TW297826B - Polystyrene resin composition modified by rubber - Google Patents

Abstract

A styrene resin composition modified by rubber comprising a matrix phase of styrene/acrylic copolymer and a dispersed phase of butadiene rubber particles, in which the styrene/acrylic copolymer is composed ofacrylonitrile monomer and/or methacrylic ester monomer, styrene monomer,and other copolymerizable unsaturated ethylenic monomer which may optionallybe added, and characterized by that the residual amount of the styrenemonomer in the resin composition is bellow 1500 ppm, the residual amount of the butadiene dimer is below 150 ppm, the average diameter of the rubber in the resin composition is 0.08 to 0.35 (muon)m, the number of the rubber particles having a diameter smaller than 0.1 (muon)m is 19.5 to 99% to the total number of the rubber particles, the number of the rubber particles having a diameter of 0.1 to 0.25 (muon)m is 0.5 to 60% to the total number of the rubber particles, and the number of the rubber particles having a diameter greater than 0.25 (muon)m is 0.5 to 80% to the total number of the rubber particles.

Description

A7 B7 Employee consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Du Yince V. Description of the invention (The present invention relates to a rubber-modified styrene resin composition, except that the prepared composition has excellent falling ball impact Resin composition with high strength, high tensile strength, good gloss, and no odor in molded products. As everyone familiar with this technical field knows, styrene strip resin composition is a rubber-like graft copolymer dispersed in styrene strip In the matrix of the copolymer, an impact-resistant resin composition is made. In terms of application, such resin materials used in the housing of home appliances and automobile molded products must have both impact resistance and high gloss, and ABS resin It is a typical representative styrene strip resin composition material that can meet the above requirements, so it has been widely used for many years. However, generally, the higher the impact resistance, the lower the tensile strength and gloss are. The higher the tensile strength and gloss of the resin, the lower the impact resistance; this is due to the impact resistance, tensile strength and gloss of the resin and the rubber in the resin The content is related to the rubber particle size. From previous studies, it can be seen that the more the rubber content in the resin or the larger the rubber particle size, the better the impact resistance; when the rubber content in the resin is lower or the rubber particle size is smaller, The higher the tensile strength and the glossiness, the resin materials with different rubber particle size distributions and the impact resistance, high tensile strength and good gloss resin materials have been studied for a long time. In terms of production, the injection molding industry has recently tended to increase the molding temperature from the standpoint of reducing costs and attaching importance to the appearance of molded products. Generally, styrene resins are molded in the process of high-temperature injection molding or extrusion molding. The product may produce odor. The source of the above odor is generally suspected because the styrene resin is added with sulfur enzyme Uercaptan during the polymerization process). Page 03 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm)- -一 ------. 装 ------ 定 ------ ^ 旅 * (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

This paper scale is applicable to the Chinese National Standard (CNS> A4 specification (210X297mm) A7 B7. V. Description of the invention (2) It is produced by molecular weight regulator, because mercaptan has low volatility and is easy to remain in the resin; in order to improve As mentioned above, US Patent No. 3951932 mentions that tertiary butyl mercaptan is used as molecular weight regulator, and vacuum stripping is used to remove residual mercaptan, which can reduce styrene. Resin processing and odors on molded products, but the improvement effect is not ideal. Obviously in the production of styrene strip resins, the source of odors does not come entirely from the residue of molecular weight regulators. , When manufacturing thermoplastic styrene resin, it is not easy to obtain good falling ball impact strength, high tensile strength, high glossiness, and the shortcomings that can not improve the molded product when it is molded, which will produce odor. A novel resin composition to improve the aforementioned deficiencies. To this end, the object of the present invention is to provide a ball falling impact strength, high tensile strength , High gloss, odorless molded product (refers to no odor or very little odor, the same applies below) rubber modified styrene resin composition. The present invention is to offer: rubber modified The styrene pad resin composition consists of acrylonitrile pad monomer and / or methacrylate pad monomer, styrene pad monomer, and benzene composed of other copolymerizable unsaturated vinyl pad monomer if necessary The matrix phase of the ethylene-propylene-based copolymer and the butadiene-based rubber particles dispersed in the matrix; in the resin composition, the residual amount of styrene-based monomers is less than 1500 ppm, and the residual amount of butadiene dimer Below 150 ppm, the butadiene strip dimer is 4-vinylcyclohexene; and the number average particle diameter of the rubber in the resin composition is 0.08 ~ 0.35%, its ^^^^ 1 it— n ^ ^ ^ 1 (Please read the precautions on the back before filling in this page) --¾ A7 B7 printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs V. In the description of invention ($), rubber particles with a particle diameter below 0.1% account for The total number of rubber particles is 19.5 ~ 99%, and the particle diameter is 0.1 ~ The rubber particles of 0.25% account for 0.5 to 60% of the total number of rubber particles, and the rubber particles with a particle diameter of 0.25 wn or more account for 0.5% to 80% of the total number of rubber particles. The matrix of the styrene resin composition of the present invention is benzene Ethylene-propylene-based copolymer, which is composed of styrene-based monomer 50 ~ 90wtS !, propylene-based monomer and / or methacrylic ester-based monomer, propylene-based monomer 10 ~ 50wt%, and other available The copolymerized monomer is composed of 0 ~ 40wtS !, and its average molecular weight is between 40,000 and 300,000, preferably between 60,000 and 250,000; where: The styrene monomer can be: styrene, α-methylstyrene, α-chlorostyrene, P-third butyl styrene, P-methylstyrene, 〇-cyanostyrene, P-ambient styrene, 2,5-difluorostyrene, 3,4-difluorobenzene Ethylene, 2,4,6-tribromostyrene, and 2,5-dibromostyrene, divinylbenzene, etc., among which styrene or α-methylstyrene is preferred. Acrylonitrile strip monomers can be: acrylic, methacrylic, which is preferably acrylonitrile; (meth) acrylate monomers can be: (meth) methyl acrylate, (meth) acrylic, Ethyl acetate, propyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, hexyl (meth) acrylate, cyclohexane (meth) acrylate, (A. Base) Acrylic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, 7_ (meth) propionic acid-Xiangpropyl-Third methyl gas-based sand burned (7 -methacryl hydroxy-propyl tri-ntethoxy silane), and (meth) methacrylic acid dimethylaminoethyl, etc., among which methyl methacrylate is preferred. Page 05 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) (please read the precautions on the back before filling in this page). Installed.-= ° Employee Consumption Cooperation of Central Falcon Bureau of the Ministry of Economic Affairs Printed A7 B7 V. Description of the invention (4) There is no particular restriction on the use ratio of the above-mentioned acrylic fine monomer and (meth) acrylic acid ester monomer. If emphasis is placed on the impact strength and oil resistance of the resin, acrylic eyes are used. The amount should be large. If the surface hardness and light transmittance of the resin are important, the amount of (meth) acrylate ester monomers, especially methyl methacrylate, should be large, and they should be used separately according to the requirements of physical properties. Co-monomers include maleimide strip monomers, such as: maleimide, N-methylmaleimide, H-isopropylmaleimide, N-butylmaleimide Imine, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide Imine, 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 -Tolylmaleimide, N-2,3-nitrophenylmaleimide, H-2,4-gas phenylmaleimide, 1 &lt; -2,3-bromophenylimide Laimide, 1 &lt; -2,4-bromophenylmaleimide. Other copolymerizable monomers are: (meth) acrylic strip monomers, anhydrous maleic acid, anhydrous methine succinate Acid, anhydrous methyl maleic acid, anhydrous tricarinic acid and non-shaving and carboxylic acid strip compounds and their ester strip monomers, ethylene, propylene, 1-butene, 1-pentene, 4-methyl- 1 Monopentene, ethylene nitride, vinylidene fluoride, ethylene tetrafluoride, ethylene chlorotrifluoride, propylene hexafluoride, butadiene, propylene amine, isobutylene amine, vinyl acetate, ethyl mono Vinyl ether, methyl-vinyl ketone, etc. Butadiene dispersed in a styrene-propylene-based copolymer matrix. Page 06 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in this page). DESCRIPTION OF THE INVENTION (s) A7 B7 The printed particles of the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs are rubber-like graft copolymers. The above-mentioned butadiene rubber is composed of: 1,3-butadiene 100 ~ 50 v »U and Copolymerizable monomers with CHa = C <group 0 ~ 5〇Wt: C; for example, butadiene such as polybutadiene, butadiene-styrene, butadiene-vinyl toluene copolymer An aromatic vinyl compound copolymer, butadiene-acrylic acid copolymer, butadiene-methacrylic acid B cyanine copolymer and the like butadiene-unsaturated slender compound copolymer; butadiene-acrylic acid si copolymer, butadiene-ethyl acrylate copolymer, butadiene-butyl acrylate copolymer, butadiene-2-ethyl acrylate copolymer, butadiene-alkyl acrylate copolymer; butylene Butadiene monomethacrylate copolymers such as diene monomethyl methacrylate copolymers, butadiene monoethyl methacrylate copolymers, etc., and those with a butadiene content of more than 50% by weight Terpolymer. The aforesaid butadiene rubber can be prepared by emulsification polymerization. During the preparation, the monomer can be directly polymerized by emulsification polymerization into a rubber emulsion of 0.05 ~ 0.35. When the particle size of the rubber emulsion is greater than 0.35 / ®, there will be odor The problem that it is not easy to remove arises, and the monomer can be prepared by emulsion polymerization with a small particle size rubber emulsion of 0.05 ~ 0.20 Yang 1, and then the small particle size rubber can be enlarged by the frozen enlargement method or the mechanical enlargement method or the additive method. Into 0.22 ~ 0.35 Qing rubber emulsion for further graft copolymerization. Among them, the additives used in the additive hypertrophy method may be: acidic substances such as acetic anhydride, vaporized hydrogen, sulfuric acid, or: sodium nitride, potassium vapor, calcium nitride, vaporized magnesium, sulfuric acid and other bases Sexual substances, and acid-containing polymer coagulants such as methacrylic acid-acrylate copolymers (eg methacrylic acid-butyl acrylate copolymer). Page 07 · * &gt; * Please read the notes on the back and then fill in the 1ST page) This paper size is applicable to the Chinese National Standard (CNS> A4 specification (210X297 mm) A7 B7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation 5. Description of the invention (b) The preparation of the butadiene rubber emulsion of the present invention can produce the rubber emulsion with the desired particle size distribution by changing the addition method of emulsifier, reaction temperature, reaction rate and monomer conversion rate. It is not necessary to use the hypertrophy method, but in order to reduce the content of the butadiene dimer contained in the butadiene rubber emulsion, the pseudo-butadiene dimer referred to in the present invention refers to 4-vinylcyclohexane 4-vinyl cyclohexene, a rubber made by hypertrophy. Waist emulsion after stripping treatment is better than rubber emulsion without hypertrophy in removing butadiene dimer. Performance: Butadiene and copolymerizable monomers used to polymerize butadiene strips can be used in one-time addition, batchwise or continuous addition methods, in which continuous addition can effectively remove butadiene Ene dimer. _The above rubber-like polymer may For partial crosslinking, the addition amount of the crosslinking agent is 0 ~ relative to the rubber polymer. Suitable crosslinking agents are: divinyl benzene, diallyl maleate, dilute Propyl fumarate (Diallylfumarate), diallyl acetic acid (Diallyl acetate), allyl acrylate (all ylacrylate), tetraethylene glycol dimethyl propionate (tetra ethylene glycol dimeth-acryUte), etc. The rubber content of the above-mentioned butadiene Shito rubber emulsion is not particularly limited, and usually 30 to 90% is the most suitable, and the swelling degree of the rubber with benzene as the solvent is 20 to 60. The rubbery graft The copolymer is composed of butadiene rubber and styrene monomer 50 ~ 90wta; acrylic propylene monomer and / or methacrylate ester monomer 10 ~ 50 wt! K, and other copolymerizable monomers. ~ 40 wtx by graft polymerization, the preparation of graft copolymer is usually in the presence of rubbery polymer

The paper size is applicable to China National Standard (CNS) A4 (210X297mm) (please read the precautions on the back and then fill out this page)-Packing.-= 5 or printed by the Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperative A7 B7 5. Description of the invention (7) Carry out rubber graft polymerization with the monomer mixture, using chemical bonding or grafting of at least one styrene-propylene-based copolymer on the rubber-like polymer; the above monomers and rubber Factors such as the ratio of the polymer, the polymerization conditions, the chemical properties of the rubber-like polymer, the particle size, the rate of monomer addition, the transfer agent and other factors will affect the degree of grafting; the rubber graft copolymer of the present invention The production method may be emulsification polymerization method, emulsification block polymerization method, emulsification suspension polymerization method, etc., among which emulsification polymerization method is preferred. The initiator added in the aforementioned graft polymerization reaction is usually in the range of 0.01 to 5.0 weight χ of the polymerizable monomer, preferably 0.1 to 3.0 weight! "In between; the amount of addition depends on the monomer and the required polymerization reaction, in order to make the graft polymerization reaction easier, the aforementioned initiator can be added incrementally; and the molecular weight of the graft copolymer can be The temperature during the branching reaction can be controlled, or a small amount of conventional molecular weight regulators can be combined, and temperature control and molecular weight regulators can also be combined to control. The above molecular weight regulators can be mercaptans, halides and postenes, which are more specific examples. There are: n-dodecyl mercaptan, tertiary (dodecyl) mercaptan, tetrabromobrominated, Zhao Pinoleene, α-methylstyrene dimer, and 2, 4-diphenyl -4-methyl-1-pentene, etc. In the graft polymerization of the present invention, the monomer mixture can be continuously or incrementally added to the polymerization reaction. Preferably, the initiator is added simultaneously or incrementally; the aforementioned initiator can use various conventional emulsified radical polymerization Reaction initiators, such as peroxy compounds and azo compounds, can be added at one time or continuously or incrementally; suitable peroxide initiators are, for example, alkali metal peroxides , Persulfate, perborate, peracetate, peroxylate, hydrogen peroxide, etc .; in addition, oil-soluble

‘(Please read the notes on the back before filling out this page).

• 1T 1 V. Description of the invention (Α7 Β7 initiator, for example: di-tert-butyl-pe-roxide), benzoyl peroxide, benzoyl peroxide, 10 Laoyl peroxide, oleyl peroxide, cumene hydro-eroxide, tert-butyl hydroperoxide ): In addition, other methods of free radical catalysts can also be used, such as: actinic irradiation. The graft polymerization of the aforementioned rubber emulsion and monomer mixture is mixed under inert gas at 20 ~ 100 y, also It can be pressurized to 〇 ~ 1 OOP. SI G polymerization time usually takes 2 ~ 10 hours, and 4 ~ 9 hours is better. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs &gt; detailed research results of the inventor of this case, usually through rubber At higher molding temperature and molding speed of the modified styrene-shito resin, the monomers of styrene-shito and butadiene dimer are easily released, and the residual styrene-shid contained in the rubber-modified styrene strip resin The gasification rate of the body increases, Simultaneous volatilization of the ethylene dimer has a synergistic effect, and the odor on the injection-molded or molded product should presumably come from this. To obtain the resin composition of the present invention, a good manufacturing method is carried out in an appropriate temperature and vacuum Stripping of the grafted polymer emulsion, or condensing with high-temperature steam, or using high-temperature steam under reduced pressure to reduce part of the residual styrene strip monomer and butadiene dimer, Wash the above-mentioned coagulated graft polymer with high-temperature water and dry it under vacuum. Usually, the moisture content of the dried product is controlled below 3¾. Another preferred method is not vacuum-dried and preferably U or less. ; Gather the condensed graft ^ binding line (please read the precautions on the back before filling in this page). The 10-page paper size is applicable to the China National Falcon (CNS) A4 grid (210X297 mm) Central Standard of the Ministry of Economic Affairs A7 _B7_ printed by the Bureau ’s Consumer Cooperative. V. Invention description (^) After washing with water, the compound is dewatered by a centrifugal dehydrator to a water content of less than 40¾. The extruder is then used to remove the water barrier and benzene is added. The ethylene-propylene-based copolymer is melt-kneaded and extruded. According to the present invention, to obtain a odorless, rubber-modified styrene-based resin composition, the residual styrene-based monomer composition is less than 1500 ppm, and the residual succinyl The olefin dimer is below 150 ρρπι, preferably the styrene strip monomer is below .850 ppm, and the butadiene dimer is below 100 ppro. When the rubber particles in the polymer are small particles, it is easier to reduce the butadiene dimer The amount of the polymer, so in the present invention, the rubber particles dispersed in the matrix are mostly small particles, the particle size distribution of the rubber particles is a particle diameter of 0.1 // ra rubber particles below 19.5 ~ 99% of the total number of rubber particles , Especially 50 ~ number percentage is better; and the rubber particles with a particle diameter of 0.1 ~ 0.25_ account for 0.5 ~ 60 number percentage of the total number of rubber particles, especially 1 ~ 40 number percentage is preferred; particle diameter is more than 0.25% The rubber particles account for 0.5 ~ 80% of the total number of rubber particles, especially 1 ~ 70% is preferred; when the number percentage of these particle size distributions is outside the aforementioned range, the falling ball impact of the resin is strong The degree of balance between gloss and glossiness is not good; the average particle diameter of the rubber digital scene according to the present invention is between 0.08 ~ 0.35_, and preferably 0.09 ~ 0.1. When the average rubber particle size is less than 0.08%, the ball falls The impact strength is not good; on the contrary, when the average rubber particle size exceeds 0.35, the gloss of the molded product is not good, and the tensile strength also becomes poor. Specifically, the number average particle diameter of the rubber mentioned in the present invention is obtained by dyeing the resin composition with four-gasification (〇s〇4), cutting it, and then using a transmission electron microscope (TEM) electron microscope. Electron with a magnification of 50000 times

The size of this paper is applicable to the Chinese National Standard (CNS> A4 specification (210X297mm) — I! (一 · 装 II 定 —— ί · ^ (please read the precautions on the back and then fill out this page) Central Standard of the Ministry of Economic Affairs The bureau employee consumption cooperation Du printed A7 B7 V. Description of the invention (θ) Yan Qijing mirror phase H, calculated by taking rubber particles on the area of 12 cm X 12 cm, the particle size di particle fraction f, algorithm: ( £ ^) / 11'1, the measurement of the particle size of each rubber is based on the particle (maximum diameter length + minimum diameter length) / 2. The particle size distribution of the present invention is to cut the resin K, and take photos by the above method , The phase number of the transmission electron display and withdrawal magnification is 25000 times (rubber particles 2000 bow or more), respectively, to find the number of particles of different particle sizes, the number of particles with a particle diameter below 0.1% is ηι, the particle diameter is 0.1 ~ 〇.25_ the number of particles is ns, the number of particles with a particle diameter of 0.25 / an or more is na, and N = ru + na + ti3, the particle size distribution of 0.1 or less particles is (ru / fOxiOOa ^ U indicates that the same applies hereinafter. The particle diameter distribution of 0.1 ~ 〇.25 / m is (n2 / N) x 100: particle diameter of 0.25 mm or more The distribution is (n3 / N) x 100. The rubber-like graft copolymer used in the present invention has a rubber content of 15 to 80. Reset X, preferably 45 to 75 heavy Dong, and the styrene-propylene group grafted on the rubber The ratio of the bar copolymer is the graft ratio, based on the weight of the rubber in the range of 20 ~ 150 weight, especially 25 ~ 80 weight! K is better; in order to adjust the rubber content of the resin composition of the present invention, it should be properly mixed as needed Styrene-propylene-based strip copolymer. In the mixture of rubber-like graft copolymer and styrene-propylene-based strip copolymer, the proportion of rubber component is 2 ~ 50% by weight, preferably 7 ~ 35%. , Especially 10 ~ 25 weight is better, when the rubber component ratio in the rubber-like graft copolymer is within this range, the mixing ratio of styrene-propylene based copolymer can be 0: «, even if not used Yes. The styrene-propylene-based copolymer that forms the matrix is rubber graft copolymerized

This paper uses the Chinese National Standard (CNS) Α4 specification (210X297mm) II IIII (xi clothing order I Ϊ V, (please read the precautions on the back before filling this page) A7 B7 Central Standards Bureau of the Ministry of Economic Affairs Printed by the Industrial and Consumer Cooperative Society V. Description of the Invention (丨 丨) The ungrafted styrene-propylene-based strip copolymer formed in a free state on the object, and the aforementioned styrene-propylene-based Shito copolymer mixed for adjusting the rubber content. When polymer blending, in order to reduce the residual amount of styrene monomer and butadiene dimer at the same time, a more specific method is to use an extruder with multiple degassing ports, and then decompress the vacuum from the degassing port part. Method to remove residual vinyl aromatic monomer and butadiene dimer, the preferred method is to use an extruder with more than two degassing ports, and increase the vacuum degree to increase the effect of removing volatiles; When extruding and mixing, adding water or n-hexane, n-octane and other volatile organic solvents can strengthen the removal of styrene monomer and butadiene dimer; when water or volatile organic solvents are added, by water or Solvent Hair characteristics, can enhance the escape of the aforementioned volatiles; generally speaking, relative to the resin composition by weight, the amount of water or organic solvent added is 0.1 ~ 15 reset parts, especially 0.5 ~ 10 parts by weight It is better to add the above-mentioned water or organic solvent and other devolatilization aids during resin blending, in the extruder melting and kneading process, from the cylinder feeding end (feeding hopper) of the extruder and the degassing port The injection port, or the injection port between the two degassing ports, is pressed and added, and the extrusion conditions are selected to facilitate the removal of volatiles. In the resin composition of the present invention, in order to reduce the styrene strip monomer and the butadiene dimer The residual amount can be described by the following methods, such as the selection of particle size distribution in the butadiene rubber particle polymerization stage, post-treatment stage, butadiene rubber particle enlargement process during graft polymerization, The dryness of the graft copolymer, the amount of devolatization aid added in the extruder, vacuum desorption

This paper uses the Chinese National Standard (CNS) A4 format (210X297mm) (please read the precautions on the back before filling out this page) • Install. -D-Travel V. Description of Invention (丨 Top) Cost Invention This invention added additives, slip fillers, coupling agents, polymerization reaction gas inhibitors, phosphorus bars in an amount of 0. 8 Yuan (Ethylene Glycol Bis A7 B7 Expected effect. Ming-rubber-modified styrene resin The composition can be other substances as needed, such as: anti-gasification agent, plasticizer, processing aid, ultraviolet absorber, ultraviolet stabilizer, antistatic agent, strengthening agent, colorant, flame retardant, flame retardant rib agent, Thermal stabilizers or other additives, etc. The above additives can be added during, after, before coagulation or during extruding and mixing. Chemical agents are usually suitable for use such as phenolic anti-gasification agent, thioether anti-gasification antioxidant, Chelating agents and other substances; the addition of phenolic strip antioxidants is preferably 005 ~ 2.0% by weight, and the representative ones are as follows: 10. Please read the matters on the back first and then print it by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 3, 5— Double third 4-hydroxyphenyl) propionate, tris [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3, 5-—bis-tert-butyl_4-hydroxyphenyl) propionate], 2-tert-butyl-6_ (3-tert-butyl-2-hydroxyl-6-methylbenzyl) -4 Methyl phenyl acrylate, 2, 2 'monomethylene bis (4-methyl-6-third butylphenol) and 2, 2' monothiobis (4-methyl-6-third butyl Phenol), 2, 2'-thio-diethylene group-bis [3 (3, 5-bis-tert-butyl-4 4-hydroxy-phenyl) propionate], 2, 2, ethylenediamide Amine-bis [ethyl-3- (3,5-bis-third-butyl-4-hydroxy-phenyl) propionate] etc. Thiosulfonate anti-gasification agent is preferably added in an amount of 0.005 to 2.0% by weight. Representative examples include: distearic thiodipropionate, dipalmitothiodipropionate, pentaerythritol One four one (/ 3-dodecyl methyl thiopropionate

Order Page 14 This paper standard applies to China National Standards (CNS) A4 (2 丨 0X297mm) A7 _ ^ _ B7 _ V. Description of invention (β)), dioctadecyl sulfide, etc. Phosphate anti-gasification agent is phosphite strip anti-gasification agent or phosphate ester anti-gasification agent, and its addition amount is preferably from 0.015 to 2.0% by weight. Typical examples are: tris (nonylphenyl) Phosphite, dodecyl phosphite, cyclic neopentane tetrahydro forbidden bis (octadecyl phosphite), 4, 4 'monobutylene bis (3-methyl-6-third Butylphenyl-ditridecyl phosphite), tri (2, 4-third butylphenyl) phosphite, or tetra (2, 4-third butylphenyl) -4, 4 'Bisbiphenyl phosphate, 9,10-dihydro-9-gas-10-phenanthrene-10-oxygen, etc. The chelating agent is preferably added in an amount of 0.001 to 2.0% by weight. Representative examples include dibenzoylmethane, sodium salt of diethylamine tetraacetic acid, and the like. ‘The amount of the aforementioned antioxidant added is usually 0.03 to 2.0% by weight relative to the rubber-modified styrene resin composition. Representatives of the lubricants printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs include: gold stearate soaps such as calcium stearate, magnesium stearate, and lithium stearate; ethylene distearate; Compounds such as fatty acid amide, palmitic acid amide, butyl stearate, palmitic stearate, polypropionate tristearate, n-docosanoic acid, stearic acid, polyethylene wax, Octacosanoic acid wax, Carnuba wax, petroleum flat, etc .; the amount of the slip agent added is usually ◦ · 03 ~ 5 · ◦% by weight relative to the rubber-modified styrene resin composition. In order to improve extrusion moldability and thermoformability, processing aids such as methyl methacrylate can also be added; UV absorbers are typically: benzotriazoline compounds, benzophenone strip compounds, ultraviolet light Representatives of stabilizers include: blocking amine strips

^ ϋ ml * n · m ^^^ 1 — ^ ϋ mm—Λ 'R · n Ί々 &gt; (please read the precautions on the back before filling this page) -5 Printed by Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention: The addition amount of the aforementioned substances is usually 0.02 to 2.0% by weight relative to the rubber-modified styrene resin composition of the present invention. Representative examples of charge preventive agents are: low molecular weight compounds such as tertiary amine and quaternary ammonium salt compounds, or polyamide polyethers, such as 3-nitro-1,2-chloropropane polymer Permanently charged preventive high molecular strip material. Representative fillers include calcium silicate, silica, and mica. Representatives of strengthening agents include: glass following dimension, heave dimension, various crystal filaments (w h i s k e r). Representative colorants include titanium oxide, iron oxide, graphite, and phthalocyanine dyes. . Representatives of flame retardants or flame retardant additives are: decabromodiphenyl ether, tetrabromobisphenol A, brominated polystyrene oligomer, brominated epoxy resin, hexabromocyclododecane, Atmospheric polyethylene, triphenylphosphoric acid, red phosphorus, vaporized antimony, aluminum hydroxide, magnesium hydroxide, zinc borate, melamine, isocyanamide salt, silicon gas powder, polytetrafluoroethylene powder, expanded graphite, etc. . Representatives of thermal stabilizers are: dibutyltin maleate, basic magnesium aluminum hydroxy acid salt, etc .; and the thermal discoloration preventing agent may be a low molecular weight styrene-anhydrous maleic acid copolymer, which is added The amount is 0.1 to 1.0% by weight relative to the rubber-modified styrene pad resin composition of the present invention, usually a total amount. Representative examples of coupling agents include: silane, peptidate and oxalate compounds. In order to improve the styrene resin composition of the present invention, suitable

The size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) -------- H installed ------ ordered ------ (Read the precautions on the back and then fill in This page) Employee consumption cooperation of the Central Sample Bureau of the Ministry of Economic Affairs made A7 B7. 5. Description of the invention (丨 5) When using additives of polymer bars, such as block polymerization method, solution polymerization method, block suspension polymerization method, etc. , That is, it can be produced by methods other than emulsification polymerization, modified styrene strip resin by rubber, such as acrylonitrile-butadiene-styrene resin, rubber other than butadiene rubber such as EPD Μ, butyl acrylate Rubber modified AES resin, AAS resin and other styrene resins, anhydrous maleic acid-styrene copolymer, styrene-maleimide copolymer, maleimide content exceeds 40% by weight! (; Styrene-acrylic acid-anhydrous maleic acid copolymer, styrene-acrylic acid-anhydrous maleic acid copolymer imidized with aniline, bridging rubber without grafting such as acrylonitrile-butadiene rubber, gas Vinyl resin, polymethyl methacrylate, polysulfonate resin, Polyamide resin, polybutylene terephthalate, styrene-based thermoplastic elastomer, various compatibilizers, etc., the amount of use is relative to 100 parts by weight of the rubber-modified styrene-based resin composition of the present invention. 3 to 200 parts by weight. The following examples illustrate the present invention in detail, but the scope of the present invention is not limited to these examples. &Lt; Production Examples &gt; (I -1) Butadiene Shito Rubber Emulsion Production of (A1): Put the following raw materials into a reaction tank equipped with a stirring device, a heating device, and a raw material feed pipe. Fig_iiL 雷 詈 装 butadiene 100.0 Thirteen-dodecyl mercaptan 0 pyrophosphate 3 Page 17 This paper standard uses the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back and then fill in ft? This page). ·,-* 1. 0.3 140.0 93.0 7.0 0.2 3.0 1.5 0.15 140.0 kl B7 V. Description of the invention (...) Potassium oleate potassium persulfate deionized water starts at 45Ό, and as the conversion rate increases, the reaction temperature gradually increases until the reaction reaches 50 hours; The conversion rate of the prepared rubber emulsion is above 90%, and the polymerization is completed After the unreacted butadiene is removed by steam distillation, the solid content in the latex is 41%, the average particle size of the rubber in the emulsion is 0.14_, hereinafter referred to as A1. (1-2) Butadiene rubber Manufacture of emulsion (A2): Put the following raw materials into a reaction tank equipped with a stirring device, a heating device, and a raw material feed pipe. Phosphate potassium oleate potassium persulfate deionized water is fed at 70 l: After the reaction is continued for 12 hours, it can be cooled to reach the end of the reaction; the conversion rate of the rubber emulsion obtained after the reaction is 92% As mentioned above, unreacted butadiene is removed by steam distillation after the end of the polymerization. The solid content in the latex is 40%. The average particle size of the rubber in the emulsion is 0.06 _, hereinafter referred to as A2. Page 1δ The size of this paper uses the Chinese National Standard (CNS) Α4 specification (210X297mm). Ϊ. (J binding ^ '^ (please read the precautions on the back before filling this page) Employee consumption of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative Du Printed ·

A7 V. B7 Description of the invention (丨 7) (1-3) Manufacture of butadiene rubber emulsion (A3): For example, the formulation amount of (1-2) will be 20% of the total monomer amount and 20% of oil The aqueous solution of potassium acid and potassium persulfate was reacted in the manner of simultaneous addition. The remaining 80% of the total monomer amount and 80% of the aqueous solution of potassium oleate and potassium persulfate were added in a continuous manner for 5 hours and proceeded at 6 5 Ό 9 After hours, let it cool to end the reaction. The conversion rate of the rubber emulsion prepared after the reaction is more than 85%. After the polymerization is completed, the unreacted butadiene is removed by steam distillation. The solid content in the latex It is 39%, and the average particle size of the rubber in the emulsion is 0.07 / an, hereinafter referred to as A3. (II) Synthesis of acid group-containing copolymer emulsion with hypertrophy effect: its components are as listed below. _iiL Chongpansong--1 ----- (installed-(please read the notes on the back before filling in this page) Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs η-Acrylic Ethyl Acrylic Acid 312 Alkyl mercaptan potassium oleate dioctyl sulfosuccinate sodium hydroperoxide cumene formaldehyde sodium hyposulfite sodium water 85.0 15 0 200 0 Place the aforementioned components in the polymerization device and polymerize at 70 · Ό It can be prepared in four hours: the conversion rate is more than 98%, the pH value is 6.1, the number average particle size is 0.07_latex. U -1) The manufacture of hypertrophic rubber emulsion (C1): Page 19 Applicable to China National Kneading (CNS) Α4 specifications (2 丨 0X297mm), y9 li, both A7 _B7_ V. Description of invention (π) In the dry weight of butadiene rubber emulsion (Α2) is 100 parts by weight, five It can be prepared by stirring and adding in seconds, and the acid-containing copolymer emulsion (II) with a hypertrophy effect has a dry weight of 1.5 parts by weight, and the inorganic electrolytes Na, S〇4 are continuously searched and mixed for 30 minutes. · A hypertrophic rubber emulsion with a number average particle size of 0.38 mm, hereinafter referred to as C1. (I-2) Manufacture of hypertrophic rubber emulsion (C2): In a dry weight of butadiene rubber emulsion (A2) of 100 parts by weight, it is added with stirring for five seconds and contains an acid containing a hypertrophy effect The dry weight of the base copolymer emulsion (I) is 1.8 parts by weight, and it is mixed with the inorganic electrolyte Na-S0 «, continuous performance ft for 30 minutes, and it can be prepared: an enlarged rubber emulsion with a number average particle size of 0.45%, hereinafter referred to as C2 . U: 3) Manufacture of hypertrophic rubber emulsion (C3): When the dry weight of butadiene rubber emulsion (A3) is 100 parts by weight, the same hypertrophy treatment as (m-2) is adopted to obtain an average number of granules The hypertrophic rubber emulsion of diameter 0.43 township, hereinafter referred to as C3. "Example 1" (1) Manufacture of graft copolymer: Printed by the Beigong Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) In the reactor after replacement with krypton, Add 100 parts by weight (/ u) of butadiene rubber rubber emulsion (/ u) as shown in Schedule 1 and dry weight of chain transfer agent third-dodecyl mercaptan (TDM) 0.2 as shown in Schedule 1 Parts, and 0.32 parts by weight of cumene hydroperoxide, 0.2 parts by weight of sodium formaldehyde sulfoxylate, 2 parts by weight of potassium oleate, 200 parts by weight of water, after adding 70 parts by weight of styrene and 30 parts by weight of acrylonitrile The continuous addition was performed at 60 Ϊ: reaction temperature for the second. Page dm This paper scale is applicable to the Chinese National Standard (CNS) M specifications (210x297 mm) A7 B7 5. Description of the invention (丨 P) After 8.5 hours of graft polymerization, a graft copolymer of 94% conversion rate can be obtained, rubber The particle size distribution and number average particle size are shown in Table 2. (2) Manufacture of resin composition: Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs --- r ------- (Please read the precautions on the back before filling this page) Add 5% sulfuric acid aqueous solution After the above graft copolymer emulsion was stored and stirred at 90t for 10 minutes, the coagulated precipitate slurry was stripped with 112C and 4 kg / cni2 steam for 60 minutes, then dehydrated and washed with 80 1C hot water After drying at 80 ℃ and 120 Torr for 1 hour, the graft copolymer powder was obtained; then the styrene-propylene resin of the aforementioned graft copolymer (the composition weight ratio is: acrylonitrile / styrene = 30 / 70, with a molecular weight of 12,000) and 2,6-di-tert-butyl-4-methylphenol (0.1 lwtS;), tris (nonylphenyl) phosphite with respect to the resin composition of 100 wt! U Ester (p.lwt%), ethylene bis-stearamide (2.0wt%), etc., mixed with the above-mentioned graft copolymer powder to form a mixture with a total rubber content of 19 «t, with German Werner &amp; Pf leiderer ZSK-35 Type dual-axis extruder extruded at 2 4 0 1C, and the vacuum degree of the first degassing port (VI) and the second degassing port (V2) of the extruder were 150 Torr 60Torr, and the injection ports between the inlet and the first degassing port (VI) and between the first and second degassing ports (V1.V2), as shown in Table 3, add the devolatile aid n-hexane The amount added is 2.5 parts by weight and 1.8 parts by weight with respect to 100 parts by weight of the resin composition, respectively. "Examples 2 to 7" The same treatment method is used as in Example 1, except that various graft copolymers or mixtures thereof as shown in Table 2 are used. The name and amount of each graft copolymer are listed in Attached Table 1 is the first support; the subsequent performance of the graft copolymer coagulation slurry is as shown in Attached Table 3, adjusting different stripping, drying and page 21. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 Cli) A7 B7_ _ printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (^) The final resin composition was obtained under the conditions of extruding. "Example 8" (―) Production of graft copolymer: In the reactor after replacement with krypton, 200 parts by weight (dry weight) of the butadiene rubber emulsion (A1) and the hetero transfer agent "_methyl 0.2 parts by weight of styrene dimer, 0.32 parts by weight of tertiary butyl hydrogen peroxide, 0.2 parts by weight of sodium formaldehyde sulfoxylate, 2 parts by weight of potassium oleate, and 200 parts by weight of water were injected into the reactor. 70 parts by weight of ethylene and 30 parts by weight of acrylonitrile are mixed and continuously added, and the graft polymerization reaction is carried out at 60 C for 8.5 hours to obtain a graft copolymer with a conversion rate of 93.6%, and the amount of rubber The average particle size is 0.14 mm, and its particle size distribution is 0.1 _ or less, accounting for 62.4! (;, 0.1 ~ 0.25 / ίπ, accounting for 32.4S ;, 0,25_ or more, accounting for 5.2SC. (Two 5 resin composition manufacturing: will 5% sulfuric acid aqueous solution was added to the above graft copolymer emulsion, and stirred at 90 ° C for 10 minutes to coagulate to precipitate a slurry, which was then dehydrated and washed with water at 40 ° C to obtain a water content of 31.2¾ Graft copolymer powder; then the styrene-acrylonitrile-N-phenylmaleimide copolymer (the composition weight ratio is : Acrylonitrile / styrene / N-phenylmaleimide = 22/70/8, the molecular weight is 108,000) and 2,6-di-tributyl-4 relative to the resin composition at 100 wt% -Methylphenol (0.1 wtX), tris (nonylphenyl) phosphite (O.lwU), ethylene bis-stearamide (2.0 Wt! «), Etc., mixed with the above graft copolymer powder to form a total The mixture with a rubber content of 19 wU was extruded at 24 Ot using a Japanese-made Toshiba TEM-35 type twin-screw extruder. The vacuum degrees of the first and second degassing ports (V1, V2) were 90 Torr. Applicable to China National Pickup Vehicle (CNS &gt; Α4 specification (210Χ297mm> ίίΙίίΙ '; Ι {Please read the notes on the back before filling this page)

J ilcml: ^^ 二. ·-The Ministry of Economic Affairs Central Standards Bureau employee consumption cooperation du printing A7 —__ B7_ i, invention description (Ν) and 20Torr. "Example 9" (―) Production of graft copolymer: In the presence of nitrogen, 200 parts by weight (dry weight) of butadiene strip rubber emulsion (A1), 0.2 parts by weight of bond transfer agent TDM, and third butyl are added 0.32 parts by weight of hydrogen peroxide, 0.2 parts by weight of sodium formaldehyde sulfoxylate, 2 parts by weight of potassium oleate, and 200 parts by weight of water. After addition, 70 parts by weight of styrene and 30 parts by weight of acrylonitrile are mixed and added successively 4 Ο Ό reaction temperature for 8.5 hours of graft polymerization, the conversion rate of 94.2% of the graft copolymer can be obtained, the number average particle size of the rubber particles is 0.14 / m, and the particle size distribution is 62.3 below 0.1 wn, 32.4% from 0.1 to 0.25%, and 5.3¾ from 0.25 to above. (2) Manufacture of resin composition: Add 5% sulfuric acid aqueous solution to the above graft copolymer emulsion, and at 9 Ο After stirring for 10 minutes, the coagulated precipitated slurry was stripped with 1 1 2 &quot; C, 4 kg / cm8 of steam for 90 minutes, then dehydrated and washed with 80 t of water to obtain a water content of 29.8¾ Graft copolymer powder; then styrene-acrylonitrile resin (its composition weight ratio: propylene please / styrene = 30 / 70, molecular weight is 120,000) and 2,6-di-tert-butyl-4-methylphenol (0.1 wt5H), tris (nonylphenyl) phosphite (0.1 wU) relative to the resin composition at 100 wtS: ), Ethylene bis-stearaldamine (2.0wt! U), etc., mixed with the above graft copolymer powder to form a mixture with a total rubber content of 19 v »U, using a Japanese-made Toshiba TEM-35 type biaxial extruder. 2 4 0 ¾ Press down, the vacuum degree of the first and second degassing ports (V1, V2) are 150 respectively. Page 23 This paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm> _---- : ------ ^ ^-(Please read the notes on the back before filling out this page)

Employee of the Central Bureau of the Ministry of Economic Affairs. Printed by the consumer cooperative A7, ______B7 _ V. Description of invention (heart)

Torr and 60 Torr, and at the injection port between the feed port, VI and V2 '(two degassing ports), press in the addition amount of 2.5 parts by weight and 1.8 parts of n-hexane relative to 100 parts by weight of the resin composition Parts by weight. "Example 10" (―) Cracking of the graft copolymer: In the presence of nitrogen, 300 parts by weight (dry weight) of butadiene rubber emulsion (A 1) was added, and the bond transfer agent α-methylstyrene di 0.2 parts by weight of polymer, 0.32 parts by weight of cumene hydroperoxide, 0.2 parts by weight of sodium formaldehyde sulfoxylate, 2 parts by weight of potassium oleate, and 200 parts by weight of water. After addition, 60 parts by weight of styrene, α- 10 parts by weight of methyl styrene, 2 parts by weight of methyl methacrylate and 28 parts by weight of acrylic acid were mixed and added successively, and the graft polymerization reaction was carried out for 8 hours at 6 Ot: to obtain a conversion rate of 9 3.6% graft copolymer, the number average particle size of rubber particles is 0.14wm, and its particle size distribution is less than 0.1% (32.0¾, 0.1 ~ 0.25% accounted for 33.61 0.25 / απ or more accounted for 4. «〇 ( 2. Production of resin composition: Add 5% sulfuric acid aqueous solution to the above graft copolymer emulsion, and stir at 90 ° C for 10 minutes. After coagulation, the slurry is precipitated and stripped with steam of 112Ό, 4kg / cma for 60 minutes After dehydration and washing with hot water at 80 °, the graft copolymer powder with a water content of 29.2¾ is obtained; Ene-α — methylstyrene-acrylonitrile-methyl methacrylate resin (the composition weight ratio is: acrylonitrile / styrene / α —methylstyrene / methyl methacrylate = 28/50/18 / 4. The molecular weight is 132,000) and relative to 100wtS; the resin composition of 2,6-di-tert-butyl-4-methylphenol (0.1, p. 24) The paper standard uses the Chinese National Standard (CNS ) A4 said grid (210X297mm) —: (Please read the precautions on the back before filling in this page)

J A7 _____B7_ V. Description of the invention (Μ) Tris (nonylphenyl) phosphite (0.1 wtx), ethylene bis-stearamide (2.0 wU), etc., mixed with the above graft copolymer powder The formed rubber contains a mixture of 19 »^%, which is extruded at 24 01C with a Japanese-made Tos-hibaTEM-35 type dual-axis extruder. The vacuum degree of the first and second degassing ports (vi, V2) are respectively 120 Torr and 40 Torr. "Comparative Examples 1 to 4" and Ben Shi Example 1 use the same treatment method, the difference is that various graft copolymers or their mixtures as shown in Table 2 are used, and the subsequent treatment of the graft copolymer coagulation slurry is as follows Table 3 adjusts different stripping, drying and extruding conditions to obtain the final resin composition. The resin compositions obtained in the foregoing examples and comparative examples were used as test Η and used to test the physical properties of falling ball impact strength, surface gloss and tensile strength and residual monomers, odor, etc. The results are shown in Table IV. Test methods The impact strength of the falling ball is as follows: A round test plate with a radius of 50 mm and a thickness of 3 μ is injected with an injection molding machine. At a temperature, a 5 kg steel ball hits the center of the test plate to determine the maximum force to break the test plate. The unit is kg / cm. 2. Surface gloss: Injection molding machine is used to inject 50mm (寛) X 90mm (length) X 3 mm (thickness) plate-shaped moldings at 2 8 0 υ molding temperature; ° Measure the average value of the five-component profile with the incident angle, the unit is 3. Tensile strength: Page 25 This paper scale is applicable to the Chinese National Standard (CNS &gt; Α4 specification (2 丨 0 &gt; &lt; 297mm) --- ------ ¾.-: i (Please read the precautions on the back before filling this page)-• -φ

Line A • Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention (called) Tested according to ASTM D-638 method, its unit is kg / cm2. Four: Residues of styrene monomer and 4-vinylcyclohexene: The styrene strip monomer and 4-vinylcyclohexene components mentioned in the present invention are the resin composition dissolved in dimethyl methyl Dimethyl formamide (DMF), and the resin composition solution is then analyzed by Hewl-ettpa-cka "d company No. 5890A gas chromatograph with an ion flame test device. V. Molded product odor Test: The resin composition obtained according to the experiment is obtained by extruding and cutting the pellets to obtain spherical rubber pellets. 150g of the rubber pellets are placed in a sealed glass jar to be cooled. Ten sensuous people open the glass jar to test its odor The degree is determined according to the number of people who are identified as having odors and marked with the following symbols. The number of persons who are identified as having odors is indicated below 2 people ◎ 2-4 people Ο 4-8 people △

More than 8 people X "Conclusion" From the results in Table 4, it can be seen that the rubber-modified styrene resin composition of the present invention has a residual styrene resin monomer content of 1500 ppm or less, and residual 4-vinyl groups. Cyclohexene is below 150 ppm, and adjusting the average particle size and particle size distribution of appropriate rubber particles can have excellent high falling ball impact strength and high tensile strength, and at the same time have good gloss, which can be greatly increased during molding To reduce the forming odor, and obtain the odor-free property. The standard of the paper on page 26 is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) I --- Μ ----- {装-(please Read the precautions on the back before filling this page), ιτ, Λ

A7 B7 V. Description of the invention (a) The molded product; its composition is not only novel, but also has industrial use value, and an application for an invention patent is filed according to law. However, the above is only a preferred and feasible embodiment of the present invention. Anyone who is familiar with this art and who makes modifications or changes in accordance with the spirit of the present invention should be included in the scope of the patent application in this case. --- r ----- (install II (please read the notes on the back before filling in this page)

, 1T Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economics __ p. 27 This paper standard applies to the national government (CNS) from the country (public director)

Claims (1)

A8 B8 C8 D8 VI. Patent application range 0) 1. A rubber-modified styrene resin composition consisting of a matrix phase of styrene-propylene-based strip copolymer and butadiene dispersed in the matrix phase It consists of rubber particles; the above styrene-acryl-based copolymer is composed of acrylonitrile-based monomers and / or methacrylate-based monomers, styrene-based monomers, and other copolymerizable polymers that may be added if necessary. It is composed of a vinyl monomer; and its pending content is: the residual amount of styrene monomer in the resin composition is below 1500 ppm, and the residual amount of butadiene dimer is below 150 ρρπι, this butadiene dimerization The material is vinylcyclohexene; and the average number of rubber particles in the resin composition is 0.08 ~ 0.35, and the rubber particles with a particle diameter of less than 0.1% account for 19.5 ~ 99% of the total number of rubber particles. The rubber particles between 0.1 and 0.25 percent account for 0.5 to 60 percent of the total number of rubber particles, and the rubber particles with a particle diameter of more than 0.25 / an account for 0.5 to 80 percent of the total number of rubber particles. '2. Printed by the rubber-modified styrene Shitoya Central Standards Bureau SW Gongxiaot Cooperative Society as described in item 1 of the patent application scope of the stall .................... ....... Installed ..... (please read the precautions on the back and then fill in this page) thread resin composition; where the rubber particles with particle diameter below 0.1% account for 50 ~ of the total number of rubber particles 98% by number, rubber particles with a particle diameter of 0.1 ~ 0.25 / an account for 1-40% of the total number of rubber particles, and rubber particles with a particle diameter of 0.25_ or more account for 1 ~ 70% of the total number of rubber particles. 3. The rubber-modified styrene-based resin composition according to item 1 of the patent application scope; wherein, the average particle diameter of the rubber number is between 0.09 and 0.14 ium. Page 28 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 Gongluan) V: A8 B8 C8 _D8_ VI. Patent application scope P) 4. Based on the rubber-modified benzene described in item 1 of the patent application scope Ethylene-based resin composition; among them, the residual amount of styrene-based monomer is 850 ppm or less. 5. The rubber-modified styrene resin composition according to item 1 of the patent application scope; wherein the residual amount of 4-vinylcyclohexene is less than 100 ppih. / (Please read the precautions on the back and then fill in frT page) Installation-§1- Printed by the Ministry of Economic Affairs, Central Standards Bureau, Mgongf Cooperative Co., Ltd. Page 29 This paper scale is applicable to China National Standards (CNS) A4 (210X297 Mm) Hun hydrazone: 1. TDM drunken the river — + &quot; reed » 2. a-Methyl Styrene Dimer ^ a--EBlw ^ iNlsu ^^ Monomer conversion rate of graft polymerization u) Linkage ^ Portion of the composition of the mixture of grafting and repolymerization ^ Types of butadiene rubber emulsion graft copolymerization Article number a -Methyl Styrene Dimer H a 2 CD 〇1 〇ro &gt; H- * ο CD ω ΓΟ 〇Γ0 1 &gt; Η- · ο C \ D CD 仁 σι 1 〇ro &gt; ro Q 00 CD Ren DO 1 〇 &gt; CO ο CD CO ① 1 〇ro o Q ai CD IX) 00 o ro 1 oh ~ * QO) CD CO 00 1 〇n ro a CD 〇1 〇10 o 00 a CO number average particle size (Township))% of rubber rubber radial molecular cloth Graft copolymer type mmm Bracelet i〇.25 / an or more 0 · 1 ~ 0.25 Qingi OAm or less 〇Κ-ώ 01 [NJ 32.4 0) DO RenQ 1 — »I—1 M 〇h- * Γ0 〇CNJ σι (J) CO 01 1 G2 j G5 | DO 〇►—» — t \ 3 00 Γ0 Ο OD Ί G3 1 G5 00 〇Γ0 00 22.0 1 -n! U1 DO G3 G6 Ren 〇1— »CO 1— * 1— * 00 〇74.2 1 G 3-丨 CJ1 o Γ0 00 34.5 μ-» CO Ο 01 VO σι G3 G7 CD 〇 »—4 Γ0 Γ0 μ- * CO σ) -j 00 (X) G4 G8 j 〇h- * 01 Γ0 00 CO Ren① VO Q — μ- * C? 〇1— »01 0 ω \ &gt; square kernel (X) Ren square (- * [\ D square | _Λ 01 Γ0 C0 ro A CD ro 1 G2 CO 1 0.075 1 billion square CO Γ0 CD ① C0 5 0 ο @: ν‘ον = ^ ίφΕΕ · Dip ± 3 Lu 1 芑 璐 ::: All poor ^ ¾: All "Zhuang invites Wei to enter for prosperity.歘 都 · 砩 aw 蹓 _ I drag 5 W Μ Β 'Μ Extruder degassing port vacuum degree (Torr) 1 __ _—— J Moisture content of the graft copolymer after drying (%) |! Eypuhan N- Jtf η mm Inlet between V 1 and V 2 and between V 1 V2 (* 1) V 1 (* 1) I—1 00 [\ 3 01 〇1— »01 〇〇b- ^ Μ h—4 00 IX ) Γ0 -nI 〇h-1 00 〇Ο CO ro 1 σι 00 o 〇αι CO 1 H- * 〇0 1-k Γ0 oj 24 0 〇CO 逋 1 | __k 00 00 〇 ~ n) 〇ο CO europium cn t »—1 00 X fO I— * ool—1 CO o ο 0) Europium cn 1 μ-Α CO ro 〇24 0 ο IX) m -n! 1 CO O) 〇S3 Tarsus, K- * rp II —4 00 1— * 00 〇-0 〇ο 〇Ί Europium Γ0 1 00 oh ~ * cn o ο αι Miscellaneous ω 1! ~ 1 CO 〇ω 〇〇ο C0 2j78 ^ 6 Residual 4-vinylcyclohexene (ppdi) Residual styrene strip monomer (ppm) Tensile strength (kg / cm2) ifi sphere drop impact strength (kg · cm) Total rubber content (wt%) Test items Experiment number 〇1 ◎ 1 &gt; 3 μ_ι CD o Η-1 αι 〇Γ0 o CO 01 CO ◎ 〇00 ω CD Η- * Γ0 C0 〇03 IX »〇CO run CO ◎ 01 00 ΓΟ CO CD ι- ^ GO Γ0 〇ο 払 〇① 00 ◎ ① CD ΓΟ CD CD h- »〇〇ο 〇CO σ &gt; Ren CO ◎ C71 Xin ro ① 00 1— * αι 00 01 t \ D o CD) ™ ι ① Ren 〇1— * C0 1— »CD 1— * t— * 0) 〇〇〇〇o CO CO ◎ 〇μ- * CO CD 1—» 01 C0 Ο) 仁 〇CD V-1 -si 〇〇Γ0 〇CO H- * 00 〇〇ω — 〇CD αι ◎ -J 00 f— · CD of— ^ CO 〇ΓΟ σι DO 〇CD ① CO ο 00 1— »CO CD ① Γ0 ΓΟ 00 o CO o X ω Η- * C0 Ren F 00 σ &gt; t— »ζ〇〇l ·-» 〇ο ΓΟ o CO Γ0 00 Ren X Ί h-4 CD o h- »DO CO 〇Ι \ ϊ o CD 0) Ren X 00 DO CD o 1— * CO 〇00 CO o CD 00 [\ 3 ◎ CD Q0 CD CO Γ0 〇U1 O ) o CD χα 益 t vj-f Game 3IIH