TW506973B - Transparent styrenic resin composition - Google Patents

Abstract

The present invention provides a transparent styrenic resin composition composed of: (I) 100 parts by weight of transparent styrenic resin; and (II) 0.01-5 parts by weight of ester compounds of pentaerythritol. Wherein, in the transparent styrenic resin, the content of the resin soluble in dichloromethane, having a molecular weight of less than 350, and not including monomers and the solvent is less than 2.0 wt% of all the soluble parts. The transparent styrenic resin composition can have excellent transparency and processibility, and will not result in mold pollution while molding by adding the ester compounds of pentaerythritol and controlling special low molecular weight of the transparent styrenic resin.

Description

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2. Description of the invention (1) B? &Quot; It is about a kind of transparent styrenic resin composition, especially Heben t: B "resin with pentaerythritol vinegar compound, and is processed with" Fangshu Yue Yue " " Temperature's low molecular weight content is used to obtain good transparency and mechanical properties. At the same time, it is a resin composition during molding. fThe transparent styrene button of the mold is not produced. The styrene resin is a material with good strength and processability. In particular, the transparent styrene resin can be used in household products and household appliances such as transparent food packaging materials. Products and 〇a machines'. Because of the current processing of styrenic resins, the processing conditions have strict requirements for thinning and large-sized products. Therefore, in order to improve the resin without compromising physical properties, In the known art, the processability of the molded product is to add a small amount of slip to the styrene resin to be used as an adjuvant during the molding process to improve the processing fluidity of the molded product; and- The processing aids generally used in styrene resins are, for example, metal salts of fatty acids, of which, stearin, zinc stearate, and amines of fatty acids (such as ethylene distearylamine) do have processability. The improvement effect is as described in the Japanese Patent Application No. 2-52923. When the styrene resin is manufactured, the reaction tank is filled with "丨 parts by weight of ethylene distearate" Solution, can improve the addition of resin. Japan = Kaizhao No. 63-33455 In the patent application, it is mentioned that adding calcium stearate or zinc stearate to styrene resin and kneading can improve the resin molding. In addition, it is described in Japanese Patent Application Laid-Open No. 7_82439 that butyl stearate is added to styrene resin (X-butyl and less X- Printed by A7, Consumer Cooperative of the Central Standards Bureau, Ministry of Economic Affairs- ------- B7 Description of the invention g) --- ~ Triglyceride, which can improve the fluidity and impact resistance of the resin; however, a slip agent is added to the transparent styrene resin Additives such as release agents and release agents can improve the processability and release properties of the resin, but the aforementioned additives will cause the resin's transparency to deteriorate, and stupid vinyl resins with good transparency cannot be obtained; some additives will also In the case of injection molding, the forks are contaminated and the like, especially in high temperature and thin meat injection molding. The problem will be more serious; the present invention intends to solve the shortcomings of the foregoing prior art. Therefore, the present invention is to provide A transparent styrenic resin composition that has good transparency and processability and does not cause mold contamination during molding. The transparent styrenic resin composition of the present invention is composed of: < I > 100 parts by weight of transparent Styrene resin; < Π > 0.01 to 5 parts by weight of pentaerythritol ester compound j Among which, the molecular weight i of the digas methane soluble matter in the transparent styrene resin is less than 350 and the low molecular weight polymerization The content of the transparent styrene-based resin of the present invention means that it has transparency, and generally, it means a light transmittance of 60% or more before further processing and coloring. Ben Mingming's transparent benzyl resin can be divided into two types, namely transparent styrene resin modified by rubber and transparent styrene resin without rubber. The transparent styrene-based resin without rubber refers to a styrene-based resin containing 30% by weight or more of a styrene-based monomer, that is, a styrene-based monomer ---- page 14 This paper is applicable to China Standard (CNS) A4 specification (210X297mmt) (Please read the precautions on the back before filling this page)

1. Line 1T !! Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 —_____ B7 V. Description of the Invention (3)-Purchase 0% by weight and other copolymerizable monomers 0 ～ 70% by weight. The above other copolymerizable monomers are not particularly limited as long as they can be copolymerized with styrene monomer to achieve transparency. Specific examples of the copolymerizable monomer of the rubber-free transparent styrene-based resin of the present invention may be: (meth) acrylate-based monomer, acrylonitrile-based monomer, maleimide-based monomer, (methyl ) Acrylic, anhydrous maleic acid, and ethylene glycol methacrylate, where (meth) acrylate monomers can be: methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methyl Ethyl acrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, methacrylic acid 2 -Hydroxyethyl ester, glycidyl methacrylate, and diamidoethyl methacrylate, etc. Among them, methyl methacrylate is preferred. The acrylonitrile-based monomer may be acrylonitrile or α-methacrylonitrile. Among them, acrylonitrile is preferred. The maleimide-based monomer may be selected from: N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide Amine, N-octylmaleimide, N-dodecylmaleimide, N_cyclohexylmaleimide, N-phenylmaleimide, N-2,3- Tolyl maleimide, N-2,4-tolyl maleimide, N-2,3-ethylphenylmaleimide, Ν-2,4-ethylphenylmaleimide Amine, N-2,3-butylphenylmaleimide, N-2,4-butylphenylmaleimide, N-2,6-tolylmaleimide, N-2, 3-Gaphenylmaleimide, N-2,4-chlorophenylmaleimide, N-2,3-bromophenylmaleimide, N-2,4-benzyl Malay imine, etc. 'where' is Ν-the base _____ page 5 ____ This paper size applies Chinese National Standard (CNS) A4 specifications (210 × 297 mm) (Please read the precautions on the back before filling in this Page), 1T line ·! 506973 A7 5. Description of the invention (4) Maleimide is the best. Specific examples of rubber-free transparent styrene-based resins include polystyrene-based, styrene-acrylonitrile-based copolymers, styrene-based methacrylic acid, copolymers, and styrene-based substituted maleic acid. Imine-acrylonitrile-based copolymer, styrene-based substituted maleimide-based imide-based copolymer, styrene-based (meth) acrylate-N-substituted maleimide-based imine-based copolymer, styrene-based _ Ν-Substituted maleimide-propylene-based materials _ (meth) acrylic acid-based copolymers and other printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page), 1T Another type of transparent styrene-based resin of the present invention: transparent styrene resin modified by rubber, preferably transparent styrene resin modified by dilute rubber. It can be a mixture of rubber and transparent styrene resin without rubber 'or obtained by graft polymerization of rubber with styrene-based monomers and other copolymerizable monomers. The aforementioned rubbers are, for example, butadiene , Butadiene-styrene dilute or random or block copolymers. The rubber-modified transparent styrene-based resin obtained by graft polymerization has a preferable structure: a rubber particle dispersed phase (A) formed of a rubber-like polymer, and a total of 100 parts by weight of monomers. From 12 to 70 parts by weight of styrene-based monomer, 20 to 80 parts by weight of (meth) acrylic acid-based monomer, 0 to 20 parts by weight of acrylonitrile-based monomer, and 0 to 0 of other copolymerizable monomers 40 parts by weight of the continuous phase of the copolymer (consisting of the composition. The rubber-like polymer described in 'J' is preferably composed of 5 to 50% by weight of a styrene-based monomer and 95% of a diene-based monomer. ~ 50% by weight; the above-mentioned rubbery copolymer is an organic lithium compound as an initiator in the presence of an organic solvent, and is anionic with a styrene-based monomer, an olefin-based monomer, and an appropriate amount of a solvent A block copolymer produced by polymerization. The woody paper size of the above copolymers is in accordance with Chinese National Standard (CNS) page 210X297 mm. / Ό Λ7 B7 V. Description of the invention (5 (Moony) viscosity (MLi + 4) Viscosity of 5% to 5% by weight of styrene monomer solution The degree is 3 to 60 cps, and the a vinyl structure in the diene unit accounts for more than 8% by weight, and the content of the polystyrene block accounts for 5 to 35% by weight of the rubber-like copolymer. The structure of the rubber-like copolymer may be The structures are all: homopolymer block structure, partially disordered block structure, taper-block structure with increasing composition, linear structure, and branch structure. The representative structure can be : 1. Linear block copolymer: d) (AB) n (2) AfBA) n (3) n In the above formula, A is a polymer block with styrene as the main component, and B is a diene. The polymer block as the main component, the boundary between the a block and the b block does not necessarily need to be clearly distinguished, n = 1 or an integer 2 or more (please read the precautions on the back before filling this page) Standard Bureau staff consumer cooperative prints branched block copolymers: (2) [(AB t ~ 7i-m_2 X (3) [(B-Ai—to ~~ X (4) [(AB 于 丁 ^ 十. x In the above formula, A and B are the same as described in item 1. X is a coupling agent residue (for example, silicon tetraoxide, tin tetrachloride, etc.), or a polyfunctional organolithium compound residue, η and m 1 to 10 Integer. The mixture of any form of item 1 and item 2 is described. Page line ·! This paper size Tongzhou T country winter standard (CNS) A4 specification (210X 297 mm) 5. Description of the invention (6 separately created , Or specific examples are DD / SS DSD / SS DSD / SSD SDD / SS D / SSDS SD / SS (SD / S) n. The gradually increasing block structure belongs to the newly added block structure, which can be Styrene-based gradual discrete block structure

(SD / S) nS D / S-(SD / S) n X-[(SD / S) n] m + 1 X-[(D / SS) n) m + 1 X-[(SD / S) nS] m + 1 X-[(D / SS) nD / S] mH DD / SS-SD / SD Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, where 'S is a polystyrene block and D is a poly Diene block, D / s is a styrene-diene copolymer block with increasing styrene- or dilute component content, X is a polyfunctional initiator group or a polyfunctional coupling agent group, ㈣ Is an integer of u. In the above specific examples, DD / s_s or D_S_D / S_S and D_D / SSSD / S 'are preferred. For the purposes of the present invention, it is more appropriate to construct a progressive funnel. The aforementioned styrene-based monomer may be: styrene, α-fluorenylstyrene, p-methylstyrene, m-fluorenylstyrene, o-methylstyrene, ethylstyrene, 2,4-bis Fluorenylstyrene, p-third-butylstyrene, α-methyl_p-methylstyrene, bromo-styrene, dibromo-styrene, 2,4,6-tribromostyrene, etc. These styrene-based monomers may be used alone or in combination. The diene monomer is selected from: 1,3 · butadiene, 2-methyl_1,3-butadiene, 2-methyl-1,3-isoprene, 2,3-di- Methyl-1,3-butadiene, 1,3-isoprene, hexamethylene. 'The above compounds can be used alone or on the page. This paper applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) Li) (Please read the notes on the back before filling in this page}

506973 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (7) Two or more types are used in combination, of which 1,3-butadiene or 1,3-isoprene is preferred. The organolithium compound catalyst used in the aforementioned rubbery copolymer is a compound containing more than one lithium atom in the molecule, and may be selected from the group consisting of ethyl lithium, n-pentyl lithium, isopropyl lithium, n-butyl lithium, Secondary butyl lithium, hexyl lithium, cyclohexyl clock, phenylene chain, benzyl chain, naphthyl, third-butyl clock, trimethylene dilithium, tetramethylene dilithium, butadiene bis One or two or more of lithium and isoprene dilithium are used in combination. The polymerization rate of the aforementioned rubbery copolymer during polymerization, the ethylene content, and the reactivity ratio and disordered state of the diene monomer and the styrene monomer may be polar compounds or disordered ( random) chemical agents to adjust, the above polar compounds or disordering agents are selected from the group consisting of ethers, amines, thioetheramines, alkylbenzenes, sulfon acids, and potassium or sodium alkyl oxides salt. In addition, the copolymer continuous phase (B) of the present invention is composed of 12 to 70 parts by weight of a styrene-based monomer, 20 to 80 parts by weight of a (meth) acrylate-based monomer, and 0 to 20 parts by weight of acrylonitrile. And other copolymerizable monomers of 0 to 40 parts by weight. Specific examples of the styrene-based monomers are the styrene-based monomers of the aforementioned rubber copolymers, and are not repeated here. . The (meth) acrylate-based monomer includes fluorenyl acrylates and acrylates, and the methacrylates may be, for example, methyl methacrylate, ethyl methacrylate, or butyl methacrylate. Acrylates, etc., and acrylates are, for example: ethyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylpentyl acrylate, 2-ethylpentyl acrylate, octyl acrylate, etc. Phenyl methyl acrylate and methyl acrylate are better _ page 9 This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling out this page} 、 1 · hair·!

V. Description of the invention (8) One ~ one ... · ———— ~ One one one — Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The acrylonitrile monomer of the present invention may be acrylonitrile, α-methacrylonitrile, or the like. The copolymerizable monomer in the continuous phase (B) of the copolymer of the present invention is 0 to 40 parts by weight. There is no particular limitation on the type of the monomer. The content ratio and inflection ratio of each copolymerizable monomer can be adjusted as needed to make the final It is necessary for the resin composition to achieve transparency. Specific examples of the above copolymerizable monomers include unsaturated fatty acids such as itaconic acid, maleic acid, fumaric acid, butenoic acid, and cinnamic acid; N-methyl maleic acid Imine, Ν-ethylmaleimide, butylmaleimide, N_octylmaleimide, Ν-isopropylmaleimide, Ν_phenylmaleimide Amines, N-p-bromo-phenylmaleimide, swimming o-gas-phenylmaleimide, ... cyclohexylmaleimide and other maleimides; maleic anhydride Unsaturated carboxylic acid anhydrides such as itaconic anhydride, scorconic anhydride; allylamines, (meth) aminoethyl ethyl methionate, aminopropyl (meth) acrylate and other unsaturated compounds , Propofolamine compounds such as acrylamine and N-methacrylamide. The weight average molecular weight of the copolymer continuous phase (B) in the resin composition of the present invention is not particularly limited, but is generally 50,000 to 300,000, preferably 60,000 to 200,000, and more preferably 7 〇〇〇〇〇〇〜１００００〇, when the weight average molecular weight ΐ is less than 50,000, the impact strength of the resin composition is poor, and when the weight average molecular weight is less than 300,000, the fluidity of the resin composition will decrease Poor processability and poor transparency; In addition, the weight average particle diameter of the rubber particles of the resin composition of the present invention is also not particularly limited, and is generally 〇1 ~ 2〇 # m, preferably 0.1 ~ 1.5 // m ', more preferably 0.2 ~ l.〇 // m, when the weight average particle diameter of the rubber particles is less than 0.1 / zm, the impact strength of the resin composition decreases. If the weight is ________ page 10, the Chinese paper standard (CNS) A4 applies Specifications (210xT ^ f) _-- ~ 1 (Please read the precautions on the back before filling this page)

5. Description of the invention (9) ~~-~ ^ ϊ If the average particle diameter is greater than 2.0em, the transparency of the resin composition is poor. The weight-average particle diameter of the rubber particles is a photograph obtained by an ultra-thin sectioning method of a transmission electron microscope. The photograph has a minimum of 300 particles or more, and the weight-average particle diameter is measured by the following formula.

EniD i4 weight average particle size =-

EniD i3 In the above formula, ni is the number of rubber particles with a particle size Di. The gel content in the resin composition of the present invention, that is, the content of insolubles in toluene / acetone (weight ratio 1/1) is not particularly limited, and is generally [] to ⑽wt%, preferably 8 to 35wt%, more It is preferably 12 to 30% by weight. In addition, the swelling index in the resin composition of the present invention is not particularly limited, but is generally 2 to 25, preferably 3 to 20, and more preferably 5 to 15. Among the methylene chloride solubles of the transparent styrene resin printed by the employee's cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, the low molecular weight polymer with a molecular weight of less than 350 accounts for less than 20% by weight of the total solubles, preferably 1.0 When the content of the low-molecular-weight polymer less than 350 in the molecule is more than 20% by weight, the phenomenon of mold contamination is likely to occur during processing and molding of the styrene-based resin, and production may occur. Mouth defects, the so-called dichloromethane-soluble molecular weight of the styrenic resin: low molecular weight polymer at 350 'refers to the addition of styrenic resin to the solvent of chloroform: ¾ Part (soluble fraction WGC-mass (gas chromatograph_mass spectrometer) measures the content of low-molecular-weight polymers with a molecular weight of less than 350 (in terms of styrene standard area). The transparent styrene resin of the present invention Four pentagrams of paper contained in the composition, paper rule, money account 506973 Λ7 B7 V. Description of the invention (10) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Ester The compound is an ester compound formed by the reaction of pentaerythritol with a carboxylic acid compound. Among them, the carboxylic acid compound can be: lauric acid (also known as lauryl acid), palmitic acid (also known as palmitic acid) ), Stearic acid (also known as steric acid), arachidonic acid, behenic acid (also known as behenic acid), lignoceric acid, Insecticidal acid Cerotic acid), montanic acid (also known as montanic acid), oleic acid (also known as oleic acid), elaidic acid, erucic acid, flax Linoleic acid, linolenic acid, linolenic acid, oxalic acid (also known as oxalic acid), malonic acid, succinic acid, glutaric acid ( glutaric acid), adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, azelaic acid ( nonane dicarboxylic acid), decane dicarboxylic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid, eicosane dicarboxylic acid, Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itconic acid), eyeloproane dicarboxylic acid, cyclobutane Carboxylic acid (cyclobutane dicarboxylic acid), cyclopentadiane dicarboxylic acid, camphor acid, hexahydrophthalic acid, phthalic acid, tetraphthalic acid (Terephthalic acid), isophthalic acid, naphthalic acid ___ page 12 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 506973 Λ7 B? 5. Description of the invention ( 11) acid), diphenyl_o, o'-dicarboxyl acid, and the like. Specific examples of the pentaerythritol ester compounds of the transparent styrene resin composition of the present invention include pentaerythritol tristearate, pentaerythritol adipate stearate, and pentaerythritol adipate stearate. Pentaerythritol succinate stearate, pentaerythritol tetrastearate, and pentaerythritol tetralaurate. Among them, pentaerythritol tetrastearate is preferred; the above-mentioned pentaerythritol ester The production of similar compounds can be based on the esterification reaction procedure, especially the catalysts of the esterification procedure, such as organic tin compounds, and the amount of alcohols and carboxylic acid compounds used in the reaction depends on the type and stoichiometry. . The addition amount of the pentaerythritol ester compound of the present invention is 0.01 to 5 parts by weight, preferably 0.02 to 3 parts by weight, and more preferably 0.05 to 1.5 parts by weight relative to 100 parts by weight of the transparent styrene resin. When the amount is less than 0.01 part by weight, the molding processability of the styrene resin is poor, and the mold release property is poor. When the amount is more than 5 parts by weight, mold contamination is liable to occur, and the heat resistance and transparency of the resin composition are deteriorated. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The pentaerythritol ester compound addition method of the present invention is not particularly limited, and it can be added when the styrene resin is polymerized. Or add it after polymerization, or add it by extruder or static mixer. The production method of the transparent styrene resin of the present invention may be an emulsification, suspension, block (or solution) polymerization method, or a combination of the above several polymerization methods, preferably ___ page 13 _________ This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) A1 B? V. Description of the invention (12 Solution polymerization method is emulsification or block (or solution) polymerization method, more preferably block or the rubber modified by the present invention One of the manufacturing methods of transparent styrene resin is to combine with styrene-based monomer, (methacrylic-based early body, acrylonitrile-based monomer, and other polymerizable polymers if necessary). The monomers are subjected to batch or continuous block or dissolving reactions; if the dissolving reaction is taken as an example, the above rubbery copolymer and monomers are first added to an appropriate solvent to form a raw material mixed solution. The raw material mixed solution can be dissolved in traditional dissolving towels with high shear stress and high velocity. ^ Cryolysis & can be used. It has ribbon-shaped spiral scrambled leaves, spiral pulp scrambled leaves, or other Shear stress of stirring blades, etc., in sufficient In between, the above-mentioned rubber-like copolymer can be completely dissolved into a rubber solution. It can be easily pumped to the reactor for operation; the aforementioned raw material or monomer solution is continuously fed to the first reactor and / or In the second reactor and / or a subsequent reactor, a graft polymerization reaction is performed under the condition that a chain transfer agent and an initiator are added to the first and / or second and / or subsequent reactors. The above-mentioned reaction tank printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs may be a continuous stirring type reaction tank (CSTR), a plug flow type reaction tank (Plug Flow reactor), or the same as a static mixing type magic reactor. One or a combination of different types; the reaction temperature is controlled between 70 and 23, and the final monomer conversion rate can reach 30 to 95%, but preferably 50 to 90%. The transparent styrene resin of the present invention is polymerized during polymerization. At this time, the types of solvents that can be used are aromatic hydrocarbons, ketones, and esters. Among them, the best aromatic hydrocarbons are, for example, toluene, ethylbenzene, and xylene, and ketones are the most --- ------ Page 14 This paper is applicable National Standard (CNS) A4 specification (21 × X 297 mm) 506973 Λ 7 B? 5. Description of the invention (13) The best is methyl ethyl ketone, and the best ester is ethyl acetate; In addition, the invention can also be used Aliphatic hydrocarbons such as n-ethane, cyclohexane, and n-heptane are part of the solvent. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). In the production of the transparent styrenic resin composition of the present invention, the usable initiators include: benzoyl peroxide, dicumyl peroxide, and dibenzoyl peroxide ( di benzoyl superoxide), t-butyl peroxide, t-butyl hydroxy peroxide, cumene hydroperoxide, third butyl peroxide T-butyl peroxy benzoate, di-2_ ethylhexyl peroxy dicarbonate, tert, butyl peroxy isopropyl carbonate (BPIC), peroxide Cyclohexanoe peroxide, 2,2'-azo-bis-isobutyronitrile, 1,1'-azo-bis-1-cyclohexane Weinnitrile (1,15-azo-bis-1-cyclohexane carbonitrile), 2,2'-azo-bis-2-methylbutyronitrile (2,2'-azo-bis-2-methyl butyronitrile), even Nitro-bis-isobutyronitrile (& 2〇-1) 丨 8- 丨 8〇13111) ^ 011 pool 丨 16), 1,1-diperoxy third butyl cyclohexane (l, l-di -t-butyl peroxy cyclohexane (TX-22 for short), 1,1-di-peroxy third butyl-3,3,5-trimethylcyclohexane (l, l-di-t-butylperoxy-3 , 3,5-trimethyl cyclohexane (referred to as TX-29A), 2,5-dimethyl-2,5-bis- (2-ethylperoxyhexyl) hexane [2,5-dimethyl-2,5 -bis- (2-ethylhexanoxy peroxy) hexane], 4- (peroxy third butylcarbyl) -3-hexyl-6- [7- (third butylcarbonyl) heptyl] cyclohexane {4- (t-butyl peroxy carbonyl) -3-hexyl-6- [7- (t-butyl peroxy _ page 15) This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 506973 Λ7 B7 V. Description of the invention 丨 4) carbonyl) heptyl] cyclohexane}, di-third butyl Di-t-butyl-diperoxyazelate, 2,5-dimethyl-2,5-bis (benzidine peroxide) -hexane [2,5-dimethyl-2,5-bis -(benzoyl peroxy) hexane], di-t-butyl peroxy-1 ^ and 211} ^ (11 * 〇-16 代 0) 11: 1 ^ 1316, referred to as 8? 11 Ding? ), 2,2-bis (4,4-di-t-butylperoxy) cyclohexylpropane [2,2-bis- (4,4-di-t-butyl peroxy) cyclohexanyl propane], etc. The present invention In the production of transparent styrenic resin compositions, the chain transfer agents that can be used are, for example: 1) Mercaptans: methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, n-deca Dialkyl mercaptan, stearyl mercaptan, t-dodeyl mercaptan (TDM), n-propyl mercaptan, n-octyl mercaptan, Third-octyl mercaptan, third-nonyl mercaptan, and the like. 2) Alkylamines: monoethylamine, diethylamine, triethylamine, monoisopropylamine, dimonopropylamine, monobutylamine, di-n-butylamine, triamine -N-butylamine and the like. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Others such as: pentaphenylethane, α-methyl styrene dimer (a-methyl styrene dimer), terpinolene 〇 After the aforementioned polymerization reaction, take out from the reactor through a devolatilization device, remove unreacted monomers, solvents and other low-volatile components, and after polymer recovery, it can be obtained Transparent styrene resin. The ester compounds of pentaerythritol of the present invention can also be used in styrene resins. __Page 16 This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm) ΑΊ --s- ~~ s _______ V. Description of the invention ( 15)… ———— ----------- After the polymerization is completed, it is mixed with styrene resin and mixed with a Brabender plastic meter, a Banbury mixer, a kneading and mixing machine, It is made by mixing and kneading with a general dust kneading machine such as a roller duster and a shaft or two extruder. Usually, these extruder machines are used for mixing and kneading, and then the extruded objects are cooled,

For granulation, the above kneading is generally performed at 160 ~ 28 (Γ (:, and preferably at a temperature of 180 ~ MO C.) There is no particular limitation on the order of the ingredients of the aforementioned mixing and kneading. Not significant To the extent that the effect of the resin composition of the present invention is impaired, other ingredients may be blended. These other ingredients are, for example, colorants, fillers, flame retardants, flame retardant additives (antimony trioxide, etc.), and light stability. Additives, heat stabilizers, plasticizers, lubricants, release agents, tackifiers, antistatic agents, oxidation inhibitors, conductive agents, etc .; the above additives can be, for example: mineral oil, such as: butyl stearate Ester-based plasticizers, polyester-based plasticizers, such as polydimethylsiloxane-organopolysiloxanes, higher fatty acids and their metal salts, hindered amine-based antioxidants, glass fibers, etc., which can be used alone or mixed The amount of use of the above-mentioned ester-based plasticizer or mineral oil is based on 100 parts by weight of the tree. The composition is generally 0 to 5 wt%, preferably 0.05 to 2 wt%, and the organic polysiloxane The amount of alkane used is generally from 0 to 0.5% by weight. It is better to print the amount% printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 〇 [Physical property test] 1. Transparency (haze) · • Inject the resin composition into a 3mm thick test piece , And measure transparency according to ASTM D-1003 standard, the higher the Haze value, the worse the transparency. 2. Transmittance: according to ASTM-1003 test thickness ____% 17 pages This paper size applies to China Standard (CNS) A4 size (210x7 ^ cent)-printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 506973 Λ7 B7 V. Description of the invention (16) 3mm test piece, the unit is expressed in%. III. Processability (Spiral flow): The transparent styrene resin composition was molded in a Toshiba ISIOOEN injection molding machine at a cylinder temperature of 220 ° C, a mold temperature of 60 ° C, and an injection pressure of 600 kg / cm2, and was formed using a swirl mold (2mmt), and the flow length was evaluated. Flowability. 4. Melt index (MI): measured by ASTM D-1238 method. 5. Pollution of processing molds: After continuously molding 50 molds at 280 ° C, observe the pollutants on the molded products. Impact: ◎: indicates There is no pollution. △: indicates that the mold is slightly polluted. X: indicates that the mold is seriously polluted. 6. The content of the low molecular weight polymer (wt%) in the dichloromethane-soluble molecular weight of the styrene resin is less than 350. The styrene resin composition was dissolved in a dichloromethane solvent and separated by a telecentric centrifuge. The upper soluble fraction was taken and analyzed by a gas chromatography-mass spectrometer (GC-MASS). Mass spectrometer locates low-molecular-weight polymers with molecular weights below 350, such as terpolymers or dimers, and uses the standard area conversion of styrene; the above-mentioned low-molecular-weight polymers are, for example: AMS, MMS, AS, MSS, SSS, MS Etc., where A is acrylonitrile monomer, M is methyl (meth) acrylate monomer, S is styrene monomer, and the gas phase analyzer is Hewlett Packard Company No. 5890A. [Example] 丨 Implementation __ page 18 ____ This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) (please read the precautions on the back before filling this page), 11 lines' Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 506973 Λ7 B7 V. Description of the Invention (Π) Using a continuous polymerization device composed of four serially connected fully-mixed reaction tanks with a capacity of 40 liters to produce transparent resin components 8.4 parts by weight of a rubbery copolymer (styrene / butadiene content = 25/75% by weight, 1,2-vinyl content = 15.4%, Mooney viscosity 45 increasing block copolymer), and 23.4 weight by styrene Parts, 38.2 parts by weight of methyl methacrylate, 30 parts by weight of ethylbenzene, 0.08 parts by weight of dodecyl mercaptan, 0.045 parts by weight of pentaerythritol tetrastearate, and dibenzoyl peroxide 0.08 A part by weight is formed into a feed solution, which is continuously supplied to the reaction tank at a flow rate of 35 kg / hr using a pump for polymerization. The temperature of the first reaction tank is 109 ° C, the temperature of the second reaction tank is 114 ° C, and the third The temperature of the reaction tank was 130 ° C. The fourth reaction The temperature is 140 ° C, total polymerization conversion rate of 60%. After the polymerization, the reaction tank was continuously supplied to the devolatilization device through the polymerization solution, and the vacuum degree of devolatilization was controlled to 200 Torr. The volatile substances such as unreacted monomers and organic solvents were separated, and then the resin was extruded through an extruder. Pellets. The continuous phase of the composition contains 36 parts by weight of a styrene structural monomer and 64 parts by weight of methyl methacrylate. The pentaerythritol tetrastearate content of the transparent styrene resin composition is 0.1 part by weight (based on 100 parts by weight). Parts of transparent styrene resin), the average particle size of the dispersed phase rubber particles is 0.42 μm, and the content of low-molecular-weight polymers with a molecular weight of less than 350 in the dichloropyrene solubles accounts for 0.62% by weight of the total solubles. . Example 2 丨 A continuous polymerization device composed of four serially connected complete mixing reaction tanks containing 40 liters was used to manufacture a transparent stupid vinyl resin composition. 8.4 parts by weight of a rubbery copolymer (styrene / butylene) Second dilute content = 25/75% by weight, ______ page 19 ^ Paper size applies Chinese National Standard (CNS) Α4 specifications (21〇 ---- (Please read the precautions on the back before filling this page), 1T line · Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 506973 A7 _____ B7 V. Description of the invention (18) 1,2-vinyl content = 15.4%, Mooney viscosity 45 increasing block copolymer), and stupid ethylene 23.4 weight Parts, 38 parts by weight of methyl methacrylate, 30 parts by weight of ethylbenzene, 0.09 parts by weight of dodecyl mercaptan, 0.14 parts by weight of pentaerythritol tetrastearate, and dibenzoyl peroxide 009 A part by weight is formed into a feed solution, which is continuously supplied to the reaction tank at a flow rate of 35 kg / hr using a pump to perform polymerization. The temperature in the first reaction tank is ，, the temperature in the second reaction tank is 107 ° C, and the third The temperature of the reaction tank was 122 ° C. The temperature of the fourth reaction tank The degree is 132 C, and the total polymerization conversion rate is 60%. After polymerization, the polymerization solution is continuously supplied to the devolatilization device from the polymerization solution, and the vacuum degree of devolatilization is controlled to 130 Torr. Unreacted monomers and organic solvents, etc. The volatile matter is separated, and the resin pellets are pelletized by an extruder. The continuous phase of the composition contains 36 parts by weight of a styrene structural monomer and 64 parts by weight of methyl methacrylate, and pentaerythritol of a transparent styrene resin composition. Tetrastearate content is 0.3 parts by weight (based on 100 parts by weight of transparent styrene resin), the weight average particle size of the dispersed phase rubber particles is 0.41, and the molecular weight in the dichloromethane soluble fraction is less than The content of low molecular weight polymer of 350% accounts for 0.43% by weight of the total solubles. Bundle Example 3 | Using a continuous polymerization device composed of four series-connected reaction tanks with a total mixing capacity of 40 liters to produce transparent styrene resin Composition, 8.4 parts by weight of a rubbery copolymer (styrene / butadiene content = 25/75% by weight, 1,2-vinyl content == 15.4%, Mooney viscosity 45 increasing block copolymer), With styrene 2 2.8 parts by weight, 37.0 parts by weight of methyl methacrylate, 1-8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, and dodecyl mercaptan 0φ1 by weight—r —___ page 20 Standard (CNS) Α4 specification (210x297 public camera) I " " (Please read the precautions on the back before filling this page)

、 1T _line · —Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 506973 Λ7 ----- ___ ^ R7 V. Description of the invention (19) Known, pentaerythritol tetrastearate 0.32 parts by weight, and Dibenzyl oxide was formed into a feed solution by weight, and was continuously supplied to the reaction tank at a flow rate of 35 kg / hr using a pump for polymerization. The temperature of the first reaction tank was 102, and the second reaction tank The temperature was 10 ° C, the temperature in the third reaction tank was 117t, and the temperature in the fourth reaction tank was 127t :, the total polymerization conversion rate was 60%. After the polymerization, the reaction tank was continuously supplied to the devolatilization device through the polymerization solution, and the vacuum degree of devolatilization was controlled to 80 T0rr. The volatile substances such as unreacted monomers and organic solvents were separated, and then the resin pellets were extruded through an extruder. Into. The continuous phase of the composition contains 34 parts by weight of styrene structural monomer, 63 parts by weight of methyl methacrylate, 3 parts by weight of acrylonitrile, and the pentaerythritol tetrastearate content of the transparent styrene resin composition is 〇7. Parts by weight (based on 100 parts by weight of transparent styrene resin), the weight average particle size of the dispersed phase rubber particles is 0.35 μm, and the content of the low molecular weight polymer in the dioxane-soluble fraction is less than 35. It is 0.22% by weight of the total solubles. Example 4 丨 A continuous styrenic resin composition was manufactured using four continuous polymerization devices composed of four fully-mixed reaction tanks with a capacity of 40 liters in series, and 8.4 parts by weight of a rubbery copolymer (styrene / butadiene content = 25/75% by weight, 1,2-vinyl content = 15.4%, MOONY viscosity "increasing block copolymer", with 22.8 parts by weight of styrene and 37% by weight of methacrylate , 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0 parts by weight of dodecanyl mercaptan, 0.91 parts by weight of pentaerythritol tetrastearate, and 0.1 parts by weight of diphenyl peroxide. The feed solution was continuously supplied to the reaction tank at a flow rate of 35 kg / hr using a pump for polymerization. The temperature of the first reaction tank was ι〇2 ^ -7 ------ ^ 21 pages Noodles (CNS) Α4 specifications (2Λ〇7297 ^ Υ ~ (Please read the precautions on the back before filling in this page)

Line 1T ·! Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Λ7, ^, ___ B7 A, Description of Invention (20) —— The temperature of the second reaction tank is 106 ° C, and the temperature of the third reaction tank is U7t: The temperature of the fourth reaction tank is 127 ° C, and the total polymerization conversion rate is 60%. After the polymerization, the reaction tank was continuously supplied to the devolatilization device through the polymerization solution, and the vacuum degree of devolatilization was controlled at 80 Torr. The volatile substances such as unreacted monomers and organic solvents were separated, and then the resin pellets were extruded through an extruder. Into. The continuous phase of the composition contains 34 parts by weight of a styrene structural monomer, 63 parts by weight of methyl methacrylate, and 3 parts by weight of acrylonitrile. The pentaerythritol tetrastearate content of the transparent styrene resin composition is 200% by weight. Parts (based on 100% transparent styrene resin), the weight average particle size of the dispersed phase rubber particles is 0.35 μm, and the content of low-molecular-weight polymers with a molecular weight of less than 35 in the dichloromethane solubles accounts for all Soluble content was 0.21% by weight. fExample 5 丨 A continuous styrenic resin composition was produced by using a continuous polymerization device composed of four series-connected full-mixing reaction tanks with a capacity of 40 liters, and 8.4 parts by weight of a rubbery copolymer (styrene / butadiene Content = 25/75% by weight, 1,2-vinyl content = 15.4%, Mooney viscosity 45 increasing block copolymer), with 22.8 parts by weight of ethyl acetate, methyl methacrylate " ο weight Parts, 1-8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 1 part by weight of dodecyl mercaptan, and 0.1 parts by weight of dibenzoyl peroxide, forming a feed solution, using a pump at 35 kg / hr. The flow rate was continuously supplied to the reaction tank for polymerization. The temperature in the first reaction tank was 102 ° C, and the temperature in the second reaction tank was 106. ○, the temperature of the third reaction tank was 117 ° C, and the temperature of the fourth reaction tank was 127. 〇, the total polymerization conversion rate is 60%. After the polymerization, the reaction tank is continuously supplied to the devolatilization device through the polymerization solution, and the vacuum degree of devolatilization is controlled to 80 Torr. The unreacted ________ page 22 This paper applies the Chinese National Standard (CNS) A4 specification （21〇x] 97 公 嫠） ~ -------- (Please read the notes on the back before filling this page), ^ τ 506973 Λ7 η ________ B? V. Description of the invention (21) Monomer and organic solvent The volatile materials are separated, and then the resin is pelletized by an extruder. Thereafter, 100 parts by weight of the above stupid vinyl resin was mixed with 0.3 part by weight of 1 part of pentaerythritol tetrastearate, and then the mixture was mixed and extruded through an extruder to pelletize. The continuous phase of the composition contains 34 parts by weight of a styrene structural monomer, 63 parts by weight of methyl methacrylate, and 3 parts by weight of acrylonitrile. The pentaerythritol tetrastearate content of the transparent styrene resin composition is 0.3 parts by weight. (Based on 100 parts by weight of transparent styrene resin), the weight average particle diameter of the dispersed phase rubber particles is 0.33 μm, and the content of the low molecular weight polymer with a molecular weight of less than 35 in the dichloromethane soluble fraction accounts for all the soluble Parts of 0. 24% by weight.啐 Comparative example 1 丨 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Manufactured using a continuous polymerization device composed of four serially connected reaction tanks with a capacity of 40 liters Transparent styrene resin composition, 8.4 parts by weight of rubber-like copolymer (styrene / butadiene content = 25/75% by weight, 1,2-vinyl content = ΐ5.4%, Mooney viscosity 45 gradually increasing Block copolymer) 'with 22.8 parts by weight of styrene, 37.0 parts by weight of methyl methacrylate, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 006 parts by weight of dodecyl mercaptan, and pentaerythritol 0.48 parts by weight of tetrastearate and 0_05 parts by weight of dibenzoylperoxide were fed into a reaction tank at a flow rate of 35 kg / hr: ^ using a pump to perform polymerization. The first reaction tank The temperature is U4C> c, the temperature in the first reaction tank is 120 ° C, the temperature in the third reaction tank is 135 ° C, the temperature in the fourth reaction tank is 155 ° C, and the total polymerization conversion rate is 64%. After polymerization, Continuously supplied from the reaction tank through the polymerization solution to the devolatilizing device to control The vacuum degree of devolatilization is 250T0rr, and the volatility of unreacted monomers and organic solvents will be reduced._ 第 烈 页 The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm). Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 506973 hi —-__________ B7 V. Description of the invention (22) The hair substance is separated, and then the resin gel is pelletized by an extruder. The continuous phase of the composition contains a styrene structural monomer 34 parts by weight, 63 parts by weight of methyl methacrylate, 3 parts by weight of acrylonitrile, and the pentaerythritol tetrastearate content of the transparent styrene resin composition is 10 parts by weight (based on 100 parts by weight of transparent styrene Series resin), the dispersed phase rubber particles have a weight-average particle diameter of 0.45 μm, and the content of the low-molecular-weight polymer in the dichloromethane-soluble fraction of less than 350,000 accounts for 2.2% by weight of the total soluble fraction. Comparative Example 2 丨 A transparent styrenic resin composition was manufactured by using a continuous polymerization device composed of four serially-equipped 40-liter fully-mixed reaction tanks in series, and 8.4 parts by weight of a rubbery copolymer (styrene / butadiene With = 25/75% by weight, 1,2-vinyl content = ΐ5.4%, Mooney viscosity 45 increasing block copolymer), with 22.8 parts by weight of styrene, 37.0 parts by weight of methyl methacrylate, propylene 1.8 parts by weight of nitrile, 30 parts by weight of ethylbenzene, 0.01 parts by weight of dodecyl mercaptan, and 01 parts by weight of dibenzoylperoxide were fed into a feed solution, which was continuously supplied to the pump at a flow rate of 35 kg / hr. Polymerization was performed in the reaction tank. The temperature of the first reaction tank was 102.0, the temperature of the second reaction tank was 106.0, the temperature of the third reaction tank was 117 ° C, and the temperature of the fourth reaction tank. 127t: The total polymerization conversion rate is 60%. After the polymerization, the reaction tank was continuously supplied to the devolatilization device through the polymerization solution, and the vacuum degree of devolatilization was controlled to 80 Torr, and the volatile substances such as unreacted monomers and organic solvents were separated, and then extruded through the extruder. Resin gum is granulated. The continuous phase of the composition contains 34 parts by weight of styrene structural monomer, 63 parts by weight of methyl methacrylate, and 3 parts by weight of acrylonitrile. Based on 100 parts by weight _____________ page 24 This paper applies Chinese national standards ( CNS) Α 槻 格 (21〇 ^ 97 public f (please read the notes on the back before filling out this page), 1T · I-I-5, Λ7 B? Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs It is stated that the weight average particle diameter of the dispersed styrene resin of the transparent styrene resin of (23) is 0.37 μm, and the content of the low-molecular-weight polymer having a molecular weight of less than 35 in the dichloromethane solubles accounts for the total solubles. 0.25% by weight, the obtained resin composition had poor mold release properties during injection molding. Comparative Example 3 | A continuous styrenic resin composition was produced by using a continuous polymerization device composed of four series-connected complete mixing reaction tanks with a capacity of 40 liters. 8.4 parts by weight of a rubbery copolymer (styrene / butadiene content = 25/75% by weight, 1,2-ethylene content = 15.4%, Mooney viscosity 45 increasing block copolymer), With styrene 22.8 weight , 37 parts by weight of methyl methacrylate, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 009 parts by weight of dodecyl mercaptan, and 0.1 part by weight of dibenzoyl peroxide forming feed The solution was continuously supplied to the reaction tank at a flow rate of 35 kg / hr using Pu to polymerize. The temperature in the first reaction tank was 102 ° C, the temperature in the second reaction tank was 106. 0, and the temperature in the second reaction tank was 117. ° C, the temperature of the fourth reaction tank is 127, and the total conversion rate is 60%. After the polymerization, the reaction tank is continuously supplied to the devolatilization device through the polymerization solution, and the vacuum degree of the devolatilization is controlled to 80 Torr. The volatile substances such as the anti-monomer and the organic solvent are separated, and then granulated by the resin of the extruder. After mixing 100 parts by weight of the above styrene resin with 6 parts by weight of the pentaerythritol four hard purpose, The extruder is mixed and extruded and granulated. The continuous phase of the composition contains 34 parts by weight of styrene structural monomer, 63 parts by weight of formic acid, 63 parts by weight, and 3 parts by weight of acetonitrile, and pentaerythritol tetra, a transparent styrene resin composition. The stearic acid content is 60 parts by weight (based on 100 parts) To the amount of A (Please read the precautions on the back before filling this page}

Private paper size applies to Chinese National Standard (CNS) A4 size 3 25 pages (210x297 mm) A7 '—------- B7 V. Description of the invention (24) 1--parts by weight of transparent styrene resin ), The weight average particle diameter of the dispersed phase rubber particles is that the content of the low molecular I polymer having a molecular weight of less than 350 in the dichloromethane-soluble fraction accounts for 0.24% by weight of the total soluble fraction. (Please read the precautions on the back before filling out this page) [^ Example 4 丨 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs using a 40-liter full-mixed reaction tank in the valley. The device was used to make a transparent resin composition, and 8.4 parts by weight of a rubbery copolymer (styrene / butadiene content = 25/75% by weight, 1,2-vinyl content = 15.4%, M_ey Viscosity shirt's increasing block copolymer) 'with 22.8 parts by weight of acetophenone, 37 parts by weight of methyl methacrylate, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, and dodecyl mercaptan. 9 parts by weight and 0.09 parts by weight of dibenzoyl peroxide were used to form a feed solution, which was continuously supplied to the reaction tank at a flow rate of 35 kg / hr using a pump for polymerization. The temperature of the first reaction tank was 103. 〇, the temperature of the second reaction tank is 107t :, the temperature of the second reaction tank is 123 ° C, the temperature of the fourth reaction tank is 131, and the total polymerization conversion rate is 60%. After the polymerization, the reaction tank was continuously supplied to the devolatilization device through the polymerization solution, and the vacuum degree of devolatilization was controlled to be 130 Torr. The volatile substances such as unreacted monomers and organic solvents were separated, and then extruded through the extruder. Resin gum is granulated. 100 parts by weight of the above styrene-based resin and 2 parts by weight of methyl stearate were mixed uniformly, and then granulated through an extruder. The continuous phase of the composition contains 34 parts by weight of a styrene structural monomer, 63 parts by weight of methyl methacrylate, and 3 parts by weight of acrylonitrile. The content of methyl stearate in the transparent styrenic resin composition is 2 mm. Parts by weight (based on 100 parts by weight of transparent styrenic resin), the weight average particle size of the dispersed phase rubber particles is 0.4 μm η ′ Low molecular weight polymerization with a molecular weight of less than 350 in the gas-soluble sintering — page 26 ^ The paper size applies the Chinese National Standard (CNS) A4 specification (2 × 297 mm) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 ------- 一 ~~ _____ B? V. Description of Invention (25) — … — ^ ―'— — ~~ The content of one substance accounts for 0.43% by weight of the total solubles. ^ WWs \ A continuous polymerization device composed of four series-connected complete mixing reaction tanks with a capacity of 40 liters was used to manufacture a transparent stupid vinyl resin composition. 8.4 parts by weight of a rubbery copolymer (styrene / butadiene content = 25/75% by weight, 1,2-vinyl content = 15.4%, an incremental block copolymer of Money viscosity shirt), with 22.8 parts by weight of styrene and 37.0 parts by weight of methyl methacrylate 1, such as 1.8 parts by weight of propylene, 30 parts by weight of ethylbenzene, 008 parts by weight of dodecyl mercaptan, and 0.08 parts by weight of dibenzoylperoxide to form a feed solution, using a pump at 35 kg / The flow rate of hr was continuously supplied to the reaction tank for polymerization, and the temperature of the first reaction tank was 104. (: The temperature of the second reaction tank is 109.0. The temperature of the second reaction tank is 125X :, the temperature of the fourth reaction tank is 135 ° C, and the total polymerization conversion rate is 60%. After the polymerization, the reaction tank The polymerization solution is continuously supplied to the devolatilization device, and the vacuum degree of devolatilization is controlled to 2000 Torr. The volatile substances such as unreacted monomers and organic solvents are separated, and then the resin is pelletized through an extruder. 100 parts by weight of the styrene resin and 2 parts by weight of hard butyl vinegar are mixed and extruded and granulated by an extruder. The continuous phase of the composition contains 34 parts by weight of styrene structural monomer, 63 parts by weight of methyl acrylate, 3 parts by weight of acrylonitrile, and butyl stearate content of the transparent styrene resin composition was 2.0 parts by weight (based on 100 parts by weight of the transparent styrene resin), dispersed The weight average particle size of the phase rubber particles is 0.41 μm, and the content of the low-molecular-weight polymer having a molecular weight of less than 350 in the dichloromethane-soluble fraction accounts for 0.62% by weight of the total soluble fraction. Comparative Example 6 | ___ page 27 This paper size applies to Chinese National Standards (CNS ) A4 size (210X 297 mm) (Please read the notes on the back before filling out this page) Order_line ·· Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 506973 A7 ----------- -______ V. Description of the invention (26) A continuous polymerization device composed of four serially connected complete reaction tanks with a capacity of 40 liters is used to manufacture a transparent styrene resin composition. 8.4 parts by weight of a rubbery copolymer (benzene Ethylene / butadiene content = 25/75% by weight, 1,2-vinyl content = 15.4%, Mooney viscosity 45 increasing block copolymer), and 22.8 parts by weight of ethylene, methyl methacrylate 37.0 parts by weight of ester, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, weight of dodecyl mercaptan, and 0.1 parts by weight of dibenzoyl peroxide were used to form a feed solution, using a pump at 35 kg The flow rate of 1 / hr was continuously supplied to the reaction tank for polymerization. The temperature of the first reaction tank was 102 ° C, the temperature of the second reaction tank was 106 ° C, and the temperature of the third reaction tank was 117T: The temperature of the fourth reaction tank is 127 ° C, and the total polymerization conversion rate is 60%. After the polymerization, the reaction tank passes the polymerization solution. Continue to supply to the devolatilization device, control the vacuum degree of devolatilization to 80 Torr, separate the volatile materials such as unreacted monomers and organic solvents, and then granulate the resin through an extruder. The styrene above 100 parts by weight of resin is mixed with 2 parts by weight of ethylene distearylamine, and the granules are kneaded and extruded through an extruder to form granules. The continuous phase of the composition contains 34 parts by weight of styrene structural monomer and methyl methacrylate. 63 parts by weight of ester, 3 parts by weight of acrylonitrile, ethylene bisstearylamine content of the transparent styrenic resin composition is 2.0 parts by weight (based on 100 parts by weight of the transparent styrenic resin), and dispersed phase rubber The weight-average particle size of the particles is 0.35 μm, and the content of the low-molecular-weight polymer having a molecular weight of less than 35 in the digas methane soluble fraction accounts for 0.2% by weight of the total soluble fraction. A continuous styrenic resin composition is manufactured by using a continuous polymerization device composed of four series of fully mixed reaction tanks with a capacity of 40 liters. The size of this paper applies to Chinese National Standards (CNS). ) ----- *-(Please read the notes on the back before filling this page}

Line 1T printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ^ 06973 A7 _______B7 V. Description of the Invention (27) ~ — 8.4 parts by weight of colloidal copolymer (styrene / butadiene content = 25/75% by weight 1,2-vinyl content = 15.4%, Mooney viscosity 45 increasing block copolymer), with 22.8 parts by weight of stupid ethylene, 37.0 parts by weight of methyl methacrylate, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.91 parts by weight of dodecyl mercaptan, 0.91 parts by weight of white wax oil, and 01 parts by weight of dibenzoyl peroxide were fed into the feed solution continuously using a pump at a flow rate of 35 kg / hr. Polymerization in the reaction tank 'The temperature of the first reaction tank is 10 ° C, the temperature of the second reaction tank is 106 ° C, the temperature of the third reaction tank is ii7cC, and the temperature of the fourth reaction tank is 127 C, The total polymerization conversion was 60%. After the polymerization, the reaction tank was continuously supplied to the devolatilization device through the polymerization solution, and the vacuum degree of devolatilization was controlled to 80 Torr. The volatile substances such as unreacted monomers and organic solvents were separated, and then the resin gum was extruded through an extruder. Granulated. The continuous phase of the composition contains 34 parts by weight of a styrene structural monomer, 63 parts by weight of methyl methacrylate, and 3 parts by weight of acrylonitrile. The content of the white oil of the transparent styrene resin composition is 2.0 parts by weight (based on 100 parts by weight of transparent styrene resin), the weight average particle size of the dispersed phase rubber particles is 0.37 μιη, and the content of the low molecular weight polymer in the dichloromethane soluble fraction is less than 350, accounting for 0.21 of the total soluble fraction. weight%.啐 Comparative Example 8 丨 A continuous styrenic resin composition was manufactured by using a continuous polymerization device composed of four series-connected fully-mixed reaction tanks with a capacity of 40 liters, and 8.4 parts by weight of a rubbery copolymer (styrene / butadiene Content = 25/75% by weight, 1,2-vinyl content = 15.4%, Mooney viscosity 45 increasing block copolymer), with 22.8 parts by weight of styrene, 37.0 parts by weight of methyl methacrylate, Page _____ This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page)

506973 A7 B7 Printed invention description printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (28) ~ 1.8 parts by weight of acrylonitrile, 30 denier of ethylbenzene ^, richet and dodecyl mercaptan 0.1 grave injury, peroxide 70% by weight of benzamidine was cut into a feed solution, and the pump was continuously polymerized at a flow rate of 35 kg / hr using a pump to polymerize the reaction solution in the reaction tank. The temperature was 10%, the temperature of the first reaction tank was 106 ° C, the temperature of the third reaction tank was urc ', the temperature of the fourth reaction tank was hungry, and the total polymerization conversion rate was 6G%. * After the synthesis, the reaction tank is continuously supplied to the devolatilization device through the polymerization solution. The vacuum degree of devolatilization is controlled at ⑽W to separate unreacted monomers and organic solvents such as volatile matter f, and then the resin glue is extruded through an extruder. Granulated. Then, 100 parts by weight of the above styrene-based resin and 2 parts by weight of a polyethylene weir (PE Wax) were mixed uniformly, and then extruded and granulated by an extruder. The continuous phase of the composition contained 34 parts by weight of a styrene structural monomer, 63 parts by weight of methopropionate, 3 parts by weight of fenpropyronitrile, and a polyethylene wax content of the transparent styrenic resin composition is 2.0 parts by weight (based on i 〇〇parts of transparent styrene Resin), the dispersed phase rubber particles have a weight-average particle size of 0.37 μm, and the content of the low-molecular-weight polymer with a molecular weight of less than 350 in the gas-fired soluble fraction accounts for 0.22% by weight of the total soluble fraction. Table 1 shows the comparison of the physical properties of the above Examples 1 to 5 and Comparative Examples 1 to 8. Example 6 丨 Using 100 parts by weight of polystyrene (CHIMEI Corporation POLYREX PG383) and 0.6 parts by weight of pentaerythritol tetrastearate are mixed and extruded and granulated by an extruder, and the methane gas is measured. The content of the low-molecular-weight polymer with a molecular weight of less than 35 in the soluble fraction is 0.65% by weight, the processability (MI) is 3.6, the transparency (Haze) is 1_0%, the transmittance is 90.5%, and the release molding is released. Liang Liang (Please read the precautions on the back before filling this page) -—— ^ ϋ ϋ · ^^ — af ^ —ϋ ml ·. Order page 30 This paper size is applicable to China National Standard (CNS) A4 specifications (210X 297 Published) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Λ 7 s —--------- B7 V. Invention Description (29)… Good. Example 9 丨 Using 100 parts by weight of polystyrene (Chimei p0LYRE pG383) to measure the low molecular weight polymer with a molecular weight of less than 350 in the digassing solution, the content is 0.65% by weight, and the processability (] ^ 1 ) Is 30, transparency (11% is 8%, 'penetration is 90 · 8%, but the release properties of resin injection molding are poor. 100 parts by weight of styrene-acrylonitrile copolymer (Chimei Company KIBISAN PN-117) and 0.5 parts by weight of pentaerythritol tetrastearate were homogenized, and then extruded and granulated by an extruder, and measured the content of low molecular weight polymers with a molecular weight of less than 350 in the dichloromethane solubles. It is 185% by weight, the processability (MI) is 3.4%, the transparency (Haze) is 1.5%, the transmittance is 90.6%, and the release property of injection molding is good. Comparative Example 10 丨 Use of styrene-acrylonitrile 100 parts by weight of the copolymer (KIBISAN PN-117) from Chimei, the content of the low molecular weight polymer having a molecular weight of less than 3500 in the digassine-soluble product was 185% by weight, and the protective property was 3). The transparency (Haze) is 1.4% and the transmittance is 908%, but the release properties of resin injection molding are poor. From the experimental results of Comparative Example 1, it is known that when the content of the low molecular weight polymer with a molecular weight of less than 350 in the dichloromethane-soluble portion of the resin composition is higher than 20 parts by weight, mold contamination occurs during injection molding of the resin. The experimental results of Comparative Example 2 show that when pentaerythritol esters are not added to the resin, the processability of the resin is not satisfactory and the release properties of the resin are poor, and when the resin has been added _________ page 31 This paper applies to China Standard (CNS) A4 specification (21 〇χ 297) (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (30) " One ~ ——, Pentaerythritol esters of one star, mold pollution is easy to occur and transparency is reduced. This can be obtained from the experimental results of Comparative Example 3. Confirmation: According to the experimental results of Comparative Examples 4, 5, and 7, it is known that when methyl stearate, butyl acetate and white wax oil are added to the transparent styrene resin, mold contamination and poor transparency will occur. . It is also known from the experimental results of Comparative Examples 6 and 8 that when ethylene-stearylamine and polyethylene wax are added to the resin, the transparency of the resin is poor. Referring to the embodiments of the present invention, the present invention adds a specific content of pentaerythritol ester compounds to the transparent styrene resin, and controls the specific low molecular weight content of the digasmethane solubles in the resin, which can indeed make the resin composition have Good transparency and processability, and at the same time, mold pollution will not occur during resin molding. Therefore, the present invention is indeed a novel, progressive, and industrially useful resin composition. However, the above description is only a few of the preferred and feasible embodiments of the present invention. For those skilled in the art, modifications or changes made according to the spirit of the present invention should all be included in the scope of patent application in this case. Table 1: Comparison table of physical property test between each example and comparative example of the present invention. (Please read the notes on the back before filling this page)

Claims (1)

506973 8 88 8 ABCD η Patent Application Scope, Amended Patent Scope Application Patent No. 89114834, a transparent styrenic resin composition composed of: < I > 100 parts by weight of transparent styrene Series resins, which are selected from the group consisting of transparent transparent vinyl resins converted from rubber and transparent stupid vinyl resins that do not contain rubber, which do not contain transparent benzene of rubber, and the ratio of fat and fat. The body is composed of 100 to 30% by weight, and 0 to 70% by weight of other copolymerizable monomers. The modified styrene resin of m-rubber refers to a mixture of rubber and transparent styrene resin without rubber. Or, the sample is polymerized with stupid vinyl monomers and other epidemic polymerizable monomers: and < Π > 0. 01 to 5 parts by weight of pentaerythritol ester compounds; 〇 The low molecular weight polymer content of the soluble molecular weight of the dichloromethane compound in the transparent styrene resin is less than 3.5, accounting for 2.0% by weight or less of the total soluble content. According to the transparent styrenic resin composition described in item 1 of the scope of the patent application, the star-rubber modified transparent styrene resin is a transparent styrene resin modified by a diene rubber. 2. The transparent styrene-based resin composition according to item 1 of the scope of the patent application, wherein the rubber-modified transparent styrene-based resin is composed of: a dispersed phase of rubber particles (A ), And a total of 100 parts by weight of monomers, 12 to 70 parts by weight of styrene monomer, 20 to 80 parts by weight of (fluorenyl) acrylate monomer, 0 to 20 parts by weight of acrylonitrile monomer, and others Copolymer formed from copolymerizable monomers of 0 to 40 parts by weight. Page 33 This paper uses the Chinese National Standard (CNS) A4 specification (210 × 297 mm). (Please read the precautions on the back before filling out this page.) 41 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 506973 A8 B8 C8 Consists of continuous phase (B). 4. The transparent styrene-based resin composition according to item 3 of the scope of the patent application, wherein the rubbery copolymer contains 5 to 50% by weight of a styrene-based monomer and 95 to 50% of a diene-based monomer. Copolymer by weight. 5. The transparent styrene-based resin composition according to item 3 of the patent application scope, wherein the rubbery copolymer is a block copolymer. 6. The transparent styrenic resin composition according to item 5 of the patent application scope, wherein the block copolymer is a block copolymer with increasing composition. 7. According to the transparent styrenic resin composition described in item 3 of the scope of the patent application, wherein the weight average particle size of the dispersed phase (A) of the rubber particles is 0.1 to 2 μm 〇8, according to the first scope of the patent application The said transparent styrenic resin composition 'wherein the ester compound of pentaerythritol is formed by the reaction of pentaerythritol and a tymonic acid compound. 9. The transparent styrenic resin composition according to item 1 of the scope of the patent application, wherein the pentaerythritol ester compound may be: pentaerythritol tristearate, pentaerythritol adipate stearate (Pentaerythritol adipate stearate), pentaerythritol succinate stearate, pentaerythritol tetrastearate, pentaerythritol tetrastearate, and pentaerythritol tetralaurate. 10. The transparent styrenic resin composition according to item 1 of the scope of the patent application, wherein the dichloromethane soluble content of the transparent stupid ethylene-based resin is page 34. The paper size applies to Chinese National Standard (CNS) A4 Specifications (210x297 public directors) (Please read the notes on the back before filling out this page) 'Installed · Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 506973 A8 B8 C8 -_____ D8 VI. The molecular weight of the patent application scope is less than 350 The molecular weight polymer content is 1.0% by weight or less of the total solubles. 1 1. The transparent styrenic resin composition according to item 丄 _ in the scope of the patent application, wherein the transparent styrenic resin is selected from one or more polymers; the above polymers may be selected from: polybenzene Ethylene-based polymers, styrene-acrylonitrile-acrylonitrile-based copolymers, styrene- (meth) acrylate-based copolymers, styrene-based substituted maleimide-acrylonitrile-based copolymers, styrene -N-substituted maleimine copolymer, styrene- (meth) acrylate-N-substituted maleimide copolymer, styrene-N-substituted maleimide -Acrylonitrile- (meth) acrylate-based copolymer. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Page 5 3 First Rule I-Paper Standard Home Country A4 cm 7 29