile components are preferably supplied to the reaction tank 1 again.

通過於雙軸擠出機型脫單體機3之途中接近下游側之位置所設置的開口部，從雙軸擠出機型進料器5供給接枝共聚合體(A)、酯蠟(C)、有機酸單酯(D)。雙軸擠出機型進料器5較佳係具有加熱裝置，藉由將接枝共聚合體(A)依半熔融或熔融狀態供給至雙軸擠出機型脫單體機3，可使混合狀態良好。接枝共聚合體(A)之加熱溫度一般為100~220℃。作為雙軸擠出機型進料器5可舉例如：由螺桿、滾筒及螺桿驅動部所構成，且滾筒具有加熱・冷卻機能的雙軸擠出機型進料器。The graft copolymer (A) and the ester wax (C) are supplied from the twin-screw extruder feeder 5 through an opening provided at a position close to the downstream side in the middle of the twin-screw extruder de-monomer 3 ), organic acid monoester (D). The twin-screw extruder type feeder 5 preferably has a heating device, and by supplying the graft copolymer (A) in a semi-molten or molten state to the twin-screw extruder type de-monomer 3, mixing can be achieved. in good condition. The heating temperature of the graft copolymer (A) is generally 100 to 220°C. As the twin-screw extruder type feeder 5, for example, a twin-screw extruder type feeder which is constituted by a screw, a roller, and a screw drive part, and the roller has a heating and cooling function, can be mentioned.

於雙軸擠出機型脫單體機3之連接於雙軸擠出機型進料器5的位置，為了抑制因其後去除未反應單體之操作所造成的橡膠成分之熱劣化，較佳係使未反應單體之含量降低至10質量%以下、更佳係5質量%以下。In the position where the twin-screw extruder type de-monomer 3 is connected to the twin-screw extruder type feeder 5, in order to suppress the thermal deterioration of the rubber component caused by the subsequent operation of removing unreacted monomers, it is necessary to Preferably, the content of the unreacted monomer is reduced to 10% by mass or less, more preferably 5% by mass or less.

於雙軸擠出機型脫單體機3之連接於雙軸擠出機型進料器5的位置之後屬於下游區域的熔融混練區域4內，將乙烯系共聚合體(B)、接枝共聚合體(A)、酯蠟(C)及有機酸單酯(D)進行熔融混練，從吐出口6將透明熱可塑性樹脂組成物吐出於系統外。較佳係於熔融混練區域4設置水注入口9，以添加既定量水，所注入之水及未反應單體等揮發成分係進一步由設置於下游的最終排氣口10被排出於系統外。In the melt-kneading zone 4, which is a downstream zone after the twin-screw extruder type de-monomer 3 is connected to the twin-screw extruder type feeder 5, the ethylene-based copolymer (B), graft copolymerization The compound (A), the ester wax (C), and the organic acid monoester (D) are melt-kneaded, and the transparent thermoplastic resin composition is discharged out of the system from the discharge port 6 . Preferably, a water injection port 9 is provided in the melt-kneading area 4 to add a predetermined amount of water, and the injected water and volatile components such as unreacted monomers are further discharged out of the system through a final exhaust port 10 provided downstream.

本發明之透明熱可塑性樹脂組成物可藉任意成形方法進行成形。作為成形方法，可舉例如射出成形、擠出成形、充氣成形、吹塑成形、真空成形、壓縮成形、氣體輔助成形等，較佳係使用射出成形。射出成形時的滾筒溫度較佳為210~320℃，模具溫度較佳為30~80℃。The transparent thermoplastic resin composition of the present invention can be molded by any molding method. Examples of the molding method include injection molding, extrusion molding, inflation molding, blow molding, vacuum molding, compression molding, gas-assisted molding, and the like, and injection molding is preferably used. The drum temperature during injection molding is preferably 210 to 320°C, and the mold temperature is preferably 30 to 80°C.

本發明之透明熱可塑性樹脂組成物可廣泛使用作為任意形狀的成形品。作為成形品，可舉例如薄膜、片材、纖維、布、不織布、射出成形品、擠出成形品、真空壓空成形品、吹塑成形品、與其他材料的複合體等。The transparent thermoplastic resin composition of the present invention can be widely used as a molded article of any shape. As the molded product, for example, a film, a sheet, a fiber, a cloth, a nonwoven fabric, an injection molded product, an extrusion molded product, a vacuum pressure molded product, a blow molded product, a composite with other materials, and the like can be mentioned.

本發明之透明熱可塑性樹脂組成物，由於可於維持特別高度之透明性、良好之色調之下，兼具優越的耐衝擊性及流動性，故可用於作為家電製品、通訊關聯機器、一般雜貨及醫療關聯機器等用途。 [實施例] The transparent thermoplastic resin composition of the present invention has excellent impact resistance and fluidity while maintaining a particularly high degree of transparency and a good color tone, so it can be used as home appliances, communication-related equipment, and general miscellaneous goods. and medical related equipment. [Example]

以下，列舉實施例針對本發明進行更進一步詳述，惟，本發明並不限定於此等實施例。首先，針對實施例中之評價方法進行說明。Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited to these examples. First, the evaluation method in an Example is demonstrated.

＜透明熱可塑性樹脂組成物之評價方法＞ (1)透明性(總光線穿透率) 將由各實施例與比較例所得之透明熱可塑性樹脂組成物顆粒，於80℃之熱風乾燥機中乾燥3小時後，填充於滾筒溫度設定為230℃之住友重機械工業(股)製SE180EV-A成形機內，即時成形厚4mm之方板成形品。使用東洋精機股份有限公司製直讀式霧度計，針對所得方板成形品各5個，根據ISO 13468之方法測定總光線穿透率(%)，並算出其數量平均值。 <Evaluation method of transparent thermoplastic resin composition> (1) Transparency (total light transmittance) The transparent thermoplastic resin composition pellets obtained in each of the Examples and Comparative Examples were dried in a hot air dryer at 80°C for 3 hours, and then filled with SE180EV-A manufactured by Sumitomo Heavy Industries, Ltd., whose drum temperature was set to 230°C. In the forming machine, a square plate with a thickness of 4mm is instantly formed. Using a direct-reading haze meter manufactured by Toyo Seiki Co., Ltd., the total light transmittance (%) was measured according to the method of ISO 13468 with respect to each of the obtained 5 square plate molded articles, and the number average value thereof was calculated.

(2)耐衝擊性(夏比衝擊強度) 將由各實施例與比較例所得之透明熱可塑性樹脂組成物顆粒，於80℃熱風乾燥機中乾燥3小時後，填充於滾筒溫度設定為230℃之住友重機械工業(股)製SE-50DU成形機內，即時成形厚4mm之啞鈴型試驗片。針對所獲得啞鈴型試驗片各5個，根據ISO179之方法測定夏比衝擊強度，並算出其數量平均值。 (2) Impact resistance (Charpy impact strength) The transparent thermoplastic resin composition pellets obtained in the respective Examples and Comparative Examples were dried in a hot-air dryer at 80°C for 3 hours, and then filled with SE-50DU manufactured by Sumitomo Heavy Industries, Ltd., whose drum temperature was set to 230°C, and molded. Inside the machine, a dumbbell-shaped test piece with a thickness of 4 mm is instantly formed. For each of the five dumbbell-shaped test pieces obtained, the Charpy impact strength was measured according to the method of ISO179, and the numerical average value thereof was calculated.

(3)流動性(熔融流動速率(MFR)) 將由各實施例與比較例所得之透明熱可塑性樹脂組成物顆粒，於80℃熱風乾燥機中乾燥3小時後，依測定溫度220℃、負重98N的條件，根據ISO113之方法測定MFR。 (3) Fluidity (melt flow rate (MFR)) After drying the transparent thermoplastic resin composition pellets obtained in each example and comparative example in a hot air dryer at 80°C for 3 hours, MFR was measured according to the method of ISO113 under the conditions of a measurement temperature of 220°C and a load of 98N.

＜接枝共聚合體(A)之製造＞ (製造例1)接枝共聚合體(A-1) 在具備攪拌葉片之聚合槽中，填裝作為橡膠質聚合體之聚丁二烯乳膠(橡膠之質量平均粒徑0.30μm、折射率1.516)50質量份(固形份換算)、純水130質量份、月桂酸鈉0.4質量份、葡萄糖0.2質量份、焦磷酸鈉0.2質量份、硫酸亞鐵0.01質量份，經氮置換後，溫度調節為60℃，一邊攪拌、一邊歷時45分鐘初期添加苯乙烯3.6質量份、丙烯腈0.6質量份、甲基丙烯酸甲酯10.8質量份及第三(十二基)硫醇0.15質量份的單體混合物。 <Production of graft copolymer (A)> (Production Example 1) Graft Copolymer (A-1) In a polymerization tank equipped with a stirring blade, 50 parts by mass (in terms of solid content) and 130 parts by mass of pure water were filled with polybutadiene latex as a rubbery polymer (mass average particle diameter of rubber: 0.30 μm, refractive index: 1.516) , 0.4 parts by mass of sodium laurate, 0.2 parts by mass of glucose, 0.2 parts by mass of sodium pyrophosphate, 0.01 part by mass of ferrous sulfate, after nitrogen replacement, the temperature was adjusted to 60°C, and while stirring, 3.6 parts of styrene was initially added for 45 minutes. A monomer mixture of parts by mass, 0.6 parts by mass of acrylonitrile, 10.8 parts by mass of methyl methacrylate, and 0.15 parts by mass of third (dodecyl) mercaptan.

接著，歷時5小時連續添加異丙苯過氧化氫0.3質量份、屬於乳化劑之月桂酸鈉1.6質量份及純水25質量份的起始劑混合物。同時並行歷時5小時連續追加添加苯乙烯8.4質量份、丙烯腈1.4質量份、甲基丙烯酸甲酯25.2質量份及第三(十二基)硫醇0.36質量份的單體混合物。追加添加單體混合物後，保持1小時使聚合結束。聚合結束後，相對於接枝共聚合體(A-1)100質量份，將對甲苯酚‧二環戊二烯‧異丁烯之反應生成物與參(2,4-二第三丁基苯基)亞磷酸酯之乳化分散體，依對甲苯酚‧二環戊二烯‧異丁烯之反應生成物以固形份計0.42質量份、參(2,4-二第三丁基苯基)亞磷酸酯以固形份計0.21質量份進行添加。將所得接枝共聚合體乳膠藉由1.5質量%硫酸凝固後，利用氫氧化鈉中和，並進行洗淨、離心分離、乾燥，獲得粉狀之接枝共聚合體(A-1)(單體比率：苯乙烯24質量%、丙烯腈4質量%、甲基丙烯酸甲酯72質量%)。Next, a starter mixture of 0.3 parts by mass of cumene hydroperoxide, 1.6 parts by mass of sodium laurate which is an emulsifier, and 25 parts by mass of pure water was continuously added over 5 hours. At the same time, a monomer mixture of 8.4 parts by mass of styrene, 1.4 parts by mass of acrylonitrile, 25.2 parts by mass of methyl methacrylate, and 0.36 parts by mass of third (dodecyl) mercaptan was continuously added in parallel for 5 hours. After additionally adding the monomer mixture, it was held for 1 hour to complete the polymerization. After the completion of the polymerization, the reaction product of p-cresol·dicyclopentadiene·isobutene was added to ginseng (2,4-di-tert-butylphenyl) with respect to 100 parts by mass of the graft copolymer (A-1). The emulsified dispersion of phosphite is based on the reaction product of p-cresol·dicyclopentadiene·isobutylene, 0.42 parts by mass in solid content, and (2,4-di-tert-butylphenyl) phosphite as 0.21 mass part of solid content was added. The obtained graft copolymer latex was coagulated with 1.5 mass % sulfuric acid, neutralized with sodium hydroxide, washed, centrifuged, and dried to obtain a powdery graft copolymer (A-1) (monomer ratio). : 24 mass % of styrene, 4 mass % of acrylonitrile, 72 mass % of methyl methacrylate).

所得接枝共聚合體(A-1)之丙酮不溶份之折射率係1.517，與橡膠質聚合體間之折射率差為0.001。接枝率為47%。The refractive index of the acetone-insoluble portion of the obtained graft copolymer (A-1) was 1.517, and the difference in refractive index with the rubbery polymer was 0.001. The graft ratio was 47%.

(製造例2)接枝共聚合體(A-2) 於具備攪拌葉片之聚合槽中，裝填作為橡膠質聚合體之聚丁二烯乳膠(橡膠之質量平均粒徑0.30μm、折射率1.516)50質量份(固形份換算)、純水130質量份、月桂酸鈉0.4質量份、葡萄糖0.2質量份、焦磷酸鈉0.2質量份、硫酸亞鐵0.01質量份，經氮置換後，溫度調節為60℃，一邊攪拌、一邊歷時45分鐘初期添加苯乙烯3質量份、甲基丙烯酸甲酯12質量份及第三(十二基)硫醇0.07質量份之單體混合物。 (Production Example 2) Graft Copolymer (A-2) In a polymerization tank equipped with a stirring blade, 50 parts by mass (in terms of solid content), 130 parts by mass of pure water, 50 parts by mass of polybutadiene latex (mass average particle diameter of rubber, 1.516 in refractive index) as a rubbery polymer were charged. 0.4 parts by mass of sodium laurate, 0.2 parts by mass of glucose, 0.2 parts by mass of sodium pyrophosphate, and 0.01 part by mass of ferrous sulfate, after nitrogen substitution, the temperature was adjusted to 60°C, and 3 mass parts of styrene were initially added over 45 minutes while stirring. parts, 12 parts by mass of methyl methacrylate and 0.07 parts by mass of the third (dodecyl) mercaptan.

接著，歷時5小時連續添加異丙苯過氧化氫0.3質量份、屬於乳化劑之月桂酸鈉1.6質量份及純水25質量份的起始劑混合物。同時並行歷時50分鐘連續追加添加苯乙烯2質量份、甲基丙烯酸甲酯8質量份及第三(十二基)硫醇0.08質量份的單體混合物後，歷時130分鐘連續添加苯乙烯7.5質量份、甲基丙烯酸甲酯17.5質量份及第三(十二基)硫醇0.17質量份之單體混合物。單體混合物追加添加後，保持1小時使聚合結束。聚合結束後，相對於接枝共聚合體(A-2)100質量份，將對甲苯酚‧二環戊二烯‧異丁烯之反應生成物與參(2,4-二第三丁基苯基)亞磷酸酯之乳化分散體，依對甲苯酚‧二環戊二烯‧異丁烯之反應生成物以固形份計0.42質量份、參(2,4-二第三丁基苯基)亞磷酸酯以固形份計0.21質量份進行添加。將所得接枝共聚合體乳膠藉由1.5質量%硫酸凝固後，利用氫氧化鈉中和，並進行洗淨、離心分離、乾燥，獲得粉狀之接枝共聚合體(A-2)(單體比率：苯乙烯25質量%、甲基丙烯酸甲酯75質量%)。Next, a starter mixture of 0.3 parts by mass of cumene hydroperoxide, 1.6 parts by mass of sodium laurate which is an emulsifier, and 25 parts by mass of pure water was continuously added over 5 hours. Simultaneously, after continuously adding 2 mass parts of styrene, 8 mass parts of methyl methacrylate and 0.08 mass parts of third (dodecyl) mercaptan, the monomer mixture was added continuously for 50 minutes, and then 7.5 mass parts of styrene was continuously added for 130 minutes. parts, 17.5 parts by mass of methyl methacrylate, and 0.17 parts by mass of the third (dodecyl) mercaptan. After the additional addition of the monomer mixture, it was held for 1 hour to complete the polymerization. After the completion of the polymerization, the reaction product of p-cresol·dicyclopentadiene·isobutylene was mixed with ginseng (2,4-di-tert-butylphenyl) with respect to 100 parts by mass of the graft copolymer (A-2). The emulsified dispersion of phosphite is based on the reaction product of p-cresol·dicyclopentadiene·isobutylene, 0.42 parts by mass in solid content, and (2,4-di-tert-butylphenyl) phosphite as 0.21 mass part of solid content was added. The obtained graft copolymer latex was coagulated with 1.5 mass % sulfuric acid, neutralized with sodium hydroxide, washed, centrifuged, and dried to obtain a powdery graft copolymer (A-2) (monomer ratio). : 25 mass % of styrene, 75 mass % of methyl methacrylate).

所得接枝共聚合體(A-2)之丙酮不溶份之折射率係1.516，與橡膠質聚合體間之折射率差為0.000。接枝率為50%。The refractive index of the acetone-insoluble portion of the obtained graft copolymer (A-2) was 1.516, and the difference in refractive index with the rubbery polymer was 0.000. The grafting rate is 50%.

＜酯蠟(C)＞ Emery Oleochemicals Japan製「LOXIOL」(註冊商標)G129(主成分：甘油單硬脂酸酯)(C-1) Emery Oleochemicals Japan製「LOXIOL」(註冊商標)G1206(主成分：甘油二硬脂酸酯)(C-2) Emery Oleochemicals Japan製「LOXIOL」(註冊商標)EP218(主成分：甘油三硬脂酸酯)(C-3) Emery Oleochemicals Japan製「LOXIOL」(註冊商標)G15(主成分：蓖麻子硬化油)(C-4) 日油股份有限公司製「UNISTER」(註冊商標)M-9676(主成分：硬脂酸硬脂酯)(C-5) 日油股份有限公司製「UNISTER」(註冊商標)M-2222SL(主成分：二十二酸二十二酯)(C-6) 日油股份有限公司製「UNISTER」(註冊商標)H-476D(主成分：季戊四醇二硬脂酸酯)(C-7) 日油股份有限公司製「UNISTER」(註冊商標)H-476(主成分：季戊四醇四硬脂酸酯)(C-8)。 <Ester Wax (C)> Emery Oleochemicals Japan "LOXIOL" (registered trademark) G129 (main ingredient: glycerol monostearate) (C-1) Emery Oleochemicals Japan "LOXIOL" (registered trademark) G1206 (main ingredient: Glyceryl distearate) (C-2) Emery Oleochemicals Japan "LOXIOL" (registered trademark) EP218 (main ingredient: glyceryl tristearate) (C-3) Emery Oleochemicals Japan "LOXIOL" (registered trademark) G15 (main ingredient: hardened castor bean oil) (C-4) "UNISTER" (registered trademark) M-9676 (main ingredient: stearyl stearate) (C-5) manufactured by NOF Corporation "UNISTER" (registered trademark) M-2222SL (main ingredient: behenate behenate) (C-6) manufactured by NOF Corporation "UNISTER" (registered trademark) H-476D (main ingredient: pentaerythritol distearate) (C-7) manufactured by NOF Corporation "UNISTER" (registered trademark) H-476 (main ingredient: pentaerythritol tetrastearate) (C-8) manufactured by NOF Corporation.

＜有機酸單酯(D)＞ (製造例3)有機酸單酯(D-1) 於安裝了溫度計、滴下裝置、逆流冷凝器、攪拌裝置之30L反應裝置中，填裝順丁烯二酸酐2,003g、甲基乙基酮3,289g、環己烷3,289g。其後，將反應容器內以氮氣置換，升溫至87~88℃，於其中歷時2.0小時滴下使硬脂醇5,262g加熱溶解於甲基異丁基酮3,289g、環己烷3,289g的溶液。滴下結束後，進行後攪拌7.0小時。反應結束後，冷卻反應液，依47.5℃添加種晶使結晶析出。在反應液溫成為15℃時進行過濾，得到順丁烯二酸單硬脂酯之白色濕潤結晶6,556g。(相對於填裝硬脂醇的產率：87.2mol%)。 <Organic acid monoester (D)> (Production example 3) Organic acid monoester (D-1) 2,003 g of maleic anhydride, 3,289 g of methyl ethyl ketone, and 3,289 g of cyclohexane were charged in a 30-L reaction apparatus equipped with a thermometer, a dropping device, a countercurrent condenser, and a stirring device. Then, the inside of the reaction container was substituted with nitrogen gas, the temperature was raised to 87 to 88° C., and a solution obtained by heating and dissolving 5,262 g of stearyl alcohol in 3,289 g of methyl isobutyl ketone and 3,289 g of cyclohexane was dropwise added thereto over 2.0 hours. After the dropping was completed, post-stirring was performed for 7.0 hours. After completion of the reaction, the reaction liquid was cooled, and seed crystals were added at 47.5°C to precipitate crystals. Filtration was carried out when the reaction liquid temperature became 15 degreeC, and 6,556 g of white wet crystals of maleic acid monostearyl ester were obtained. (Yield relative to packed stearyl alcohol: 87.2 mol%).

(製造例4)有機酸單酯(D-2) 除了變更硬脂醇5,262g而使用二十二醇6,355g以外，其餘依與製造例3同樣之方法製得順丁烯二酸單二十二酯之白色濕潤結晶7,554g。(相對於填裝二十二醇的產率：87.2mol%)。 (Production Example 4) Organic acid monoester (D-2) 7,554 g of white wet crystals of monobehenate maleate were obtained in the same manner as in Production Example 3 except that 5,262 g of stearyl alcohol was changed and 6,355 g of behenicol was used. (Yield relative to packed docosanol: 87.2 mol %).

(製造例5)有機酸單酯(D-3) 除了變更順丁烯二酸酐2,003g而使用琥珀酸酐2,044g以外，其餘依與製造例3同樣之方法製得琥珀酸單硬脂酯之白色濕潤結晶6,592g。(相對於填裝硬脂醇的產率：87.2mol%)。 (Production Example 5) Organic acid monoester (D-3) In the same manner as in Production Example 3, except that 2,003 g of maleic anhydride was changed and 2,044 g of succinic anhydride was used, 6,592 g of white wet crystals of monostearyl succinate were obtained. (Yield relative to packed stearyl alcohol: 87.2 mol%).

＜其他添加劑(E)＞ 旭化成Wacker股份有限公司製「GENIOPLAST」(註冊商標)GUM(主成分：聚二甲基矽氧烷膠)(E-1)。重量平均分子量為450,000。 <Other additives (E)> "GENIOPLAST" (registered trademark) GUM (main ingredient: polydimethylsiloxane gum) (E-1) manufactured by Asahi Kasei Wacker Co., Ltd. The weight average molecular weight was 450,000.

[實施例1] 使用由具有單體蒸氣之蒸發乾餾用冷凝器與螺帶葉片的2m3之完全混合型聚合槽、單軸擠出機型預熱機、雙軸擠出機型脫單體機、以及雙軸擠出機型進料器(其係依從脫單體機下游(出口)側前端側進料至前1/3長度之料管部的方式連接)構成的連續式塊狀聚合裝置，依照以下方法實施乙烯系共聚合體(B)及熱可塑性樹脂組成物之製造。 [Example 1] Using a 2m3 complete mixing type polymerization tank with an evaporative dry distillation condenser for monomer vapor and a spiral blade, a single-screw extruder type preheater, a double-screw extruder type de-monomer, and a double-screw extruder A continuous bulk polymerization device consisting of an outlet type feeder (which is connected from the front end side of the downstream (outlet) side of the de-monomerizer to feed to the first 1/3 of the length of the material pipe) is implemented according to the following method Manufacture of vinyl copolymer (B) and thermoplastic resin composition.

首先，將由苯乙烯23.5質量份、丙烯腈4.5質量份、甲基丙烯酸甲酯72質量份、正辛基硫醇0.26質量份、及1,1-雙(第三丁基過氧基)環己烷0.015質量份構成的單體混合物(b)，依150kg/小時連續地供給至完全混合型聚合槽，一邊保持聚合溫度130℃、槽內壓0.08MPa，一邊進行連續塊狀聚合。完全混合型聚合槽出口的聚合反應混合物之聚合率係控制於70±5%。First, 23.5 parts by mass of styrene, 4.5 parts by mass of acrylonitrile, 72 parts by mass of methyl methacrylate, 0.26 parts by mass of n-octyl mercaptan, and 1,1-bis(tert-butylperoxy)cyclohex The monomer mixture (b) composed of 0.015 parts by mass of alkane was continuously supplied to the complete mixing type polymerization tank at 150 kg/hour, and continuous block polymerization was performed while maintaining the polymerization temperature at 130° C. and the tank internal pressure at 0.08 MPa. The polymerization rate of the polymerization reaction mixture at the outlet of the fully mixed polymerization tank is controlled at 70±5%.

其次，將聚合反應混合物經單軸擠出機型預熱機施行預熱後，供給至雙軸擠出機型脫單體機，從雙軸擠出機型脫單體機的排氣口減壓蒸發回收未反應單體。所回收的未反應單體係連續地回流於完全混合型聚合槽。從雙軸擠出機型脫單體機下游側前端在相對於全長前1/3處，對表觀聚合率達99%以上的苯乙烯/丙烯腈/甲基丙烯酸甲酯共聚合體150kg/小時(70質量份)，利用雙軸擠出機型進料器供給3,3’-硫二丙酸二硬脂酯0.3kg/小時(0.14質量份)、酯蠟(C-1)1.07kg/小時(0.5質量份)、有機酸單酯(D-1)2.14kg/小時(1質量份)及接枝共聚合體(A-1)之半熔融狀態物64.3kg/小時(30質量份)，於雙軸擠出機型脫單體機中與苯乙烯/丙烯腈/甲基丙烯酸甲酯共聚合體進行熔融混練。於此熔融混練步驟中，從雙軸擠出機型脫單體機下游側前端在相對於全長前1/6處供應水2kg/小時。該水與其他揮發份係從在較雙軸擠出機型脫單體機更靠下游設置的排氣口進行減壓蒸發而去除。其後，使熔融混練物呈股狀吐出，利用切割刀進行切斷，獲得透明熱可塑性樹脂組成物顆粒。Secondly, the polymerization reaction mixture is preheated by a single-screw extruder type preheater, and then supplied to a twin-screw extruder type de-monomerizer, and the mixture is reduced from the exhaust port of the twin-screw extruder type de-monomerizer. Unreacted monomers were recovered by pressure evaporation. The recovered unreacted monomer system is continuously refluxed in the complete mixing type polymerization tank. 150kg/hour of styrene/acrylonitrile/methyl methacrylate copolymer with an apparent polymerization rate of 99% or more from the front 1/3 of the total length from the downstream side of the twin-screw extruder de-monomerizer (70 parts by mass), 0.3 kg/hour (0.14 parts by mass) of distearyl 3,3'-thiodipropionate, and 1.07 kg/hour of ester wax (C-1) were supplied by a twin-screw extruder type feeder. hour (0.5 parts by mass), 2.14 kg/h (1 part by mass) of organic acid monoester (D-1), and 64.3 kg/h (30 parts by mass) of semi-molten state of graft copolymer (A-1), Melt kneading with styrene/acrylonitrile/methyl methacrylate copolymer in a twin-screw extruder type de-monomerizer. In this melt-kneading step, 2 kg/hour of water was supplied from the front end on the downstream side of the twin-screw extruder type de-monomerizer at the front 1/6 of the entire length. This water and other volatile matter are removed by evaporation under reduced pressure from an exhaust port provided downstream of the twin-screw extruder type de-monomerizer. Then, the melt-kneaded product was discharged into strands and cut with a cutter blade to obtain transparent thermoplastic resin composition pellets.

[實施例2] 除了將酯蠟(C-1)設為酯蠟(C-2)以外，藉由與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 2] Transparent thermoplastic resin composition particles were obtained by the same method as in Example 1, except that the ester wax (C-1) was used as the ester wax (C-2).

[實施例3] 除了將酯蠟(C-1)設為酯蠟(C-3)以外，藉由與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 3] A transparent thermoplastic resin composition pellet was obtained by the same method as Example 1 except having used the ester wax (C-3) as the ester wax (C-3).

[實施例4] 除了將酯蠟(C-1)設為酯蠟(C-4)以外，藉由與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 4] A transparent thermoplastic resin composition particle was obtained by the same method as Example 1 except having used the ester wax (C-4) as the ester wax (C-4).

[實施例5] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為0.64kg/小時(0.3質量份)、有機酸單酯(D-1)供給量設為0.64kg/小時(0.3質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 5] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 0.64 kg/hour (0.3 parts by mass), the organic acid monoester (D-1 ), except that the supply amount was set to 0.64 kg/hour (0.3 parts by mass), transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1.

[實施例6] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)、有機酸單酯(D-1)供給量設為0.64kg/小時(0.3質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 6] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 2.14 kg/hour (1 part by mass), the organic acid monoester (D-1 ), except that the supply amount was set to 0.64 kg/hour (0.3 parts by mass), transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1.

[實施例7] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)、有機酸單酯(D-1)供給量設為0.11kg/小時(0.05質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 7] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 2.14 kg/hour (1 part by mass), the organic acid monoester (D-1 ), except that the supply amount was set to 0.11 kg/hour (0.05 parts by mass), transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1.

[實施例8] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為0.64kg/小時(0.3質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 8] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 0.64 kg/hour (0.3 parts by mass), the rest were carried out in the same manner as in Example 1. In the same way, transparent thermoplastic resin composition particles were obtained.

[實施例9] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 9] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 2.14 kg/hour (1 part by mass), the rest were carried out in the same manner as in Example 1. In the same way, transparent thermoplastic resin composition particles were obtained.

[實施例10] 除了將酯蠟(C-1)設為酯蠟(C-4)，將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)、有機酸單酯(D-1)設為有機酸單酯(D-1)與有機酸單酯(D-2)之混合物，並將有機酸單酯(D-1)供給量設為1.07kg/小時(0.5質量份)、有機酸單酯(D-2)供給量設為1.07kg/小時(0.5質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 10] Except that the ester wax (C-1) was used as the ester wax (C-4), the supply amount of the ester wax (C-4) was 2.14 kg/hour (1 part by mass), the organic acid monoester (D-1) As a mixture of organic acid monoester (D-1) and organic acid monoester (D-2), the supply amount of organic acid monoester (D-1) was 1.07 kg/hour (0.5 parts by mass), organic acid monoester (D-1) Transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1 except that the supply amount of the acid monoester (D-2) was 1.07 kg/hour (0.5 parts by mass).

[實施例11] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)、有機酸單酯(D-1)設為有機酸單酯(D-2)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 11] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 2.14 kg/hour (1 part by mass), the organic acid monoester (D-1 ) was set as the organic acid monoester (D-2), and the same method as Example 1 was followed, and the transparent thermoplastic resin composition particle was obtained.

[實施例12] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為4.28kg/小時(2質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 12] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 4.28 kg/hour (2 parts by mass), the rest were carried out in the same manner as in Example 1. In the same way, transparent thermoplastic resin composition particles were obtained.

[實施例13] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)、有機酸單酯(D-1)供給量設為4.28kg/小時(2質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 13] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 2.14 kg/hour (1 part by mass), the organic acid monoester (D-1 ), except that the supply amount was set to 4.28 kg/hour (2 parts by mass), transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1.

[實施例14] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為4.28kg/小時(2質量份)、有機酸單酯(D-1)供給量設為4.28kg/小時(2質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 14] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 4.28 kg/hour (2 parts by mass), the organic acid monoester (D-1 ), except that the supply amount was set to 4.28 kg/hour (2 parts by mass), transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1.

[實施例15] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)、有機酸單酯(D-1)供給量設為5.35kg/小時(2.5質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 15] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 2.14 kg/hour (1 part by mass), the organic acid monoester (D-1 ), except that the supply amount was set to 5.35 kg/hour (2.5 parts by mass), transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1.

[實施例16] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為5.35kg/小時(2.5質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 16] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 5.35 kg/hour (2.5 parts by mass), the rest were carried out in the same manner as in Example 1. In the same way, transparent thermoplastic resin composition particles were obtained.

[實施例17] 除了將酯蠟(C-1)設為酯蠟(C-4)以外，並將酯蠟(C-4)供給量設為5.35kg/小時(2.5質量份)、有機酸單酯(D-1)供給量設為5.35kg/小時(2.5質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 17] The supply amount of the ester wax (C-4) was 5.35 kg/hour (2.5 parts by mass), the organic acid monoester (D- 1) The transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1 except that the supply amount was 5.35 kg/hour (2.5 parts by mass).

[實施例18] 除了將酯蠟(C-1)設為酯蠟(C-5)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 18] Transparent thermoplastic resin composition particles were obtained in the same manner as in Example 1 except that the ester wax (C-1) was used as the ester wax (C-5).

[實施例19] 除了將酯蠟(C-1)設為酯蠟(C-6)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 19] The transparent thermoplastic resin composition particles were obtained in the same manner as in Example 1 except that the ester wax (C-1) was used as the ester wax (C-6).

[實施例20] 除了將酯蠟(C-1)設為酯蠟(C-7)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 20] Transparent thermoplastic resin composition particles were obtained in the same manner as in Example 1 except that the ester wax (C-1) was used as the ester wax (C-7).

[實施例21] 除了將酯蠟(C-1)設為酯蠟(C-8)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 21] The transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1 except that the ester wax (C-1) was used as the ester wax (C-8).

[實施例22] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)、有機酸單酯(D-1)設為有機酸單酯(D-3)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 22] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 2.14 kg/hour (1 part by mass), the organic acid monoester (D-1 ) was set as the organic acid monoester (D-3), and the same method as Example 1 was followed, and the transparent thermoplastic resin composition particle was obtained.

[實施例23] 除了將酯蠟(C-1)設為酯蠟(C-8)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 23] The transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1 except that the ester wax (C-1) was used as the ester wax (C-8).

[實施例24] 除了將酯蠟(C-1)設為酯蠟(C-8)，並將酯蠟(C-8)供給量設為4.28kg/小時(2質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 24] Except that the ester wax (C-1) was set to the ester wax (C-8), and the supply amount of the ester wax (C-8) was set to 4.28 kg/hour (2 parts by mass), the rest were carried out in the same manner as in Example 1. In the same way, transparent thermoplastic resin composition particles were obtained.

[實施例25] 除了將酯蠟(C-1)設為酯蠟(C-8)，並將酯蠟(C-8)供給量設為5.35kg/小時(2.5質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 25] Except that the ester wax (C-1) was set to the ester wax (C-8), and the supply amount of the ester wax (C-8) was set to 5.35 kg/hour (2.5 parts by mass), the rest were carried out in the same manner as in Example 1. In the same way, transparent thermoplastic resin composition particles were obtained.

[實施例26] 除了將接枝共聚合體(A-1)設為接枝共聚合體(A-2)，將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [實施例27] 除了將接枝共聚合體(A-1)供給量設為42.9kg/小時(20質量份)、乙烯系共聚合體(B)供給量設為171.4kg/小時(80質量份)，將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [實施例28] 除了將接枝共聚合體(A-1)供給量設為85.7kg/小時(40質量份)、乙烯系共聚合體(B)供給量設為128.6kg/小時(60質量份)，將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [實施例29] 除了將酯蠟(C-1)設為酯蠟(C-4)，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)、聚二甲基矽氧烷膠(E-1)供給量設為0.064kg/小時(0.03質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [比較例1] 除了將接枝共聚合體(A-1)供給量設為42.9kg/小時(20質量份)、乙烯系共聚合體(B)供給量設為171.4kg/小時(80質量份)，且未添加酯蠟(C)及有機酸單酯(D)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Example 26] Except that the graft copolymer (A-1) was set to the graft copolymer (A-2), the ester wax (C-1) was set to the ester wax (C-4), and the ester wax (C-4) The transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1 except that the supply amount was 2.14 kg/hour (1 part by mass). [Example 27] The ester wax ( C-1) The same method as in Example 1 was carried out except that the ester wax (C-4) was used, and the supply amount of the ester wax (C-4) was set to 2.14 kg/hour (1 part by mass). Transparent thermoplastic resin composition particles. [Example 28] The ester wax ( C-1) The same method as in Example 1 was carried out except that the ester wax (C-4) was used, and the supply amount of the ester wax (C-4) was set to 2.14 kg/hour (1 part by mass). Transparent thermoplastic resin composition particles. [Example 29] Except that the ester wax (C-1) was set to the ester wax (C-4), and the supply amount of the ester wax (C-4) was set to 2.14 kg/hour (1 part by mass), polydimethylsiloxane rubber (E-1) The transparent thermoplastic resin composition pellets were obtained in the same manner as in Example 1 except that the supply amount was 0.064 kg/hour (0.03 parts by mass). [Comparative Example 1] Except that the supply amount of the graft copolymer (A-1) was 42.9 kg/hour (20 parts by mass), the supply amount of the ethylene-based copolymer (B) was 171.4 kg/hour (80 parts by mass), and no ester was added Except for the wax (C) and the organic acid monoester (D), transparent thermoplastic resin composition particles were obtained in the same manner as in Example 1.

[比較例2] 除了未添加酯蠟(C)及有機酸單酯(D)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [比較例3] 除了將接枝共聚合體(A-1)供給量設為85.7kg/小時(40質量份)、乙烯系共聚合體(B)供給量設為128.6kg/小時(60質量份)，且未添加酯蠟(C)及有機酸單酯(D)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Comparative Example 2] Except not adding ester wax (C) and organic acid monoester (D), the same method as Example 1 was followed, and the transparent thermoplastic resin composition particle was obtained. [Comparative Example 3] Except that the supply amount of the graft copolymer (A-1) was 85.7 kg/hour (40 parts by mass), the supply amount of the ethylene-based copolymer (B) was 128.6 kg/hour (60 parts by mass), and no ester was added Except for the wax (C) and the organic acid monoester (D), transparent thermoplastic resin composition particles were obtained in the same manner as in Example 1.

[比較例4] 除了將酯蠟(C-1)設為酯蠟(C-4)以外，並將酯蠟(C-4)供給量設為2.14kg/小時(1質量份)、及未添加有機酸單酯(D)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Comparative Example 4] Except that the ester wax (C-1) was used as the ester wax (C-4), the supply amount of the ester wax (C-4) was 2.14 kg/hour (1 part by mass), and the organic acid monoester was not added Except (D), the same method as Example 1 was followed, and the transparent thermoplastic resin composition particle was obtained.

[比較例5] 除了將酯蠟(C-1)設為酯蠟(C-8)以外，並將酯蠟(C-8)供給量設為2.14kg/小時(1質量份)、及未添加有機酸單酯(D)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [比較例6] 除了將酯蠟(C-1)設為酯蠟(C-4)以外，並將酯蠟(C-4)供給量設為4.28kg/小時(2質量份)、及未添加有機酸單酯(D)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Comparative Example 5] Except that the ester wax (C-1) was used as the ester wax (C-8), the supply amount of the ester wax (C-8) was 2.14 kg/hour (1 part by mass), and the organic acid monoester was not added Except (D), the same method as Example 1 was followed, and the transparent thermoplastic resin composition particle was obtained. [Comparative Example 6] Except that the ester wax (C-1) was the ester wax (C-4), the supply amount of the ester wax (C-4) was 4.28 kg/hour (2 parts by mass), and the organic acid monoester was not added Except (D), the same method as Example 1 was followed, and the transparent thermoplastic resin composition particle was obtained.

[比較例7] 除了未添加酯蠟(C)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Comparative Example 7] Except not adding the ester wax (C), the same method as Example 1 was followed, and the transparent thermoplastic resin composition particle was obtained.

[比較例8] 除了未添加酯蠟(C)，並將有機酸單酯(D-1)供給量設為4.28kg/小時(2質量份)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Comparative Example 8] A transparent thermoplastic was obtained in the same manner as in Example 1, except that the ester wax (C) was not added and the supply amount of the organic acid monoester (D-1) was 4.28 kg/hour (2 parts by mass). Resin composition particles.

[比較例9] 除了將接枝共聚合體(A-1)設為接枝共聚合體(A-2)，且未添加酯蠟(C)及有機酸單酯(D)以外，其餘均依照與實施例1同樣的方法，獲得透明熱可塑性樹脂組成物顆粒。 [Comparative Example 9] The same procedure as in Example 1 was carried out except that the graft copolymer (A-1) was used as the graft copolymer (A-2), and the ester wax (C) and the organic acid monoester (D) were not added. method to obtain transparent thermoplastic resin composition particles.

將透明熱可塑性樹脂組成物及酯蠟、有機酸單酯之組成、及評價結果示於表1~3。The transparent thermoplastic resin composition, the composition of the ester wax, and the organic acid monoester, and the evaluation results are shown in Tables 1 to 3.

[表1]    實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 實施例 8 實施例 9 實施例 10 實施例 11 實施例 12 實施例 13 實施例 14 接枝共聚合體(A) 種類 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 質量份 30 30 30 30 30 30 30 30 30 30 30 30 30 30 乙烯系共聚合體(B) 質量份 70 70 70 70 70 70 70 70 70 70 70 70 70 70 酯蠟(C) 種類 C-1 C-2 C-3 C-4 C-4 C-4 C-4 C-4 C-4 C-4 C-4 C-4 C-4 C-4 質量份 0.5 0.5 0.5 0.5 0.3 1 1 0.3 1 1 1 2 1 2 有機酸單酯(D) 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 /D-2 D-2 D-1 D-1 D-1 質量份 1 1 1 1 0.3 0.3 0.05 1 1 0.5/0.5 1 1 2 2 夏比衝擊值 kJ/m ² 9.6 9.9 10.2 10.0 9.1 10.3 10.3 9.1 10.3 10.3 10.3 10.4 10.3 10.4 MFR g/10min 23 23 23 23 20 20 19 23 23 24 23 23 28 28 總光線穿透率 % 87.6 87 84 88.1 88.4 87.9 87.9 88.4 87.9 87.9 87.9 87 87.9 87 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Graft Copolymer (A) type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 parts by mass 30 30 30 30 30 30 30 30 30 30 30 30 30 30 Ethylene-based copolymer (B) parts by mass 70 70 70 70 70 70 70 70 70 70 70 70 70 70 Ester Wax (C) type C-1 C-2 C-3 C-4 C-4 C-4 C-4 C-4 C-4 C-4 C-4 C-4 C-4 C-4 parts by mass 0.5 0.5 0.5 0.5 0.3 1 1 0.3 1 1 1 2 1 2 Organic acid monoester (D) type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 /D-2 D-2 D-1 D-1 D-1 parts by mass 1 1 1 1 0.3 0.3 0.05 1 1 0.5/0.5 1 1 2 2 Charpy shock value kJ/m ² 9.6 9.9 10.2 10.0 9.1 10.3 10.3 9.1 10.3 10.3 10.3 10.4 10.3 10.4 MFR g/10min twenty three twenty three twenty three twenty three 20 20 19 twenty three twenty three twenty four twenty three twenty three 28 28 total light transmittance % 87.6 87 84 88.1 88.4 87.9 87.9 88.4 87.9 87.9 87.9 87 87.9 87

[表2]    實施例 15 實施例 16 實施例 17 實施例 18 實施例 19 實施例 20 實施例 21 實施例 22 實施例 23 實施例 24 實施例 25 實施例 26 實施例 27 實施例 28 實施例 29 接枝共聚合體(A) 種類 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-2 A-1 A-1 A-1 質量份 30 30 30 30 30 30 30 30 30 30 30 30 20 40 30 乙烯系共聚合體(B) 質量份 70 70 70 70 70 70 70 70 70 70 70 70 80 60 70 酯蠟(C) 種類 C-4 C-4 C-4 C-5 C-6 C-7 C-8 C-4 C-8 C-8 C-8 C-4 C-4 C-4 C-4 質量份 1 2.5 2.5 0.5 0.5 0.5 0.5 1 1 2 2.5 1 1 1 1 有機酸單酯(D) 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-3 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 2.5 1 2.5 1 1 1 1 1 1 1 1 1 1 1 1 其他(E) 種類 — — — — — — — — — — — — — — E-1 質量份 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.05 夏比衝擊值 kJ/m ² 10.3 10 10 10.2 10.4 9.9 10.5 10.3 10.6 10.6 10.3 10.3 9.2 13.4 11.8 MFR g/10min 30 23 30 23 23 23 23 23 23 23 23 23 25 20 23 總光線穿透率 % 87.9 86.5 86.5 83.8 83.2 87.6 83.2 87.9 82 81.3 80.2 88.3 88.1 87.8 87.9 [Table 2] Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Graft Copolymer (A) type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-2 A-1 A-1 A-1 parts by mass 30 30 30 30 30 30 30 30 30 30 30 30 20 40 30 Ethylene-based copolymer (B) parts by mass 70 70 70 70 70 70 70 70 70 70 70 70 80 60 70 Ester Wax (C) type C-4 C-4 C-4 C-5 C-6 C-7 C-8 C-4 C-8 C-8 C-8 C-4 C-4 C-4 C-4 parts by mass 1 2.5 2.5 0.5 0.5 0.5 0.5 1 1 2 2.5 1 1 1 1 Organic acid monoester (D) type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-3 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 2.5 1 2.5 1 1 1 1 1 1 1 1 1 1 1 1 Other (E) type — — — — — — — — — — — — — — E-1 parts by mass 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.05 Charpy shock value kJ/m ² 10.3 10 10 10.2 10.4 9.9 10.5 10.3 10.6 10.6 10.3 10.3 9.2 13.4 11.8 MFR g/10min 30 twenty three 30 twenty three twenty three twenty three twenty three twenty three twenty three twenty three twenty three twenty three 25 20 twenty three total light transmittance % 87.9 86.5 86.5 83.8 83.2 87.6 83.2 87.9 82 81.3 80.2 88.3 88.1 87.8 87.9

[表3]    比較例 1 比較例 2 比較例 3 比較例 4 比較例 5 比較例 6 比較例 7 比較例 8 比較例 9 接枝共聚合體(A) 種類 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-2 質量份 20 30 30 30 30 30 30 30 30 乙烯系共聚合體(B) 質量份 80 70 70 70 70 70 70 70 70 酯蠟(C) 種類 — — — C-4 C-8 C-4 — — — 質量份 0 0 0 1 1 2 0 0 0 有機酸單酯(D) 種類 — — — — — — D-1 D-1 — 質量份 0 0 0 0 0 0 1 2 0 夏比衝擊值 kJ/m ² 7.5 8.1 10.5 10.3 10.6 10.5 8.1 8.0 8.1 MFR g/10min 20 17 13 19 18 20 22 26 17 總光線穿透率 % 88.7 88.6 88.5 87.9 82.3 87.2 88.4 88.2 89 [table 3] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Graft Copolymer (A) type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-2 parts by mass 20 30 30 30 30 30 30 30 30 Ethylene-based copolymer (B) parts by mass 80 70 70 70 70 70 70 70 70 Ester Wax (C) type — — — C-4 C-8 C-4 — — — parts by mass 0 0 0 1 1 2 0 0 0 Organic acid monoester (D) type — — — — — — D-1 D-1 — parts by mass 0 0 0 0 0 0 1 2 0 Charpy shock value kJ/m ² 7.5 8.1 10.5 10.3 10.6 10.5 8.1 8.0 8.1 MFR g/10min 20 17 13 19 18 20 twenty two 26 17 total light transmittance % 88.7 88.6 88.5 87.9 82.3 87.2 88.4 88.2 89

如實施例1~29的評價結果所示，本實施形態之透明熱可塑性樹脂組成物係於維持特別高度之透明性、良好之色調之下，兼具優越的耐衝擊性及流動性。另一方面，比較例2及比較例9由於未添加酯蠟(C)及有機酸酯(D)，故耐衝擊性及流動性差。比較例4~比較例6由於未添加有機酸酯(D)，故流動性差。比較例7及比較例8由於未添加酯蠟(C)，故流動性差。 (產業上之可利用性) As shown in the evaluation results of Examples 1 to 29, the transparent thermoplastic resin composition of the present embodiment has both excellent impact resistance and fluidity while maintaining a particularly high degree of transparency and a good color tone. On the other hand, in Comparative Example 2 and Comparative Example 9, since the ester wax (C) and the organic acid ester (D) were not added, impact resistance and fluidity were poor. In Comparative Examples 4 to 6, since the organic acid ester (D) was not added, the fluidity was poor. In Comparative Example 7 and Comparative Example 8, since the ester wax (C) was not added, the fluidity was poor. (Industrial Availability)

本實施形態之透明熱可塑性樹脂組成物及成形品，係可廣泛利用於家電製品、通訊關聯機器、一般雜貨及醫療關聯機器等用途。The transparent thermoplastic resin composition and molded article of the present embodiment can be widely used in home appliances, communication-related equipment, general miscellaneous goods, and medical-related equipment.

1:反應槽 2:預熱機 3:雙軸擠出機型脫單體機 4:熔融混練區域 5:雙軸擠出機型進料器 6:吐出口 7:攪拌機(螺帶葉片) 8:排氣口 9:水注入口 10:最終排氣口 1: Reaction tank 2: Preheater 3: Double-shaft extruder type de-monomer machine 4: Melt kneading area 5: Biaxial extruder type feeder 6: Spit out 7: mixer (ribbon blade) 8: exhaust port 9: water inlet 10: Final exhaust port

圖1為用於製造本發明之透明熱可塑性樹脂組成物之製造裝置的一實施態樣的概略圖。FIG. 1 is a schematic view of one embodiment of a manufacturing apparatus for manufacturing the transparent thermoplastic resin composition of the present invention.

Claims (7)

一種透明熱可塑性樹脂組成物，係含有下述者而成：於橡膠質聚合體(r)存在下，使至少含有芳香族乙烯系單體(a1)及(甲基)丙烯酸酯系單體(a2)之單體混合物(a)進行接枝共聚合而得的接枝共聚合體(A)；使至少含有芳香族乙烯系單體(b1)、(甲基)丙烯酸酯系單體(b2)及氰化乙烯系單體(b3)之單體混合物(b)進行共聚合而成的乙烯系共聚合體(B)；下述酯蠟(C)；及下述有機酸單酯(D)； 酯蠟(C)：選自由甘油脂肪酸酯類(c1)及脂肪酸酯(c2)所構成群之至少一種酯蠟；該脂肪酸酯(c2)係由碳數12~30之直鏈飽和單羧酸、與選自由碳數14~30之直鏈飽和單元醇及碳數2~30之2~6價之多元醇所構成群之至少一種醇所得； 有機酸單酯(D)：由二羧酸酐、與碳數14~30之直鏈飽和單元醇所得之有機酸單酯。 A transparent thermoplastic resin composition comprising at least an aromatic vinyl-based monomer (a1) and a (meth)acrylate-based monomer ( The graft copolymer (A) obtained by the graft copolymerization of the monomer mixture (a) of a2); it contains at least an aromatic vinyl monomer (b1) and a (meth)acrylate monomer (b2) A vinyl-based copolymer (B) obtained by copolymerizing a monomer mixture (b) of a vinyl cyanide-based monomer (b3); the following ester wax (C); and the following organic acid monoester (D); Ester wax (C): at least one ester wax selected from the group consisting of glycerol fatty acid esters (c1) and fatty acid esters (c2); the fatty acid ester (c2) is composed of a straight-chain saturated monolayer having 12 to 30 carbon atoms. Carboxylic acid, and at least one alcohol selected from the group consisting of straight-chain saturated unit alcohols with 14-30 carbon atoms and 2-6 valent polyols with 2-30 carbon atoms; Organic acid monoester (D): an organic acid monoester obtained from dicarboxylic acid anhydride and a straight-chain saturated unit alcohol having 14 to 30 carbon atoms. 如請求項1之透明熱可塑性樹脂組成物，其中，相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，上述酯蠟(C)之含量為0.4質量份以上且2質量份以下。The transparent thermoplastic resin composition according to claim 1, wherein the content of the ester wax (C) is 0.4 parts by mass or more relative to 100 parts by mass in total of the graft copolymer (A) and the vinyl copolymer (B) and 2 parts by mass or less. 如請求項1或2之透明熱可塑性樹脂組成物，其中，相對於接枝共聚合體(A)及乙烯系共聚合體(B)之合計100質量份，上述有機酸單酯(D)之含量為0.1質量份以上且2質量份以下。The transparent thermoplastic resin composition according to claim 1 or 2, wherein the content of the organic acid monoester (D) is 100 parts by mass in total of the graft copolymer (A) and the vinyl copolymer (B). 0.1 mass part or more and 2 mass parts or less. 如請求項1至3中任一項之透明熱可塑性樹脂組成物，其中，上述有機酸單酯(D)為順丁烯二酸單酯。The transparent thermoplastic resin composition according to any one of claims 1 to 3, wherein the organic acid monoester (D) is a maleic acid monoester. 如請求項1至4中任一項之透明熱可塑性樹脂組成物，其中，上述酯蠟(C)為蓖麻子硬化油。The transparent thermoplastic resin composition according to any one of claims 1 to 4, wherein the ester wax (C) is castor bean hardened oil. 一種透明熱可塑性樹脂組成物之製造方法，係調配：於橡膠質聚合體(r)存在下，使至少含有芳香族乙烯系單體(a1)及(甲基)丙烯酸酯系單體(a2)之單體混合物(a)進行接枝共聚合而得的接枝共聚合體(A)；使至少含有芳香族乙烯系單體(b1)、(甲基)丙烯酸酯系單體(b2)及氰化乙烯系單體(b3)之單體混合物(b)進行共聚合而成的乙烯系共聚合體(B)；下述酯蠟(C)；及下述有機酸單酯(D)，並進行熔融混練； 酯蠟(C)：選自由甘油脂肪酸酯類(c1)及脂肪酸酯(c2)所構成群之至少一種酯蠟；該脂肪酸酯(c2)係由碳數12~30之直鏈飽和單羧酸、與選自由碳數14~30之直鏈飽和單元醇及碳數2~30之2~6價之多元醇所構成群之至少一種醇所得； 有機酸單酯(D)：由二羧酸酐、與碳數14~30之直鏈飽和單元醇所得之有機酸單酯。 A method for producing a transparent thermoplastic resin composition, comprising: in the presence of a rubbery polymer (r), at least an aromatic vinyl-based monomer (a1) and a (meth)acrylate-based monomer (a2) are prepared. The graft copolymer (A) obtained by graft copolymerizing the monomer mixture (a); at least containing aromatic vinyl monomer (b1), (meth)acrylate monomer (b2) and cyanide The vinyl-based copolymer (B) obtained by copolymerizing the monomer mixture (b) of the vinyl-based monomer (b3); the following ester wax (C); and the following organic acid monoester (D), and the melt mixing; Ester wax (C): at least one ester wax selected from the group consisting of glycerol fatty acid esters (c1) and fatty acid esters (c2); the fatty acid ester (c2) is composed of a straight-chain saturated monolayer having 12 to 30 carbon atoms. Carboxylic acid, and at least one alcohol selected from the group consisting of straight-chain saturated unit alcohols with 14-30 carbon atoms and 2-6 valent polyols with 2-30 carbon atoms; Organic acid monoester (D): an organic acid monoester obtained from dicarboxylic acid anhydride and a straight-chain saturated unit alcohol having 14 to 30 carbon atoms. 一種成形品，係將請求項1至5中任一項之透明熱可塑性樹脂組成物進行成形而成。A molded article obtained by molding the transparent thermoplastic resin composition of any one of claims 1 to 5.

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