TW322504B - Styrene resin composition having good impact resistance - Google Patents

Abstract

A styrene resin composition comprising: (1) 100 parts by weight of styrene resin (A) which comprises 100 to 10 wt.% of graft copolymer (B) obtained by graft polymerization of 4 to 90 parts by weight (dry weight) of rubber with 96 to 10 parts by weight of copolymerizable monomer mixture comprising styrene monomer, acrylonitrile monomer and optional copolymerizable monomer, and 0 to 10 wt.% of styrene copolymer (C) obtained by polymerizing 45 to 90 parts by weight of styrene monomer, 10 to 50 parts by weight of acrylonitrile monomer and 0 to 40 parts by weight of optional copolymerizable monomer; (2) 0.01 to 2.0 parts by weight of a sulfide-free stereo hindrance phenol antioxidant (D); and (3) 0.01 to 2.0 parts by weight of a sulfide-containing stereo hindrance phenol antioxidant (E); in which the weight ratio of sulfide-free stereo hindrance phenol antioxidant to sulfide-containing stereo hindrance phenol antioxidant is from 0.2 to 4.0, the total amount of dimers or trimers resulting from the styrene monomer and/or acrylonitrile monomer in the styrene resin composition is lower than 25000ppm, and the amount of residual styrene monomer is lower than 200ppm.

Description

Printed by the Consumers ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 322504 A7 B7 V. Description of the invention (/) This invention is like a stupid vinyl strip resin composition, especially one that has good impact resistance, less smoke during processing, and lower Olympic The resin composition is suitable for manufacturing molded products. As is known to those skilled in the art, the rubber waist-shaped graft copolymer can be divided into styrene strip copolymers, and the resulting product is a balance-resistant styrene strip resin composition, which can be Lotus is used in injection molding, extrusion molding, odor molding, blow molding, or thermoforming, etc .; in order to make the stupid vinyl strip resin composition have practical value, it is usually added to the resin for improvement in manufacturing The thermal stability is thin against gasification, and because the resin will generate free radicals and overgassing during processing, the first two components are the main cause of the cracking in the reaction process. Therefore, in the production process of styrene strip resin composition Two kinds of anti-gasification are added to stabilize the free radicals and gasification compounds respectively. Generally speaking, sterically hindered phenol-based anti-chemical agents are mostly used to stabilize free radicals in the polymerization process, and for example, thiodistearic acetyl Di stearyl thio dipropionate (DSTDP) sulfur anti-gasification agent, or tris nonylphenyl phosphite (TNPP) phosphorus strip anti-aeration agent, generally used Come Stabilize the over-gasification, thereby improving the thermal stability of the resin; but according to the literature, the anti-gasification agent of the ether strip has sulfur components, so the use of such anti-gasification agents will cause the production process or the finished product. Heavier Austrian flavor, and the use of phosphoric acid anti-gasification agent will cause the lack of smoke overhang during processing. Therefore, how to have good thermal stability, and at the same time, make the resin have less smoke and low oxygen during processing The taste is a subject that has long been a breakthrough for those who are familiar with this technical field. Love is, the main purpose of the present invention is to provide an impact-resistant, page 03 paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) —l · ------- installed- ----- Order ------ ^ Travel (please read the precautions on the back before filling in this page) S22504 Α7 A 7 B7 5. Description of the invention (2) There is less smoke and low odor during processing, and Styrene strip resin composition with good thermal stability. However, the styrene strip resin composition of the present invention mainly includes: (1) 100 parts of styrene strip resin (A), which consists of: in the presence of 4 ~ 90 parts of rubber (dry weight), and Styrene strip military mules, propylene strips, and copolymerizable monohydrate mixtures filled with 96 to 10 parts by weight of graft copolymers (B) 100 to 10 parts by weight, and made from benzene Ethylene strip single waist 45 ~ 90 replacement parts, propylene bladder single waist 10 ~ 50 replacement parts, and optional styrene-least copolymer obtained by copolymerization of single waist 0 ~ 40 parts by weight (C) 0 ~ 90 reset X composition; (2) 0.01 ~ 2.0 parts by weight of sterically hindered phenolic anti-gasification agent (D) without thioether group; and (3) 0.01 ~ 2.0 parts by weight of thioether group The anti-gasification of sterically hindered phenols (E); Among them, the anti-gasification agent of sterically hindered phenolic strips without thioether groups (D) The weight ratio is 0.2 ~ 4.0; the total content of dimers or trimers formed by the styrene strip single plaque and / or acrylonitrile strip monomer contained in the aforementioned styrene strip resin composition is less than 25000ρρ ·, residual Styrene strips in 2000 ρρ · below. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) The styrene resin (A) of the present invention consists of 100 to 10 MX graft copolymers (B) and 0 ~ 90 weight ΛΧ of styrene strip copolymer (C), the graft copolymer (B) is in the presence of 4 ~ 90 parts by weight of rubber mash, and 96 ~ 10 parts by weight of a mixture of monolean graft polymerization And, among them, the single waist compound is based on the single weight Dong based on 100 weight Dong X, 45 ~ 90 weight X styrene. Page 04 This paper scale uses the Chinese National Standard (CNS) A4 specification (210 X 297 Mm) Printed Α7 Β7 by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (3) Ene Shidan, 10 to 50 weight X propylene W monohydrate, and 0 to 40 heavy Nang X copolymerizable orders The composition of monomers. The above graft copolymer (B) can be prepared by other block, solution, sickle or emulsion polymerization, or by a combination of these polymerizations, such as emulsification-block Or block-suspension polymerization: preferably emulsification polymerization method, block polymerization method and solution polymerization method, especially The chemical polymerization method is preferred: the graft copolymer (B) obtained by emulsification polymerization is preferably provided in the presence of rubber emulsion nipple, together with styrene strips », propylene ffi strips« and copolymerizable military Emulsion obtained by fishy graft polymerization has an average particle size of 0.05 ~ 0.8. The powder is then grafted (B) by coagulation, release, dryness, etc .; the above-mentioned emulsified graft copolymerization The rubber content of the substance is usually 15 ~ 85 heavy Dong X, preferably 45 ~ 80 reset X, and the rubber sperm emulsion can be diene strip rubber sleep emulsion, ethylene-propylene strip rubber emulsion (such as EPDM), acrylic Ester strip rubber emulsions, etc., the aforementioned diene emulsified rubber emulsion contains 100 ~ 60 weight ftX of conjugated diene monohull, and 0 ~ 40 weight ΛΧ of the same homopolymer formed by the copolymer or its copolymer Thing, which can be expressed as follows:

R

I CH. = C-CH = CH »Among them, R can be hydrogen, methyl or amino, etc., not europium and single mole can be styrene, single monomer, propylene strip monomer, (meth) acrylate strip Single insult. The above-mentioned diene-tooth rubber beta emulsion may be polybutadiene, butadiene-styrene copolymer, butadiene-propylene copolymer, butadiene-silver methacrylate copolymer, and isoprene- Butyl acrylate copolymer, etc .; the preparation of the aforementioned rubber emulsion can be directly polymerized to form a weight average particle size of 0. Page 05 This paper size is applicable to China National Standard Rate (CNS) Α4 specifications (210X297 mm). dw (please read the precautions on the back before filling in this page)-* Τ 22504 A7 _B7 printed by the Employee Consumer Cooperative of the Central Escalation Bureau of the Ministry of Economic Affairs V. Invention description (4) Polymers from 05 to 0.8_, or pre-polymerizable After forming a small particle size rubber emulsion with a diameter of 0.05 ~ 0.18, then use the traditional rubber enlargement method to enlarge the small particle size rubber sleeping emulsion of 0.05 ~ 0.18 畑 into a rubber emulsion of 0.2 ~ 0.8π; The rubber hypertrophy method can be a chemical hypertrophy method adding organic acids, metal salts, or a molecular coagulant containing a carboxylic acid group, a mechanically agitating mechanical hypertrophy method, or a freezing hypertrophy method; etc .; It is possible to use, for example, butyl acrylate monomethyl Acrylic copolymer. The graft copolymer (B) (hereinafter referred to as emulsified graft copolymer) obtained by the above-mentioned emulsion polymerization has a unimodal particle size distribution or a bimodal particle size distribution, wherein the average particle size of the unimodal particle size distribution is 0.05 ~ 0.8 / β, and the average particle size of the bimodal particle size distribution is 0.05 ~ 0.18 / «and 0.2 ~ 0.8_. The production method of the graft copolymer (B) obtained by block or solution polymerization preliminarily dissolves diene rubber, ethylene-propylene rubber, etc. in the monomer mixture and the solvent as required by the box. In, the single "mixture includes 45 ~ 90 weight! I; the styrene vinegar monomer, 10 ~ 50 weight! Ϊ propylene bladder monomer and 0 ~ 40 weight X of copolymerizable monomers, then the resulting solution Pumped into the reaction tank and mixed evenly to carry out the graft polymerization reaction. During the reaction, a suitable bond transfer agent such as tertiary-dodecyl saccharomyces can be added to control the molecular weight of the polymer. It can be composed of multiple eaves, preferably a kettle-type reaction tank with a powerful stirrer; the solvent used can be toluene, xylene, ethylbenzene, methyl-ethyl sulfonate, ethyl acetic acid, etc. The above-mentioned diene rubber is preferably obtained by anionic polymerization, for example: butadiene rubber, isoprene rubber, chloroprene rubber, butadiene-acrylonitrile rubber, butadiene -Styrene mash, etc., of which butadiene rubber Page 06 This paper size is applicable to China National Standard (CNS) Α4 specification (210X297mm) ------- r --- Λ'installation-- (please Read the precautions on the back before filling out this page)

X Duo Printing Package A7 of the Ministry of Economic Affairs Central Bureau of Standards for Consumer Consumption, ^ ~ _B7_ V. Explain (5 ") The content of Hi-Cis and low cis (Lo * -Cis) etc. • • In the high-cis rubber, the typical weight composition of the Cis / Vinyl is 94 ~ 98JK / 1 ~ 5X, and the rest is the Trans structure, and the Mooney viscosity is 20 ~ 120 The molecular weight range is preferably 100,000 ~ 800,000; for low cis rubber, the typical weight composition of cis / vinyl is 20 ~ 40X / 1 ~ 20X, and the rest is trans structure, and its Mooney viscosity is 20 ~ 120. ; The styrene / butadiene copolymerization suitable for the present invention is false, and its polymerization type can be two-stage (di-block) copolymerization, three-stage (tri-block) copolymerization, random copolymerization (rand 〇) or star type copolymer (star type); the above styrene / butadiene copolymer rubber styrene / butadiene weight ratio Fan Teng preferably 5/95 to 80/20, molecular weight range Preferably, it is 50,000 to 600,000; in the block-shaped or solution-grafted copolymer of the present invention, suitable rubber knots are preferably butadiene rubber and styrene / butadiene rubber. The graft copolymer (B) (block or solution graft copolymer) obtained by polymerization by the block or solution polymerization method has an average rubber particle size of generally 0.6 to 10 μm, preferably 1.0 ~ 7.0%, the rubber content of the aforementioned block or solution graft copolymer (B) is usually 4 to 25 weight X, and 4 to 15 heavier than the MX. The graft copolymer (B) of the present invention can be said to be different In addition to the emulsified graft copolymer or block (or solution) graft copolymer before use, the two can also be used together to form a bimodal or trimodal distribution: Bimodal distribution such as: (1) Average particle size 0.2 ~ 0.8 body (emulsion), average particle weight 0.6 ~ 10 male (block or solution) :. or page 07 This paper size is applicable to China National Standard (CNS) A4 specification (2 丨 0 X 297 mm ) --- * ---.---- installed ------ booked ------ ^ travel (please read the notes on the back before filling this page) 322504 Α7 Β7 Central Bureau of Standards, Ministry of Economic Affairs Printed by Employee Consumer Cooperative V. Description of the invention () (2) Average particle size 0.05 ~ 0.18 / «(emulsification), average particle size 0.6 ~ 10 Qing (block or solution) 〇Trimodal distribution such as: average particle size 0.05 ~ 0.15 Township (emulsified), average particle size 0.17 ~ 0.8 stretched (emulsified), average particle size 0.25 ~ 7.0 (block or solution). The method for measuring the average particle size of the aforementioned rubber sleeping particles, you take four gas After osmium (OsO *) dyed the resin, the photograph was taken with a penetrating dazzle mirror, and the particle size of the acorn disperse particles photographed in phase M was taken to be about 1000, and the particle size was determined by the following formula The average particle size of Dehong Dong: The average weight of rubber waist weight = Σ η 1 D, 3 ni is the diameter of the rubber particle! ), The number of rubber mash particles The styrene strip military mule used in the present invention may be: styrene, α-methyl styrene, p-cyanobenzene, p-tert-butyl styrene, p-methyl Styrene, t-cyanostyrene, m-chlorostyrene, 2,5-dichlorostyrene, 3,4-dicyanostyrene, 2,4,6-tribromostyrene, and 2,5-dichlorobenzene Bromostyrene, etc. Among them, styrene or α-methylstyrene is preferred. The propylene bladder monomers used in the present invention may be: propylene 丨 II, α-methacrylic 丨 II, etc., among which propylene eye is preferred; the copolymerizable monomer used in the graft copolymer (B) of the present invention Fishy can be obtained from (meth) acrylate monobasic, malealimide monobasic, methacrylic acid, acrylic acid, anhydrous maleic acid and glyoxylic acid methacrylate, etc .; among them, (meth) acrylic acid Ester strips can be: methyl methacrylate, ethyl methacrylate, propyl methacrylate Page 08 This paper size is applicable to China National Standard {CNS > Α4 specification (2 丨 0X297mm> (please Read the precautions on the back first and then fill out this page) • Binding-Order A7 B7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Instructions (7), butyl methacrylate, benzyl methacrylate, methyl Acrylic acid, methacrylic acid, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dimethylamino ethyl methacrylate, methyl acrylate, acrylic acid Butyl ester, etc., of which methyl methacrylate, propylene Butyl acid esters are preferred. The maleic acid imine pad can be: maleimide, H-methylmaleimide, N-isopropylmaleimide, H-butylmaleimide Sleeping imine, H-hexylmaleimide, H-octylmaleimide, H-dodecylmaleimide, N-chenhexylmaleimide, N-phenylmaleimide Laimide, N-2,3-tolylmaleimide, N_2,4-tolylmaleimide, H-2,3-ethylphenylmaleimide, N-2, 4 -ethylphenylmaleimide, N-2,3-butylphenylmaleimide, N-2,4-butylphenylmaleimide, N-2,6-tolylimide Laimide, N-2,3-cyanophenylmaleimide, N-2,4-cyanobenylmaleimide, N-2,3-bromophenylmaleimide, Η -2,4-Bromophenylmaleimide, etc., among which N-phenylmaleimide is the best. The styrene strip copolymer (C) used in the present invention is pseudo 90 ~ 45 parts by weight of styrene strip monomers, 10 ~ 50 parts by weight of propylene ||| Strip monomers, and other copolymerizable monomers, if necessary, ranging from 40 to 40 parts by weight: from the above styrene strips Hip, C The acrylonitrile strip monomer K and the copolymerizable monomer are the same as those exemplified in the graft copolymer (B); the styrene strip copolymer (C) can also be prepared by block, solution, suspension or emulsion polymerization , But block and solution polymerization methods are preferred. Its weight average molecular weight ranges from 60,000 to 400,000 蔺, and the number average molecular weight is between 50,000 and 200,000. When page 09 (please read the precautions on the back before filling this page ) .Package. The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297mm). The Central Standards Bureau of the Ministry of Economic Affairs Employee Consumption Cooperation Duprint A7 —___ V. Invention Description (s) When the molecular weight is too far, it will lead to processing It is not easy, and if the molecular weight is too low, the impact resistance of the resin is not good. The sterically hindered phenolic strip anti-gasification agent (D) in the styrene strip resin composition of the present invention does not contain a thioether group (or thio group, DiCSC) in the molecular structure , Its weight part is between 0.01 ~ 2.0, especially between 0.05 ~ 1.0; the above compound contains at least the following functional groups:

Rw

R 'where IT is hydrogen, methyl or tertiary butyl, and R "is unsubstituted or substituted alkyl. Examples of such hindered phenolic anti-chemical agents are: 2,6-di-tertiary butyl- 4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-ethylphenol, 2,6-di-tert-butyl-4_ N-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-pentyl-4-methylphenol, 2,4,6-tri-amylpentyl- 4-methylphenol, 2- (α-methylhexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-triphenol Hexylphenol, 2,6-di-tert-butyl-4-methylamino-methyl, 2,6-di-nonyl-4-methyl 0 & 2,6-di-tert-butyl -4-Methylphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-pentyl-hydroquinone, 2,6-diphenyl-4- Octadecyl «phenol, 2,2'-methylenyl-bis (6-tert-butyl-4-methylphenol), 2,2 · -methylenyl · bis (4-ethyl-6- Tributylphenol), tetra [methylen-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 3,5-di-tert-butyl-4 -Methylphenol, 4,4 · -butylene-wen (6-tert-butyl-3-methylphenol), 2,2 · -methanylamine The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the notes on the back before filling in this page). _ Order A7 _B7_ printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. ) Yl-bis [4-methyl-6- (α-methylhexyl) phenol], 2,2 '· methylene-bis (4-methyl-6-cyclohexylphenol), 2,2' -Methylenyl-bis (6-nonyl-4-methylphenol), 2,2 · -methyl »yl-bis (4,6-secondary-tertiary-butylphenol), 2,2 ·- Ethylene bis (4,6-tributylphenol), 2,2'-ethylidene »(6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis [ 6-U-Methylbenzyl) -4-nonylphenol], 2,2'-Methylpyridyl_bis [6- (〇 (, (1-dimethyl ¥ group) -4-nonylgan] , 4,4'-Methylene-bis (2,6-di-third butylphenol), 4,4'-Methylene-bis (6 -third butyl-2-methylphenol), 1,1'-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl Group) -4 -methylphenol, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-t-butyl) -4-hydroxy-2-methylphenyl) -3 -N-dodecylhydrobutane, ethanedioxygen [3,3-bis (3'-tert-butyl-4 · -hydroxyphenyl) butyl ester], bis (3-tert-butyl- 4-hydroxy-5-methylphenyl) dicyclopentane, bis [2- (3'-third butyl-2 * -hydroxy-5'-methylbenzyl) 6-third butyl-4 -Methylphenyl] terephthalate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6 · trimethylbenzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, bis (octadecyl) -3,5-di-tert-butyl-4 -Hydroxybenzyl-phosphate, monoethyl-3,5-di-tert-butyl-4-hydroxybenzyl-phosphate calcium salt, octadecyl-3 (3,5-di-third Butyl-4-hydroxyphenyl) propionate, octadecyl-3 (5-third butyl-3-methyl-3-hydroxyphenyl) propionate, mono-acid or polyoxynol , For example, esters formed by formazan, octadecanoic acid, 1,6-hexamethylene fermentation, neopentyl fermentation, oxalase, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) iso Uric acid ester, Η, ΙΓ-bis (hydroxyethyl) urea 8 amine, and the aforementioned acid sleeping amine, page 11 (please read the notes on the back first (Fill in this page again)-installed. ^ This year's paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm) 322504 Α? Β7 V. Description of invention (Ισ) For example: Ν, Η'- 双 （3, 5-di-tert-butyl-4-hydroxyphenylpropanol) hexamethylene diamine, Ν, Η · -bis (3,5-di-tert-butyl-4-hydroxyphenylpropanol) trimethyl Pyridyldiamine, Η, Ν * -bis (3,5-di-third-butyl-yl-4-hydroxyphenylpropane) hydrazine, triethylenedioxy-bis [3 (3-tributyl- 5-methyl-4-hydroxyphenyl) propionate, etc. The weight part of the anti-chlorination resistance (_) of the sulfide group-containing sterically hindered phenolic strips in the composition of the present invention is between 0.01 and 2.0, particularly preferably between 0.05 and 1.0, which refers to the hindered phenol resistance The structure of the gasification capsule contains a sulfide group (or broken group, that is, CSC) structure, for example: 2,2'-thioxo (6-tert-butyl-4-methylphenol), 2 , 2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-th Tributyl-2-methylphenol), bis (2,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4- Hydroxybenzyl-thiosulfate acetate, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate_, {2-methyl-4,6 -Bis [(octylthio) methyl] -phenol}, 2,2 · -thio-diethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], in which 2,2 · -thio-diethylethyl-bis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] is preferred . Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back and then fill out this page) The styrene strip resin composition of the present invention does not contain sulfide group-containing hindered phenol strip anti-gasification blue (D) The weight-M ratio of the anti-gasification resistance (E) of the sulfur-containing steric hindered phenolic mixture is between 0.2 and 4.0, preferably 0.6 to 3.0; the upper steric hindered phenolic strip containing no thioether group When the resistance of Yihua Thin (D) or sterically hindered phenolic strips containing broken ether groups to anti-gasification two (E) is less than 0.01, the resin ’s anti-gasification property improvement effect cannot meet the actual requirements. If this content is away from 2.0 The paper size that may be added to the resin on page 12 is applicable to the Chinese National Standard (CNS) Α4 specification (210X 297 mm) Printed by the Central Bureau of Economics of the Ministry of Economic Affairs Beigong Consumer Cooperative A7 _B7 〆__ V. Description of invention ( Μ) Precipitated during the process, and then affect the appearance of the finished product: as for the weight ratio of the two is less than 0.2 or greater than 4.0, the resistance to gasification of the resin is not much changed. The stupid vinyl sheet mentioned in the present invention Dimers and / or trimers made from single brewing of propylene and / or propylene, where the dimers include: styrene 1 Acrylic (AS), propylene please-propylene ffi (AA), styrene-styrene (SS), and terpolymers include: acrylonitrile-propylene 丨 propylene please (AAA), styrene-styrene-benzene Ethylene (SSS), propylene, propylene, styrene (AAS), styrene-styrene-acrylonitrile (SSA), etc. In the composition of the present invention, the total dimer or trimer content of the dimer or terpolymer of the styrene pad «and / or acrylonitrile strip« is less than 25000 PP ·, and preferably 20,000 ρρβ or less, the residual styrene strip The single fishy is below 2000 ρρ ·, and preferably 1500 ρρ · or less. When the content is away from the aforementioned fan garden, the mystery of the resin cannot be effectively eliminated. Relative to the styrene strip resin composition of the present invention, other substances can be added and used as needed. Examples of such substances include slippage, ultraviolet absorption of rain, ultraviolet radiation stability, anti-banding agent, «charging_, strengthening_ , Colorant, flame retardant, flame retardant thinner, thermal stabilizer, coupling agent, or other additives, among which: the representative of slip agent such as: calcium stearate, magnesium stearate, lithium stearate, etc. Jin Yi soap, B "ammonium distearate, ammonium distearate, ammonium quinate, butyl stearate, palmitate stearate, polyglycerol monostearate_, n-two Compounds such as dodecanoic acid, stearic acid, polyethylene wax, lignite. Page 13 This paper size is applicable to China National Standard (CNS) A4 (210X297mm) (Please read the notes on the back before filling in this Page) _ 装 'Order 322504 Α7 Β7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of Invention (p) Newtan (nontan vax), Brazilian carnuba wax (Carnuba wax), oil garland; From 0.03 to 5.0% by weight of total ethylene resinRepresentatives in the ultraviolet absorption period are: benzotriazole strip compounds, benzophenone strip compounds, and ultraviolet junction stability »Representative ones are: hindered amine strip compounds: the addition of the foregoing substances ft is relative to the total benzene Vinyl strip resin is usually 0.02 ~ 2.0 reset% of the total amount; in order to improve the weather resistance of the resin, resistance to ultraviolet radiation and discoloration or deterioration of the resin's physical properties, to block the amine strip UV stabilizer / cyanoacrylate UV absorption_ 二It is better to use them in combination, for example, Uvinul 4050 H / Uvinul 3035 of BASF. Typical compounds with «preventatives such as: tertiary amine strip compounds, quaternary ammonium salt compounds, etc., low molecular strip compounds, or polyamidopolyethers, such as 3-cyano_1, 2-cyclopropane polymerization觞 之 颡 shows a permanent polymer strip with «preventive agent. Representatives of filled rain gear such as: acid 0, silica, mica. Typical examples of strengthening agents are: glass braided, mineral ore, various crystal filaments. Coloring »Representatives such as: vaporized titanium, vaporized yoke, solitary black, phthalocyanine dyes. Typical examples of flame retardants or flame retardants are: decabromodiphenyl ether, tetrabromobisphenol A, brominated polystyrene oligomer, brominated gas resin, hexabromododecane, atmosphere Polyalkylene oxide, triphenyl phthalic acid, red phosphorus, oxide, aluminum hydroxide, magnesium hydroxide, zinc acid, triamcinolamine, silicon oil, polytetraethylene powder, expandable graphite, etc. Page 14 (Please read the precautions on the back before filling in this I)-Packed. The standard paper size is applicable to China National Standards (CNS) Α4 specifications (210X297 mm) Printed by the Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperative A7 B7 Five 2. Description of the invention (6) Representatives of thermal stability masks such as: dibutyltin maleate, basic magnesium aluminum hydroxy phosphate, etc. Representative examples of coupling agents include: silane, peptide ester, and ester ester compounds. In order to modify the styrene strip resin composition of the present invention, an additive of a polymer strip can be appropriately used. The upper polymer strip is added with «representative examples such as various acrylic strips for improving the moldability Polymers (called processing aids), or vinyl chloride resins, polymethyl methacrylate, polyacrylic sugar resins, polyamido resins, polybutylene p-peptide, enol stripe polymers, Styrene Shito thermoplasticity, low molecular weight styrene-maleic anhydride copolymerization stork, silicon oil, various compatibilizers, etc. In order to explain the present invention in further detail, the following examples and physical property tests are described below. The components of the following compositions are expressed in parts by weight unless otherwise specified. The following examples illustrate the present invention in detail, but the scope of the present invention is not limited to these examples. < m _ ^ _ Example> (Please read the precautions on the back before filling in this page)-Binding · Binding < Preparation Example I 1 > Preparation of graft copolymer (Β-1): into 1,3- Butadiene 95.0 Propylene Iff 5.0 Potassium persulfate solution (IX) 15.0 Sodium pyrophosphate 3.0 Potassium oleate 1.5 Page 15 This paper size is applicable to China National Standards (CNS) Α4 specifications (210X297 mm) 322504 A7 B7 Central Ministry of Economic Affairs Printed by the Bureau of Standards and Staff Consumer Cooperative V. Description of the invention (| 4) Distilled water 140.0 Third-dodecyl broken yeast 0.2 After 12 hours of reaction at the temperature of 651 according to the above formula, the conversion rate is 94 X and the content of hip fixation is about It is a synthetic rubber and rubber latex with 40X and an average particle size of 0.1 mol in heavy ft. In addition, the following components are used to produce ionomers containing carboxylic acid groups: η ethyl acrylate, acrylic acid, 31-dodecyl thiolease, potassium oleate, dioctyl sulfosuccinic acid, cumene, hydrogenated radon. The formaldehyde and sodium hyposulfite distilled water 85 15 0.32.0 1.0 0.4 0.3 200 The reaction was carried out at 751C for 5 hours according to the above formula, to obtain a carboxyl group-containing ion agglutination blue with a conversion rate of about 95 Si and a pH of 6.0. After that, using 3 parts by weight of the carboxylic acid group-containing ionomer coagulant (dry weight) to enlarge 100 parts of the synthetic rubber waist latex (the dry weight of the obtained fattening rubber hock emulsion pH value is 8.5, weight average The particle size is 0.31 / 01. Finally, the hypertrophy rubber waist emulsion is grafted and reacted with the following formula to produce the graft copolymer (B-1): gg_iiL Fenxisong hypertrophy rubber emulsion emulsion (dry Heavy) 100.0 (Please read the precautions on the back before filling out this page) Page 16 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297mm) Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative A7 B7 V. Description of the invention (丨 5) Styrene-propylene, potassium oleate, tris-dodecyl sulfuric acid, cumene, ferrous hydrogensulfate solution (0.2%), formaldehyde sodium hyposulfite solution (10X), B After the diamine tetraacetic acid solution (0.251) distilled rubber water is obtained by coagulating with calcium chloride (CaCU), the graft copolymer (B-1) required by the present invention can be prepared. Acorn content 75 weight S :, weight average particle size is 0.31%. ≪ Preparation Example I-2 > graft copolymerization Production of (B-2): Synthetic rubber mash latex (weight average particle size of oak mummies 0.1%) prepared in < Preparation Example I -1 > is directly combined with the following table for graft polymerization to prepare Obtained oak-like graft copolymer (B-2). 25.0 20 200 — _I --.---- i ------ 'order ------ (Please read the precautions on the back first (Fill in this page) ^ _iiL Chongsong synthetic rubber latex (0.1 / um) (dry weight) 100. .0 Styrene 32., 4 Propylene II 12. .6 Oleic acid 1. .6 Thirty-one dodecane Thiol 0. 27 cumene pervaporated hydrogen 0. 67 sub-androgen sulfate solution (0.2X) Page 17 This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) A7 __B7_ V. Invention Description (丨 {>) Sodium formate acid solution (10X) 4.0 Ethylenediaminetetraoxalic acid solution (0.25X) 27.0 Steamed eel water 200.0 The emulsified graft emulsion prepared according to the above formula is then chlorinated Calcium (CaCU) is condensed, and the graft copolymer (B-2) required by the present invention can be prepared, and its rubber content is 69 weight "X, weight average particle size is 0.1 code. ≪ Preparation Example 1-3 >; Preparation of graft copolymer (B-3): economic Printed by the Central Consumer Bureau Cooperative Staff Cooperative (please read the precautions on the back before filling in this page). Start with 0.1 parts by weight of tri-dodecyl thiolease and 0.07 parts by weight of gasified benzophenone. Dissolve 6.6 parts by weight of polybutadiene (produced by Asahi Kasei Corporation, trade name 438 (^! 16 5543) in 74.4 parts by weight of styrene, 25.6 parts by weight of propylene bladder and 30 parts by weight of ethylbenzene , To form the feed solution, and then feed the feed solution into the first reactor with a volume of 45 liters. The reaction temperature is 100. The reactor is equipped with a spiral stirrer with a cooling circulation tube, which » The mixing rate is 300 rp ·, and the mixture after the reaction in the first reactor is taken out and sent to the second mule in sequence. The equipment of the second reactor is the same as that of the first reactor, as soon as the conversion of the mixture When the rate reaches 60¾, the mixture is taken out to the devolatilization device to remove unreacted monomers and volatiles, after which it is extruded and granulated, and the graft copolymer (B-3) can be obtained. The weight average particle size of the particles is about 1.1 to 1, and the weight of the rubber is 11 weights; K〇 < [Preparation] 1-1 > Preparation of styrene copolymer (C_l): Mix 70 χ of styrene, 30 χ of propylene and 30 χ of raw materials, and then mix 0.025 wt. The 31st alkyl sulfur fermentation and the volatiles removed by the reaction described below are formed by condensation of the recovered liquid. Page 18 This paper size is applicable to China National Standards (CNS) Α4 specifications (210X297 mm) Central Bureau of Standards, Ministry of Economic Affairs Employee Consumer Cooperative Printed A7 _E_ V. Description of Invention (丨 7) Merged as a feed solution to supply a continuous-type kettle-type reactor equipped with a stirrer with an internal temperature maintained at 145 υ and a capacity of 45 litres, and The ratio of toluene in the reaction solution was kept at 15X, while the polymerization rate was kept at 56X. When the reaction liquid is removed by the devolatilization device, particles of styrene-acrylonitrile copolymer can be obtained; on the other hand, the removed volatile components are condensed by a condenser as a recovery liquid, and mixed with the aforementioned raw materials by scooping The liquid is reused, and by rectifying the amount of tertiary-dodecyl sulfatase, a styrene (styrene-propylene W) copolymer (C _1) with a melt flow index of 3.2 can be prepared. Example 1-2 > Split preparation of styrene strip copolymer (C-2): Mix the raw materials of styrene 70-weight Dong X and acrylonitrile 30-weight Dong 3 !, then add 0.025 weight of ethylene distearate X. The over-gasified benzophenone, the 31st-dodecyl sulfatase, and the volatiles removed by the anti-hybrid described below are condensed and the recovered liquid formed as a bait feed solution is used to supply the internal temperature to be maintained at 108 υ And the capacity of 45 liters of the mine-type kettle reactor with agitator, and the proportion of toluene in the reaction solution was maintained at 15X, and the polymerization rate was maintained at 55¾. After the reaction solution was removed by the devolatilizing device, Styrene-acrylonitrile copolymer particles can be obtained; on the other hand The volatile components removed are condensed by a condenser as a recovery liquid, and the above-mentioned raw material mixed liquid is used again. This method adjusts the reaction speed from the amount of over-vaporized benzophenone sleep, or adjusts the 31st dodecane Based on the amount of alcohol, the styrene strip (styrene-propylene 丨 S) copolymer (C-2) with a melt flow index of 3.0 can be prepared. < Preparation Example 1-3 > Split preparation of styrene strip copolymer (C-3): Page 19 This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) (Please read the notes on the back first (Fill in this page again)

322504 at B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (θ) Mix the raw materials of 70 weight X of styrene and propylene 丨 | 30 weight X, then mix the ethylene distearate 0.025 weight X , The 31st-dodecyl thiol fermentation and the volatiles removed by post-condensation reaction are condensed to form a recovery nipple and used as a feeding liquid to feed into the internal temperature maintained at 155 and the volume of 45 liters with agitator Continuous performance kettle type reactor, and keep the proportion of toluene in the reaction solution at 15S !, and the polymerization rate at 57X. After the volatile components are removed from the reaction solution through the devolatilization device, particles of styrene-propylene copolymer can be obtained; on the other hand, the removed volatile components are condensed by a condenser as the recovery solution and mixed with the aforementioned raw materials If the liquid is reused, the styrene strip (styrene-acrylonitrile) copolymer (C-3) with a melt flow index of 3.35 can be cracked by arranging the placement of the 31st-alkyl alkyl yeast. The physical property test standards of the resin compositions prepared in Examples and Comparative Examples are as follows: 1. The total content of dimers or trimers made of styrene strip monomers and / or acrylonitrile strips: The resin composition Dissolve in acetone, and then use Hewlett Packard Company No. 5890 A gas chromatograph with a flame ion detector to analyze the resin solution. 2. Residual styrene sheet «Inclusion: The resin composition The material was dissolved in acetone, and then the gas solution with a flame ion detector attached to Hewlett Packard Company No. 5890 A was used to analyze the resin solution. 3. Anti-chemical resistance: Page 20 (please read the precautions on the back before filling in this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 _ B7_ V. Description of the invention (丨)) The test composition of the tree composition is 4 inX4 inXl / 8 in (length × width × thickness) by injection molding, and the test Η is placed in an oven of 200 t: After 30 minutes, observe the change of hue (ΔΥΙ). The lower the ΔΥΙ, the better the gasification resistance of the resin composition. 4. Austrian taste: The prepared styrene strip resin composition is extruded through a pair of culm poles and the eaves are extruded, and the taste produced by the chessman is evaluated without evaluation of the gas produced at the chessboard. Three persons (including) The judging panel composed of the above has continuously experienced 1 hour to evaluate whether the taste is acceptable and the comfort of the environment under long-term operation. The gold brewing is consistently rated as "0" when it is acceptable, and "0" when it is still acceptable Ο ”, if one person feels unwell or thinks the taste is not good, it will be evaluated as“ X ”. V. Yan Dong: The test method is roughly the same as that of Aowei, that is, when all people are consistently rated as low smoke, it is recorded as “〇”, followed by w〇, and those with more smoke are recorded as “X w”. < Fen_Jing_m > < Example 1 > Using the graft copolymer (B-1) prepared in Preparation Example 1-1 35-fold Dong X and prepared in Preparation Example I-1 Styrene strips (the weight ratio of styrene / acrylic acid mononatrix is 30/70) copolymer (Cl) 65 parts by weight X composed of 100 parts by weight of styrene resin • 0.4 parts by weight of octadecyl is added -3-(3,5-di-tert-butyl-4-hydroxy-phenyl) -propionate (made by the company: (1 & Shu 0 £ 10 ¥, trade name Irganox-1076 is not included Sterically hindered phenol-based anti-gasification agent with a broken ether group), and 2,2'-Ao-diethylene base of 0.4 parts by weight Page 21 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 Ali) (Please read the notes on the back before filling in the text)

A7 B7 Printed and printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of Invention (Q)-Bis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate (by CIBA Manufactured by GEIGY, the trade name is Irganox-1035 (ether-blocking sterically hindered phenolic strip anti-gasification agent) to form a homogenous melt. • The melt is extruded into strips and cut into Particulate, the total content of dimers or trimers made of styrene scorpions and / or propylene strips in the resin composition is 15000 ppm, and the residual styrene strip monomer content is 1200 ρρ ·, And the composition of the smell, smoke and gasification resistance evaluation, the results are shown in the attached table 1. &lt; Example 2 &gt; Repeat "steps of Example 1, in addition to I "The added amount of ganox-1076 was changed to 0.6 parts by weight, and the added amount of Irganox-1035 was changed to 0.6 parts by weight. The measured physical properties are shown in Table 1. &lt; Example 3 &gt; Repeat Example 1 Step Cuan, in addition to using the styrene strip copolymer (C-2) prepared in Preparation Example 1_2, the resin made from styrene strip monomers and / or acrylonitrile strip monomers The polymer or terpolymer junction content is 8200 pph, and the residual styrene strips are 600 pP1D, and the rest of the physical properties are shown in Table 1. &lt; Example 4 &gt; Repeat the steps of Example 1 «, except this In addition, the addition of Irganox-1076 was changed to 0.6 parts by weight, and the amount of Irganox-1035 was changed to 0.2 parts by weight. The measured physical properties are shown in Table 1. &lt; Example 5 &gt; Repeat Example 1 Step *, In addition, the paper standard of page 22 of Irganox-1076 is applicable to Chinese national standard (CNS & A4 specifications (210X297mm) --- 1 --- ^ ---- J ·, ^ Install ------ Order ------ (Please read the precautions on the back before filling in this page) A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of Invention (屮) Add Dong to 0.3 weight Jt parts, I "ganox-1035 added amount was changed to 0.5 parts by weight, the measured physical properties are shown in Table 1. &lt; Example 6 &gt; Repeat the steps of Example 1, except otherwise Use 38-weight Dong X graft copolymer (B-2) prepared by Split Preparation I-2 and 62-weight X consist of styrene strip copolymer (C-1) prepared by Preparation Example E-1 100 parts by weight of stupid vinyl resin, The total content of dimers or trimers of the styrene-based monomers and / or acrylonitrile strip monomers in the resulting composition is 14400 ppB, and the residual styrene strips are 1200 ppb. Example 7 &gt; Repeat the steps of Example 1 and use the same ingredients and heavy parts of the anti-gasification agent, except for the use of 33 weight! E from the preparation of Examples I 1-2 graft copolymer (B -2) and 30 reset X the graft copolymer (B-3) obtained in Preparation Examples 1-3, and 37 weight X the styrene strip copolymer (C-1) prepared in Preparation Examples 1-1 The composition of 100 parts by weight of styrene resin, and the resulting composition is also measured for the total content of dimers or trimers of styrene strips and / or propylene strips, and residual styrene monocrocies, as well as each The physical property test, the results are shown in Appendix 1. &lt; Example 8 &gt; Repeating the procedure of Example 1 and using the same composition and weight of anti-gasification cocoon, except using 18 times MX of the graft copolymer prepared in Preparation Example I-1 (B-1), 15 weight X graft copolymer (B-2) obtained in Preparation Example I-2, 20 reset X graft copolymer prepared in Preparation Example 1-3 (B-3 ), And 47 weight X of the styrene prepared by Preparation Examples 1-1. Page 23—1 —; ----- Ί 装 ------ 定 ------ Ύ (please Read the precautions on the back and then fill out this page) The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). The Central Government Bureau of Economic Affairs of the Ministry of Economic Affairs and Consumer Cooperation Du 322504 A7 ____B7_ V. Description of invention (2 4 ) 100 parts by weight of styrene resin composed of Shito copolymer (C-1), and the resulting composition is also tested for the absolute content of dimer or trimer of styrene strip single plaque and / or propylene ffi strip single brew , Residual styrene strips and various physical properties, the results are shown in Appendix 1. &lt; Comparative Example 1 &gt; According to the formula in Table 1, after mixing the original and auxiliary materials uniformly, the physical property test and the evaluation of the taste and smoke amount of the product were carried out as in Example 1, and the results are shown in the table- * 〇 <Comparison Example 2 &gt; Repeat Comparative Example 1, but do not add phenyl trisphosphonate (TNPP), but instead add 1 layer of thiodistearic dipropionate (DSTDP), the results are also shown in Schedule I. &lt; Comparative Example 3 &gt; The operating conditions are the same as those in Example 1, except that the styrene-toluene copolymer (C-3) prepared in Split Preparation Examples I to 3 is used instead of benzene in the composition The total content of dimers and trimers of ethylene shit monomers and / or acrylonitrile shit monomers is 31,000 ppid, and the residual styrene strip content is 2500 ppb. The results are shown in Table 1. &lt; Comparative Example 4 &gt; The procedure of Example 1 was repeated, except that the addition of Irganox-1076 was changed to 0.8 parts by weight and the addition of Irganox-1035 was changed to 0.08 parts by weight. In Schedule 1. &lt; Comparative Example 5 &gt; Step K of Example 1 was repeated, except that page 24 of Irganox-1076—I --- 1 ---- ^ * installed ------ ordered-- ---- η \ (Please read the precautions on the back and then fill out this page) This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 public daughter) 322504 A7 B7 V. Description of invention (2 3) Add device It was changed to 0.08 weight JK and Irganox-1035 was added to 0.8 weight Dong. The measured physical properties are shown in Appendix 1. The test results of Comparative Example 1 show that the addition of TNPP's phosphorous anti-gasification compound to the styrene strip resin composition will increase the smoke volume obviously. As shown in Comparative Example 2, the anti-gas of the styrene strip resin composition If the chemical agent is changed to DSTDP with thioether strips, there will be a clear smell; as shown in Comparative Example 3, when the styrene strip resin composition contains the styrene strip mono and / or the propylene fyi 糸 舣When the content of the dimer and trimer junctions is higher than 25000 ρρ ·, and the residual styrene strips are separated from the waist at 2000 ρρ ·, both the odor and the smoke will be willing to increase; then the results of Comparative Examples 4 and 5 It is shown that when the weight M of sterically hindered phenolic strip anti-gasification agent (D) without sulfur group and sulfur-containing sterically hindered phenolic strip anti-gasification dysentery (E) is less than 0.01 weight "parts, the composition The gasification resistance is slightly worse; in contrast to Examples 1 to 8, the present invention can be obtained with the impact resistance, low smoke during processing, low Austrian smell, and good thermal stability, subject to the limitations of the aforementioned ingredients and the use of Dong Styrene strip resin composition. However, the above are just a few of the preferred and feasible embodiments of the present invention. Anyone who is familiar with this technology and whose modifications or changes are made in accordance with the spirit of the present invention should be included in the scope of the patent application in this case. --- '叫-^ ---- ii Outfit ------ Subscribe ------ ^., Λ (Please read the precautions on the back before filling this page) Employee of Central Bureau of Standards, Ministry of Economic Affairs The paper printed on page 25 of the Consumer Cooperative applies to the Chinese National Standard (CNS) Α4 specification (210Χ297mm)

Claims (1)

L4 5 ο) 2 oo: ί- · 0 ABCD 1 *-Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -----------------------------------; ^ 6. Scope of patent application ⑴ Supplement No. ______—....----——- *-^ · — * W ·-No. 85110730 Application for invention patent ^ Amendment to the patent application application form ^ 〆1. A styrene strip resin composition comprising: (1) 100 parts by weight of styrene resin (A), which is composed of styrene strips in the presence of 4 to 90 parts by weight of rubber (dry weight), Acrylonitrile strip monomer and optionally copolymerizable monomer mixture 96 ~ 10 parts by weight graft copolymer obtained by graft polymerization (B) 100 ~ 10 Weight 3 :, and from styrene strip monomer 45 ~ 90 parts by weight, acrylonitrile strip monomer 10 ~ 50 parts by weight and optional copolymerizable monomer 0 ~ 40 parts by weight of styrene copolymer (C) 0 ~ 90% by weight Composition; (2) 0.01 ~ 2.0 parts by weight of sulfur-free sterically hindered phenolic strip anti-gasification agent (D); and (3) 0.01 ~ 2.0 parts by weight of sulfide-containing sterically hindered phenolic strip antioxidant (E); Among them, steric hindrance without sulfide group Shito anti-gasification agent (D) / sulfide group-containing sterically hindered phenolic strip anti-gasification agent (E) weight ratio of 0.2 to 4.0; the above-mentioned styrene Shito &gt; styrene Shito monomer contained in the resin composition And / or the total content of dimers or trimers formed by acrylonitrile strip monomers is less than 25000 ΡΡΠΠ, and the residual styrene strip monomers are below 2000 ppm. 2. The styrene-based resin composition according to item 1 of the patent application scope, wherein the hindered phenol-based antioxidant (D) containing no ether group is pseudo-selected from octadecyl-3- (3,5- Di-tert-butyl-4-hydroxy-phenyl) -propionate, triethylene glycol-bis [3 (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate, Tetra [Methylene-3- (3,5-Di-tert-Butyl-4-Hydroxybenzene Page 26 This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) ... ......... Π ------: 装 ----- (Please read the precautions on the back before filling in this page) • V-6 Μ 4-ο 522 ABCD Central Standard of Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 6. Scope of patent application ο) Propyl) propionate] methane, 3,5-di-tert-butyl-4-methylphenol, 4,4′-butylene-bis (6- Tert-butyl-3-methylphenol), 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol). 3. According to the styrene strip resin composition described in item 1 of the patent application scope, the sterically hindered phenol strip antioxidant (E) containing a thioether group is 2,2 thio-diethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. F / 4. According to the styrene strip resin composition described in item 1 of the patent application scope, which does not contain sulfur-based The weight ratio of sterically hindered phenolic strip anti-gasification agent (D) / sterically hindered phenol-based anti-gasification agent (E) containing benzene ether group is between 0.6 and 3.0. 5. According to the benzene mentioned in item 1 of the patent application scope Vinyl strip resin composition, in which the total content of dimers or trimers made of styrene strip monomers and / or acrylonitrile sterol is less than 20,000 ρρπι. 6. According to the patent application scope item 1 The styrene resin composition described above, in which the residual styrene strip monomer contained in the composition is 1500 ρρπ or less. 7. The styrene strip resin composition according to item 1 of the patent application scope, which does not contain sulfide The amount of sterically hindered phenolic strip anti-gasification agent (D) and thioether-containing sterically hindered phenolic strip anti-gasification agent (E) is 0.05 ~ 1.0 parts by weight. Page 27 of this page The Zhang scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 gong) -----.............................. One set ... ....... Order ......... Γ (Please read the precautions on the back before filling out this page) Bf: 1. Irsnox-1076 Miscellaneous +> Thistle! 6-3- (3,5- = 1-tear tuTM-4- ^ ®-tear) -21 sleep sleep 2. Irganox-1035 ^ 2,2--SHt-uiN «w-)« 【3- (3,5-u-3Ii [ll: rw-4-ilw- ^ s] 3i®®o 3. TNPP ^ ILl-iwsis ^ iiQ.risnonylphenylpilosphiter 4: .DSTDPi ^ 黎 itu ^ '昆 乱 継 uai®s (Di stearyl thio dipropionate). CT · o 6.. AN Miscellaneous 3i games sc 7.. Δ- &lt;Ι7!; 3 # AIDS step N-KHM53 $ 200rfN &gt; 濂 撖 -B-30ΦLumai ss hoe N &gt; ®s ) €> irr. no A ma Lin Antioxidant (ΔΥΙ) Residual SM of 鱳 residual 鈒 笑 Μ · 舻 U 銀 渻 Upon cone cocoon Zifeng SI 11 Yuncocoon 3) DSTDP THPP Irganox-1076 (D) / Irganox-1035 (E) Irganox-1035 (E) Irganox-1076 (D) Styrene strip copolymer (c) Graft copolymer (B) Miao m 1 * Yi (PP 丨) o 1 CO ο 1 ro ο 1 1—A 09 1 Ca »09 1 ΪΌ cc H- * Η-k CJl ο 〇〇1200 15000 O Office 〇CO tn oo cn Example 1 ro cn 〇〇1220 15300 • —ao os o σ> σ> CXI CO CJl Example 2 14.7 o ο CT &gt; cn ο 8200 H- * o Office o σ &gt; C7I oo tn Example 3 Η- * cn to 〇〇1180 14800 to o to 〇σ &gt; KJ \ CO tn Example 4 ϋl 〇〇1200 15100 o 05 o CJI oo CJI oo cn Ben Shi Example 5 I— * &lt; 〇〇〇1200 14400 o do 〇05 N5 〇〇 Example 6 μ— »do CJl 〇〇1320 16200 H- * o do o do Ca5 CO CO Example 7 1— »Do 〇〇1150 14200 o do o do s BSSS aussss Example 8 17.7 X 〇1420 15600 o do a &gt; cn CO CJl Comparative Example 1 c n 〇X 1380 15500 1— * o σ> tn B ^^^ SBSSSSBBBB Comparative Example 2 CJl CO XX 2500 31000 I— * oo Office 05 cn CO U1 Comparative Example 3 16.5 〇〇1200 15100 s 0.08 o 〇〇σ &gt; C ^ l CO CJ1 Comparative Example 4 Od OO 021250 15300 | 〇1—to 〇〇0.08 | a &gt; cn nr · -'- &quot; ·· CO cn Comparative Example 5 | 0 f