TW322489B - Styrene resin composition modified by rubber - Google Patents

Abstract

A styrene resin composition comprising (1) a continuous matrix phase of styrene copolymer (A) matrix obtained by polymerizing styrene monomer, styrene monomer, acrylonitrile monomer, acrylate monomer and other optional copolymerizable monomer, the styrene copolymer (A) matrix comprising 10 to 50 wt.% of acrylonitrile monomer repeating units, 45 to 89.9 wt.% of acrylonitrile monomer repeating units, 0 to 40 wt.% copolymerizable monomer repeating units, and 0.1 to 15 wt.% acrylate monomer repeating units; and (2) 5 to 45 wt.% relative to the styrene resin composition of rubber particles dispersed in the matrix phase, the amount of rubber particles having diameter greater than 0.20 (muon)m is more than 30 wt.% of all rubber particles; the molecular weigh distribution of THF-soluble ingredient of the styrene resin composition as analyzed by gel osmosis chromatography being that (1) those having molecular weight of 1,000 to 40,000 forms 4 to 26 wt.% of those having molecular weight of 1000 to 3,000,000, (2) those having molecular weight of 40,000 to 90,000 forms 18 to 41 wt.% of those having molecular weight of 1,000 to 3,000,000, and (3) those having molecular weight of 90,000 to 200,000 forms more than 28 wt.% of those having molecular weight of 1,000 to 3,000,000.

Description

322489 A7 _B7_ " " X, Invention Description (I) This invention is commonly used in a styrene strip resin composition modified by rubber, especially a kind with good resistance The impact resistance and physical property balance are good, and the styrene strip resin composition suitable for various processing and molding methods is well known to those skilled in the art. The rubber-like graft copolymer is dispersed in the styrene copolymer, The resulting product is an impact-resistant styrene strip resin composition, which must undergo various processing and molding methods (such as primary processing: injection molding, extrusion molding, etc., and secondary processing: vacuum molding, etc.) It can only be made into a molded product; under the gradual emphasis of the processing factory on the ease of processing of the molded product, good physical properties and better shot impact strength, it has developed a good balance of physical properties and is suitable for a wide range of products. Quality styrene strip resin has become a subject to be broken through in this technical field. In order to correct the lack of impact strength of styrenic resin products, in the known technology, like adding more rubber copolymers and modifiers to the process to increase the impact strength, but only This kind of known technology will cause other physical properties to be reduced, such as "decreased physical properties, reduced processing fluidity, etc., which will damage the physical properties of the resin." In view of this, the inventors of the present invention made improvements to the lack of predecessors, and Lu issued a styrene-based resin composition that has good impact strength and maintains a balance of physical properties such as fluidity, heat resistance, and rigidity. The main object of the present invention is to provide a rubber-modified styrene resin composition with good impact resistance, suitable for processing and molding, and good balance of physical properties such as fluidity, heat resistance, and drying properties. The present invention provides a styrene resin composition modified by rubber waist and with good physical property balance. The composition includes: Page 03 This paper standard is applicable to China National Standard (CNS) A4 specification (210Χ297mm) I J --- ί ------ installed-- (please read the notes on the back of the page 17 to fill out this page) Τ 定--线 3S2489 A7 _B7_ V. Description of the invention (2) (a)-species The ore-bearing matrix phase is composed of styrene strip copolymer, acrylate strip II, acrylate strip waist, and styrene strip copolymer (A) polymerized by copolymerizable monomers as required. Substrate, vinyl copolymer (A) in the upper stupidity contains: 10 ~ 50 weight S! Of propylene 丨 狸 糸 single thread polymerization unit, 45 ~ 89.9 weight MX styrene strip single polymerization unit, 0 ~ 40 reset The copolymerizable mono-polymerized unit of X, and the polymerized unit of acrylic ester monomer of 0.1 ~ 15 weight X; and (b) dispersed in the matrix and reset based on 100 S: styrene strip tree composition 5 ~ 45 The rubber particles of heavy MX, the above rubber particles with a particle size of 0.20 < a or more account for more than 30 weight JK of all the particles, and the styrene resin Tetra hydro-furan (THF) soluble content in the product, the molecular weight distribution measured by Gel Permeation Chromatography (GPC) is: (1) Those with a molecular weight of 1,000 ~ 40,000 , 4% to 26% of the molecular weight of 1,000 to 3,000, 000 reset; (2) MW of 40,000 to 90,000, 18 to 41 weight of the molecular weight of 1,000 to 3,000; Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (3) Those with a molecular weight of 90,000 to 200,000 account for 28 weights of MW of 1,000 to 3,000, 000 or more! Κ or more. The monomer polymerization unit referred to in the present invention refers to the monomeric polymerization unit (polynerized unit) formed by the aforementioned monomer after polymerization. The styrene strip copolymer (A) of the present invention is composed of styrene strips from 45 to 89.9 weight ftX, acrylic strips from 10 to 50 weight Dong X, and acrylic strips. Page 04 This paper size is applicable to Chinese national standards (CNS) A4 specification (210X297mm) A7-B7 Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs i, Invention Instructions (3) Qian X 0.1 ~ 15 reset X, and copolymerizable orders * 0 ~ 40 X is obtained by polymerization; the above-mentioned stupid vinyl bar copolymer (A) can be obtained in the form of bulk, solution, suspension or emulsification polymerization. Among them, the bulk or solution polymerization method is preferred, and the average molecular weight of the heavy eaves is 60,000 ~ 400,000 Between, especially 80,000 ~ 300,00 00 is better. The styrene pads used in the styrene pad copolymer (A) can be: styrene, ot-methylstyrene, p-chlorostyrene, p-third butylstyrene, p-methyl Styrene, o-chlorostyrene, m-cyanostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromostyrene, and 2,5-dichlorostyrene Bromostyrene, etc. Among them, styrene or α-methylstyrene is preferred. The acrylic monomers used for acrylonitrile can be acrylonitrile, α-methacrylonitrile, etc., of which acrylonitrile is preferred. The copolymerizable waist used in the styrene bar copolymer (Α) of the present invention may be: methacrylic sugar bar single plaque, maleimide bar single fish, methacrylic acid, acrylic acid, anhydrous maleic acid, etc .; Among them, the methacrylate ester monona can be: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, methylmethacrylate Cyclohexyl acrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, etc., among which methyl methacrylate is preferred. The single sickle of maleimine can be: maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N- Hexyl maleimide, N-octyl maleimide, N-dodecyl horse page 05 (please read the precautions on the back first 1-K fill in this page). The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 Printed by the Central Consumers ’Bureau of the Ministry of Economic Affairs, Employee Consumer Cooperatives " " ^ -_—- V. Description of Invention (Bucket) Laimide, N- Chenhexylmaleimide, N-phenylmaleimide, N-2,3-tolylmaleimide, N_2,4-tolylmaleimide, N-2,3 -Ethylphenylmaleimide, H-2,4-ethylphenylmaleimine, H-2,3-Butylbenzylmaleimide, N-2,4-Butylphenylimine Lenimide, K_2,6-tolylmaleimide, N-2,3-chlorophenylmaleimide, N-2,4-chlorophenylmaleimide, Ν-2 , 3-bromophenylmaleimine, N-2,4-bromophenylmaleimide, etc., among which N-phenylmaleimine is the best; the former can be copolymerized «If the The use of maleimide can improve the heat resistance of the resin. The acrylate strip monomers used in the styrene strip copolymer (Α) can be: methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, benzyl acrylate, hexyl acrylate, hexyl acrylate, acrylate 10 Dioxanol, isooctyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, dimethyl cyanoethyl acrylate, etc., of which butyl acrylate is preferred. The preferred preparation method of the styrene bar copolymer (Α) of the present invention can be completed by a continuous ore block or solution polymerization reactor. The upper reactor includes: a columnar flow reactor, complete Hybrid (CSTR) reactors, or tube reactors with static mixing elements, etc., which are preferably completely mixed reactors; the number of upper reactors can be one value, or two or more reactors can be used in combination, In the production of the styrene bar copolymer (Α > of the present invention, the polymerization start can be added to the reaction by thermal polymerization or the polymerization start_ includes over-gasified amides, over-gasified sugars, over-chemical For ketals, pervaporated phosphate esters, and azo compounds with nitro and cyclohexane rings, etc., the amount of the pre-polymer starter is usually based on 100 weight! K of 0.01 ~ 06 pages (please read the notes on the back 4 'fill in this page first) -installed- · The paper size of the binding book is applicable to the Chinese National Standard (CNS) Α4 specifications (210X297 public daughter) A7 B7 _ i'instructions for invention (5) 1.0 Weight X. The reaction temperature of the upper reactor is controlled at 80 ~ 200 υ, the best It should be within the range of 90 ~ 160 t: and the pressure of the reactor should be controlled between 1 ~ 5kg / CBe. As for the time that the raw material solution stays in the reactor, it should be within 1 ~ 5 hours; In addition, in order to control the polymer For the molecular weight, it is possible to use, for example, the bond transfer agent for the third one-dodecyl azoic fermentation, n-dodecyl thiol fermentation, α-methylstyrene dimer, pinolene, etc. After the conversion rate of 鰹 is 40 ~ 80, it is usually heated by the preheater to the highest temperature, and then the unreacted single gingival and volatile matter are removed by the devolatization step. The general devolatization step You can use a vacuum degassing tank device or an extruder degassing device to remove volatiles, and then collect it as a recovery liquid with a condenser, and remove the water in the recovery liquid, and then use it as a raw material solution; The volatile volatile polymer melt is extruded and granulated to obtain the styrene copolymer (Α) of the present invention. The mash particles dispersed in the matrix of the styrene strip copolymer (Α) of the present invention account for 5 to 45 The weight X, which means that the ingredients of oak fallacy account for 100 weight!); Resin composition The weight of 5 ~ 45! 1 !, and the rubber particles dispersed in the matrix you exist in the form of graft copolymer (B), such as graft copolymer of emulsified rubber mash particles and block (or solution ) Graft copolymer of rubber warm particles; the graft copolymer made of emulsified rubber particles of the present invention is in the presence of 40 to 85 parts by weight of diene rice rubber emulsion, and 90 to 50 parts by weight with styrene strips ! I ;, Propylene please strip 10 ~ 50 heavy Dong X, acrylate strips single brew 0 ~ 15 weight X, and copolymerizable 箪 缸 0 ~ 40 weight JK made of single brew mixture 60 ~ 15 parts by weight graft Grafted emulsified oak hull grafted with weight average particle size 0.05 ~ 0.8 on page 07 ____—___ This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm) nh—I— —i n-n I nl * (please read the notes on the back i-1 ·. Fill in this tribute)

TiT Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperatives Printed by the Ministry of Economic Affairs Central Counseling Bureau Employee Consumer Cooperatives A7 ---- B7 V. Description of the invention (b) Copolymer emulsion, followed by coagulation, dehydration, drying, etc. , And prepared a graft copolymer of powdery and granular emulsified rubber particles; the upper diene strip rubber emulsion contains 100 ~ 60 weight X of conjugated diene monomer ", and 0 ~ 40 weight! 1! The homopolymer formed by copolymerizing the unsaturated monomer (h〇B〇p〇lyBer) or its copolymer (copolyner), and the conjugated diene monomer can be expressed as follows:

R

I CH. = C-CH = CH. Where R can be a hydrogen group, a methyl group or a gas group, etc. The copolymerizable unsaturated monomer can be a styrene strip monomer, acrylonitrile sulfonate, methacrylate Strips, acrylate monomers or mixtures thereof. The diene strip rubber waist emulsion used in the present invention may be polybutadiene, butadiene-styrene copolymer, butadiene-propylene copolymer, butadiene-methyl methacrylate copolymer, and isopropylene Pentadiene-butyl acrylate copolymer, etc .; the pretene rubber emulsion can be directly polymerized into the form with a weight average particle size of 0.05 ~ 0.8, or it can be pre-polymerized to a size of 0.05 ~ 0.18 / « After the particle size rubber mash emulsion, the traditional rubber mash enlargement method is used to enlarge the small particle rubber emulsion of 0.05 ~ 0.18 / «into an oak emulsion of 0.2 ~ 0.8_; the former rubber enlargement method can be added organic acid, Metal salt or carboxylic acid group-containing polymer agglomeration method chemical magnification method, eaves machine stirring eaves equipment magnification method or freezing enlargement method, etc .; the polymer agglutinating agent used in the previous chemical magnification method can use, for example, butyl acrylate Methacrylic acid copolymer. The preparation of the graft copolymer cracked by the emulsified warm particles mentioned above is usually carried out by using the conventional graft polymerization technology in the presence of a rubber-like polymer, together with styrene strips, propylene m strips and single plaque, as required. The added paper can be copolymerized. Page 08 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Il · --- ^ ----- installed-- (please read the notes on the back first '+ · Fill in this page) Order line 322489 Printed by the Ministry of Economic Affairs Central Standards Bureau Negative Consumers Cooperative A7 B7__ V. Invention description _ () The single-hybrid mixture is grafted, polymerized and reacted, using at least one chemical combination or graft The hard styrene strip copolymer composed of the aforementioned graft monomers is based on the diene rubber; according to the ratio of the monomer to the diene rubber and the polymerization conditions, the graft on the diene rubber can be obtained at the same time. It is the polymer with the required graft rate; usually the polymerization temperature, initial type, physical, chemical, particle size, monomer addition rate, monomer and rubber in the graft polymerization reaction Pre-impregnation degree, chain transfer agent, emulsification Lizard and with factors such as the type, the color will be hard alumina ratio styrene graft copolymers article. The hard styrene copolymer obtained by emulsification graft polymerization of single monomers is partially chemically bonded to the diene rubber, and the other part forms a free copolyier. The free state copolymerization The object can form a part of the base of the styrene strip copolymer (A) of the present invention; and it is observed with an electronic microscope image of the rubber graft copolymer, and the rubber particles can encapsulate the aforementioned hard styrene copolymer (Occlusion), it is also possible not to encapsulate the hard styrene copolymer at all, the degree of encapsulation depends on the physical properties. The initiator or catalyst added in the aforementioned graft polymerization reaction is usually in the range of 0.01 to 5.0 parts by weight of the polymerizable monomer, preferably 0.1 to 3.0 parts by weight; Depending on the polymerization conditions, the aforementioned initial can be added in increments, which is conducive to the progress of the graft polymerization reaction. Moreover, the molecular weight of the aforementioned graft polymer can be controlled by the temperature of the grafting reaction, and / or it can be adjusted with a relatively small proportion of conventional molecules such as thiol, halide or mucene. ”Examples of scorpions that are more specific are: n-dodecyl thiol, third-dodecyl mercaptan, α-methyl stupid ethylene dimer. Page 09 L --- „------ ^ —— 1-(Please read the notes on the back C. Seven fill in this page) This paper size is applicable to China National Standard (CNS) Α4 specification (210Χ297 Cli) A7 B7 printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (name) The graft polymerization of the present invention can be added to the polymerization system by using a single beetle mixture in a continuous ore or by adding Dong, and the most It is good to add the initiator at the same time or in increments; the aforementioned initiator can use various conventional emulsified free radical polymerization reaction initiators, such as: pergasified compounds, nitrogen compounds, or sulfated compounds. For example, the starting agent of pervaporate: cumuiyl peroxide (dicuiyl peroxide), tert-butyl peroxide (tert-butyl peroxide), tert-butyl hydroperoxide (tert-butyl hydroperoxide), In case of gasification of benzoyl peroxide and cumene hydroperoxide, the polymerization reaction of the mixture of butadiene-based rubber emulsion and single plaque is inert at 20 ~ 100 C Stir under the air plaque, it can also be pressurized to 0 ~ 100 P. SIG; during reaction 90% of the monomers are polymerized, and the polymerization time usually takes 2 to 10 hours, and preferably 3 to 8 hours. The graft copolymer made of the emulsified rubber grains of the present invention uses styrene-based monomers The plaques, acrylic monomers, acrylic ester monomers, and copolymerizable monomers are the same as the single sterns illustrated in the matrix of the styrene copolymer (A), and will not be repeated here; through the previous graft polymerization After the reaction, an oak graft copolymer emulsion with a weight average particle diameter of 0.05 to 0.8 can be prepared, and the preferred weight average particle diameter is 0.06 to 0.6. The emulsion of graft copolymers with particles must be added to the graft copolymer emulsion. Appropriate coagulation is used for coagulation. Generally, the coagulants used are sulfuric acid, acetic acid and alkaline earth metal salts, such as calcium chloride calcium salt, magnesium cyanide, magnesium sulfate magnesium salt, and aluminum aluminate. Salt, among which age-earth metal salts are preferred. The coagulated polymer slurry is dehydrated through a dehydration process, and then dried. Page 10 This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm)- -^ -------- Meal-- (Please read the back side first CAUTIONS 1, -4; Complete this page)

、 TT line 322489 Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of invention (?) After drying, the graft copolymer of powdered and granular emulsified rubber particles can be prepared. The graft copolymer made of the block (or solution) rubber particles of the present invention is like a mixture of 5 ~ 45 parts by weight of rubber-like polymer, and the following list of 100 parts by weight, It is obtained by block polymerization and / or solution polymerization. The above-mentioned single warm mixture contains: 90-50 parts by weight of styrene monomer, 10-50 parts by weight of acrylic bladder, and 0-15 weight of acrylate strips. Dong Fen, and copolymerizable monomer * 0 ~ 40 parts by weight, when the conversion rate of the polymerization reaction reaches 40 ~ 90 parts by weight X, then remove the unreacted single plaque and volatile matter through the devolatization step In this way, a graft copolymer of bulk or solution acumin particles with a weight average particle size of 0.1 to 10% can be prepared. The graft copolymer of block (or solution) rubber particles of the present invention can be completed by a continuous block or solution polymerization reactor. The foregoing reactor includes: a column flow reactor, a fully mixed ( CSTR) reactor, or tube reactor with static mixing elements, etc., which is preferably a completely mixed reactor; the number of the above reactors can be one value, or two or more values can be used in combination. When the graft copolymer of block (or solution) rubber particles can be added to the reaction using a polymerization initiator, the polymerization initiator includes over- radonized aldehydes, over-vaporized esters, over-vaporized shrinkage , Over-vaporized phosphoric acid esters, as well as azo compounds with nitro and cyclohexane ring, etc., the amount of pre-polymerization start _ is usually based on 100 reset X of 0.01 ~ 1.0 weight! K! The reaction temperature of the above reactor is pseudo-controlled at 80 ~ 200 t: it is better to be controlled at 90 ~ 160 or less, and the pressure of the reactor is controlled at 1 ~ 5 kg / cm8, as for the raw material solution to stay in The time within the counter should be on page 11. I install II —— I order II line--*-(please read the notes on the back first-fill in this page) This paper standard is applicable to Chinese national standards ( CNS) A4 specification (210X297mm) A7BΊ__ printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (丨 0) ~ 5 hours; In addition, in order to control the molecular weight of the polymer, for example, the thirty-second can be used Transference of alkyl thiolease, n-dodecyl «lease, α-methyl styrene dimer, terpinene, etc. After the polymerization of the polymer is completed, the resulting copolymer solution is usually heated to the highest rent with a preheater, and then the non-reactive monomer and volatile matter are removed in the devolatization step. Generally, the devolatization step Use the device of decompression degassing tank or the degassing device of the extruder to remove the volatile matter, and then collect it into the recovery liquid with a condenser, and remove the water in the recovery liquid, and reuse it as the raw material solution; and After removing the volatile content of the polymerized molten material and extruding it into granules, a graft copolymer of blocky (or solution) acorn particles can be obtained. The rubber-like polymer suitable for the blocky (or solution) rubber knot particle graft copolymer of the present invention has a conjugated diene syrup, preferably such as: butadiene rubber yoke, isoprene rubber syrup, Atmospheric butadiene rubber, etc., of which the types of butadiene rubber are cis-type (Hi-C is) content and low-type (Low-C is) content, etc .: in cis-type rubber, the cis-type ( Cis) / vinyl (Vinyl) typical weight composition is 94 ~ 98S; / 1 ~ 5X, the rest of the composition is trans (Trans) structure, its Mooney viscosity is between 20 ~ 120, the molecular weight is preferably 100,000 ~ 800.000 ; In low cis rubber, the typical weight composition of cis / vinyl is 20 ~ 40 35/1 ~ 205; the rest is a trans structure, and its Mooney viscosity is between 20 ~ 120; other rubber materials suitable for the present invention There is still acrylic! 1 / butadiene rubber mash, styrene / butadiene rubber waist, or a mixture of the above-mentioned different rubber waists; suitable for the styrene / butadiene copolymer rubber koji of the present invention, the polymerization type can be two-stage (Di-block) copolymerization, tri-block (tri-block) copolymerization, random copolymerization (random) or star copolymerization (startype) Page 12: Please read the notes on the back first 4 Fill in this page ) • Packing. The paper size of the binding book is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 gong) The Ministry of Economic Affairs Central Standards Bureau employee consumption cooperation du printed 32s48b A7 Ξ_ V. Invention description (! 丨); Styrene / D The styrene / butadiene weight * ratio of the diene rubber is preferably 5/95 to 80/20, and the molecular weight is preferably 50,000 to 600,000; the rubber waist suitable for the present invention is butadiene rubber Kayak and styrene / butadiene rubber are better, especially butadiene rubber. As for the graft copolymers of block (or solution) rubber particles of the present invention, the styrene-based monomers, propylene-based monomers, and other copolymerizable monomers, and styrene-based copolymers ( Α) The explanations of the single exemplified in the matrix are the same and will not be repeated here. In the block-shaped (or solution) rubber particle graft copolymer of the present invention, a part of the hard styrene-copolymer formed by polymerizing the graft monomer is like a chemical bond to the diene strip oak cam, and the other part The free copolymer can form part of the matrix of the styrene strip copolymer (A) of the present invention: the inside of the rubber particles can encapsulate the aforementioned rigid styrene strip copolymer (Occlusion), the particle size is mostly between 0.01 ~ 0.5 Glow, the number of encapsulation inside the front rubber particles can be one (one encapsulation) or more than one. The graft copolymer of rubber particles obtained by polymerization in the aforementioned bulk (or solution) polymerization method has a rubber weight average particle diameter of 0.1 to 10 mm, and a preferred weight average particle diameter is 0.2 to 7.0 quintile. In addition to the use of graft copolymers of emulsified rubber mash particles or bulk (or solution) rubber mash particle graft copolymers, the oak mucus particles of the present invention can also be used to form Wenfeng or trimodal distribution: Bimodal distribution such as: (1) Average particle size 0.2 ~ 0.8 (emulsification), page 13 This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm)

Ir ---------- installed-- 1 1 (please read the first note on the back, fill in this page) -Reservation line A7 ^ ~ ______ B7_ Five 'Description of the invention (n) Average particle size 0.6 ~ 10 code (block or solution); or (2> average particle size 0.05 ~ 0.18 (emulsification) · average particle size 0.6 ~ 10 #an (block or solution). Trimodal distribution such as: average particle size 0.05 ~ 0.15 畑 (emulsification), average particle size 0.17 ~ 0.8 Township (emulsification), average particle size 0.25 ~ 7.0 code (block or solution) 〇The weight of the former oak grain particles is determined by the method of measuring the average particle size. Hungry (after 0s (h) dyeing the resin, then take a transmission electron temporal micromirror photography, take the particles of the rubber sleeping in the phase K taken about 1000 inclination to measure its particle size, and then find the following formula Obtained weight average particle diameter: Σ η ID 14 Rubber weight average particle diameter =-Σ n, D 1 3 ηι is the rubber particle diameter D, the number of rubber particles constitute the matrix of the styrene strip resin composition of the present invention your hard benzene Ethylene shit copolymer (Α), as mentioned before, it is supplied by a monomer polymerization unit of acrylonitrile strips, a monomer polymerization unit of styrene strips, and a polymer of acrylic monomers And other copolymerizable monomer polymerization units, wherein the content of acrylonitrile monomer polymerization unit is 10 ~ 50 weight! Ϋ, preferably 20 ~ 40 weight! K, styrene strip monomer polymerization unit is 45 ~ 89.9 weight X, preferably 45 ~ 80 weight X, acrylate strip monomer polymerization unit is 0.1 ~ 15 weight X, preferably 1 ~ 10 weight X, and other copolymerizable monomer polymerization unit is 〇 ~ 40 Reset 3; When the polymer unit composed of acrylic strip monomers (that is, acrylic_strip monomer polymerization unit) contains less than 0.1 weight X, the resin composition should be used. Page 14 Standard (CNS) Ad specifications (210Χ297mm) --- ^ ------ installed.-Please read the notes on the back first and fill out this page. Α7 Β7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Invention description (丨 3) The impact strength improvement effect is insufficient. If it is higher than 15 MX, the heat resistance (ie softening stickiness) of the resin composition may be lowered. This will limit the applicability of the product. The rubber waist particles dispersed in the matrix of the present invention It is 5 ~ 45 weight Dong X. When the content of the rubber grain particles is less than 5 mile X, the impact strength of the resin composition is insufficient, and when it is higher than 45 weight ft X, the fluidity and gate resistance of the composition will be deteriorated. If the weight of the aforementioned rubber particles is 0.2 or more, the average particle size needs to account for more than 30 weight X of all rubber particles. When the proportion is less than 30 weight X, the impact strength of the resin composition is insufficient. The resin composition of tetrahydrofuran (tetrahydrofuran, THF for short) is soluble, like the styrene bar resin composition modified by rubber husks dissolved in tetrahydrofuran in organic rain, and then the centrifugal eaves will be insoluble / soluble Soluble fraction separation. In the present invention, most of the insoluble fraction of the first tetrakis furan is rubber particles and hard styrene strip copolymer grafted thereon, and the soluble fraction is mainly styrene strip copolymer (A). It consists of styrene strip copolymers obtained by directly emulsifying, sloping or bulk (solution) polymerization of styrene strip monole, acrylonitrile monomer, acrylate ester monomer and copolymerizable monomers. It is produced during the graft polymerization of the ingredients of dandanyu and oak. The free-form styrene strip copolymer, that is, the styrene-copolymer that is not grafted onto the rubber particles. The above tetrahydrofuran soluble fraction is analyzed by gel permeation chromatographic analysis (Gel Peiestion chronatography, GPC for short). The molecular weight is 1,000 to 40,000, accounting for the molecular weight of 1,000 to 3,000,000. 4 to 26 weight MX, preferably It is 8 ~ 25 heavy Dong X, when the aforementioned occupation is less than 4 weight ϋ; when the resin composition has poor fluidity, the molding surface is likely to be gelled due to page 15 (please read the notes on the back ^, 4. (Fill in this page) Packing. The paper size of the binding book is applicable to the Chinese Pujia Standard (CNS) A4 (210X297mm). The Central Bureau of Economic Affairs of the Ministry of Economic Affairs of the People ’s Republic of China Consumer Cooperation Co., Ltd. A7 Β7 1. Invention description (| 4) Phenomenon of poor appearance of molded products, and when the occupancy of the chief is higher than 26%, the property of the resin composition will decrease, and the impact strength will also be poor; the soluble molecular weight of the resin composition of the present invention is 40,000 ~ 90,000 In particular, 18 to 41 weights with a molecular weight of 1,000 to 3,000,000, especially 22 to 40 weights X is preferred. When the soluble content of the current molecular ft fan garden is less than 18 weight MX. The flowability of the resin composition is not good, high At 41 weight X, the resin's impact strength is not good; If the molecular weight of the soluble in the resin composition is 90,000 to 200,000, it accounts for 28 weights M3 of molecular weight 1,000 to 3,000,000 or more, which is 29 to 60 weights Λ3ί, and when the soluble matter of the aforementioned molecular M is less than 28 weights When Dong X, the tensile strength of the resin will be reduced, and the impact strength is also poor, higher than 60 weight 3; when, the flowability of the resin is not good. The molecular weight distribution of the gel permeation chromatographic analysis method of the present invention is defined by the calibration curve obtained from various polystyrenes with different mono-distribution molecular weights. Therefore, the tetrahydrofuran of the present invention is soluble The molecular weight of a part is a relative molecular weight based on polystyrene. The molecular weight distribution of the tetrahydrofuran soluble fraction of the resin composition of the present invention is conclusive, and it is determined by the principle of condensate permeation chromatography analysis, such as the document "歹 Λ / Xikou 7 Bu Basic Edition" "(Takeda He: published by Kodansha) (PP. 97 ~ 122) described in the document. In the present invention, the measurement conditions are as follows: 1. Use the instrument of MILLIP0RE company, this instrument includes: (Α) absorption detector (Waters 486 Tuna-ble Absorbance Det ector), its setting value is: (a) wavelength (Wavelength): 270 η · _ * Page 16 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) I. IIIII Binding—Line (please read the notes on the back tv fill this page) Ministry of Economic Affairs A7 B7_ printed by the Central Standard Falcon Bureau for consumer cooperation. V. Description of the invention (l5) (b) Sensitivity: 1.00 (c) Filter: 1.0 (d) Use two "columns [column , KD-806X (7.8 a * x300, «The composition of the material is styrene-divinylbenzene copolymer, the pores are linear distribution from small to large, which can analyze the molecular weight of 2,000 ~ 4,000,000. (E) Reaction temperature (Operat ion teaperature): 35 ± 0.1Ό. (B) Auto sampler (Vaters TM 717 plusAutosaaper). (C) Pump Waters 510 HPLC puap): flow rate is 1.0 · 1 / · ίη 2. Items added in stages : Tetrahydrofuran (containing 0.U toluene). 3. Preparation of the sample: (A) Dissolve 0.015 g of sample in 10 · 1 tetrakistofuran domain, and precipitate and separate the insoluble fraction with a centrifuge. Take the upper layer of tetrakisfurfur_soluble material for condensate penetration Chromatography. (Β) Injection volume: 120 ul. 4. From the ultraviolet absorption value to the curve of the waist penetration chromatographic analysis obtained by dividing and sticking at each time, the total entanglement circle with the molecule set to 1,000 to 3,000,000 is obtained to obtain the molecular weight distribution. 5. The standard image of molecular weight for gel permeation chromatography analysis is polystyrene (manufactured by TO-SOH Corporation, 1-1-139 Akasaka Minat〇-Ku Tokyo Japan), and the molecular weights for correction are as follows: 500, 870, Twelve kinds of 2630, 5970, 9100, 18100, 37900, 96400, 190000, 355000, 706000, 2890000 and so on. The styrene resin composition of the present invention can be added and used as needed on page 17 ------- r ----- installation-- (please read the notes on the back A. fill in this page)-* The size of the lined paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). The Central Standards Bureau of the Ministry of Economy printed 322489 A7 _ _B7__, the material of the invention description (丨 t), for example: anti-oxidation Rubber, plastic ribs, processing ribs, slippery », UV absorber, UV stabilizer, anti-banding _," filler, fortifier, colorant, flame retardant, flame retardant aid, thermal stabilizer, coupling agent Or other additives, etc., additives can be added during polymerization, after polymerization, before coagulation or during extruding and mixing. The anti-gasification thin film of the present invention should preferably use phenol strip anti-gasification blue, thioether paddle anti-gasification agent, phosphorus strip anti-gasification agent, cocoon and other substances, wherein the amount of phenol strip anti-gasification agent added is 0.005 ~ 2.0 The weight X is better, and representative ones are: octadecyl-3- (3,5-di-third-butyl-4-hydroxyphenyl) -propionate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], tetra [methyl »yl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] methane, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-6-methylbenzyl) -4-methylphenyl acrylate, 2,2 ·- Methylene-bis (4-methyl-6-tert-butylphenol), 2,2 thiobis (4-methyl-6-tert-butylphenol), 2,2 * -thio-di Ethylene-bis [3- (3,5-bis-third-butyl-4-hydroxyphenyl) propionate], 2,2'-diacetaldehyde-bis [ethyl-3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate]. Thiosulfonate anti-gasification agent is added in an amount of 0.005 to 2.0 weight J: preferably, typical examples are: distearyl dipropionate, dipalmitaldehyde thiodipropionate, pentaerythritol One four one (/ 9 twelve methyl monothio propionate), dioctadecyl sulfide, etc .; pound anti-gasification agent is phosphite anti-gasification agent or phosphate anti-gasification thin ( , The added amount is preferably 0.015 ~ 2.0 weight χ, the representative ones are: tri (nonylphenyl) phosphite, dodecyl phosphite, cyclic neopentane tetrahydronaphthyl bis (ten Octaalkyl phosphite), 4,4'-butylene bis (3-methyl-6-third butylphenyl-bis tridecyl phosphite), three Page 18 ----- ------ ¥ II (please read the notes on the back first \ fill in this page)

-Order I The paper size is applicable to China National Standard (CNS) A4 specification (210X297mm). The Ministry of Economic Affairs Central Standard Falcon Bureau employee elimination cooperative printed A7. ^ B7 ----_____ V. Invention description (丨) 2,4-tert-butylphenyl) phosphite, tetrakis (2,4-tert-butylphenyl) -4,4 · -biphenylene phosphate, 9,10-dihydrin-9- Gas-10-Phenanthroline-10-Oxygen, etc. The amount of chel added is preferably 0.001 ~ 2.0 Chong Li X, the representative ones are: dibenzoylmethane, diethylamine tetraacetic acid sodium salt and so on. The added ft of the anti-gasification agent is usually 0.03 to 2.0 weight X relative to the styrene strip resin composition. Representative examples of slip agents include: calcium stearate, magnesium stearate, lithium stearate, etc., gold soap, ethylene distearate, methylamine distearate, ammonium citrate, Compounds such as butyl stearate, palm stearate, polypropionase tristearate, n-docosanoic acid, stearic acid, etc. «(Carnuba wax), petrolatum, etc .; the amount of lubricant added is usually 0.03 ~ 5.0 weight X relative to the total styrene strip resin; in order to improve the extrudability and thermoformability of the resin, you can also add such as methyl Processing aids for methyl acrylate strips: UV absorbers are typically represented by benzotriazole strip compounds, benzophenone strip compounds, and gas acrylic strip compounds, while UV stabilizers_representatives are: block The amine strip compound; the amount of the aforementioned substance added is generally 0.02 ~ 2.0 weight relative to the total styrene strip resin: K! In order to improve the weather resistance of the resin, resistance to ultraviolet radiation, or discoloration of the resin, or deterioration of the physical properties of the resin, it is better to use a combination of the two to absorb the ultraviolet absorption of the amine strip ultraviolet stabilizer acrylic strip, for example: BASF company's uvinul 4050H (0.02 ~ 1.0 weight ltX) / uvinul 3035 (0.02 ~ 1.0 weight X). Page 19 This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297mm) I, ---- 1 ------ installed-- (please read the notes on the back first 1 fill in this I) Alignment kiss 489 A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Invention Instructions (ιΜ Low-molecular strip compounds such as tertiary amine strip compounds, quaternary ammonium salt compounds, etc. , Or polyammonium poly_, such as 3-Ammonia_1, 2-Cyclo «Propane polymerization, which shows permanent clamp" Preventive polymer strip material. Representative examples of fillers such as: master acid ", silica, Mica. Representatives of strengthening agents such as: glass following dimension, fiber, various crystals (wh i sker). Representatives of colored cocoons such as: vaporized titanium, oxidized hunger, graphite, phthalocyanine dyes. Representative agents or flame retardant additives such as: decabromodiphenyl ether, tetrabromobisphenol A, brominated polystyrene oligomerization «, brominated Chen gas resin, hexabromodecdecane, cyanopoly Alkylene oxide, triphenyl manduronic acid, red phosphorus, gaseous beryllium, aluminum hydride, magnesium gas, zinc sulfate, trimeric amine, isocyanamide salt, silicon Gas powder, polytetrafluoroethylene powder, expanded graphite, etc. Representative stabilizers include: dibutyltin maleate, basic magnesium aluminum hydroxy master salt, etc .; also prevent thermal discoloration _ can be low molecular weight Styrene-anhydrous maleic acid copolymer, the addition of Li is generally 0.1 to 1.0 weight X relative to the total amount of the styrene strip resin composition of the present invention. Typical examples of couplings are: silane strips, K acid sugar 、 Acrylic acid strip compound. In order to modify the styrene strip resin composition of the present invention, additives of polymerized hip strips can be used, such as block polymerization method, dissolution polymerization method, block suspension polymerization method Etc., that is, it can be manufactured by a method other than emulsion polymerization, modified with rubber styrene resin, such as acrylonitrile butadiene, page 20—in ~ IIIII equipment—III—order IIIIII line (please read the back page first Note to fill out this page) (This paper standard applies to China National Standards (CNS) A4 specification (210X297 mm) Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 322489 A7 B7 V. Description of invention (I got) A styrene Resin, rubber other than butadiene rubber, such as EP DM, styrene resin such as AES resin modified with acrylic butadiene rubber, AAS resin, anhydrous maleic acid-styrene copolymer, benzene Ethylene-maleimide copolymer, styrene-acrylonitrile-anhydrous maleic acid copolymer with maleimine content of more than 40 ftX, styrene imidized with aniline_Acrylic 丨 S—anhydrous Maleic acid copolymer, bridging rubber without grafting such as acrylonitrile butadiene rubber, vinyl cyanide resin, polymethyl methacrylate, polyacrylate resin, polyamine resin, polybutylene terephthalate The amount of the olefin ester, the thermoplastic elastomer of the styrene strip, various compatible solvents, etc. is 3 to 200 parts by weight with respect to 100 replacement parts of the styrene strip resin composition of the present invention. In order to further explain the present invention in detail, the following examples and physical property tests are described below. Unless otherwise stated, the ingredients of the following compositions are expressed in parts by weight. The following examples are given to explain the present invention in detail, but the present invention The standard plaque is not limited to these examples. ≪ ^ M_ 艟 _m > < Preparation Example I_1 > Preparation of styrene strip copolymer (A-1): at 12 kg / hr The speed of the composition will be: styrene 70 weight X, propylene 30 weight 3! The raw materials are mixed, and then the ethylene distearate leg 3.0 g / hr, in case of gasification benzophenone, 31-dodecane The recovered liquid formed after condensation of the base-broken alcohol and the volatiles removed by the reaction described below is combined and used as a bait feed liquid to be fed into the tank. The ffi degree is maintained at 108 t: and the capacity is 45 liters. Reactor, and keep the proportion of toluene in the reaction liquid at 15X, and the polymerization rate at 55X. Page 21 This paper scale is applicable to the Chinese National Standard (CNS) A4 (210X297mm) Please read the notes on the back hf. Fill in this page) • Binding · Order-Line · Printed by the Employee Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Install A7 _____B7_ V. Description of the invention (Μ) When: the anti-stove liquid is removed through the devolatilization device, the particles of the styrene strip copolymer can be obtained; on the other hand, the removed volatile components are taken as the Recover the liquid and reuse it in combination with the above-mentioned raw materials in the mining area. In this way, the reaction rate can be adjusted from the epilepsy of the benzoyl benzoate, or the amount of the 31st alkylsulfuric acid can be used. A styrene-copolymer (Α-υ) with a melt flow index of 12.0 was prepared. ≪ Preparation Example I-2 > Preparation of styrene bar copolymer (Α-2): The composition was made at a rate of 12 kg / h The material is: styrene 68 weight X, acrylonitrile 30 weight X, butyl acrylate 2 weight X, the raw materials are mixed, and then the ethylene distearic acid amide 3.0 g / hr The dialkyl mercaptan and the volatiles removed by the reaction described below are condensed and the recovered liquid formed after condensation As a feeding liquid, a continuous-type kettle-type reactor with a stirrer with an internal temperature of 108 liters and a volume of 45 liters was supplied, and the proportion of toluene in the reaction liquid was maintained at 15¾, while the polymerization rate was maintained at 55J; When the reaction liquid meets the devolatilization device to remove the volatile components, the styrene-coated copolymer particles can be obtained; on the other hand, the removed volatile components are condensed by the condenser as the recovery liquid, and the mine is mixed with the aforementioned raw materials The liquid is reused. In this way, the styrene bar copolymer with a melt flow index of 11.5 can be prepared from the gasification benzophenone's Dong reaction speed, or the amount of the 31-dodecyl mercaptan. (A-2). ≪ Preparation Example I-3 ~ 1 2 > Preparation of styrene strip copolymers (A-3) to (A-12): Repeat the polymerization method of Preparation Example 2 and replace The composition is mixed according to the raw materials shown in Table 1, and the reaction speed is set at the time of gasification of benzoic acid. Page 22 This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) (please read the back Things to pay attention to kj. Fill in this page)-installed · 322489 A7 _B7 _ V. Description of the invention (d) The rate, or adjusting the M of the 31st-dodecyl fermented yeast, can produce styrene strip copolymers (Α-3) to (Α-12) with different flow indices. ≪ Preparation Example I One 1 > Preparation of Oak-Mut Graft Copolymer (Β-1): -------- 1 ------ installed-- (please read the notes on the back first 1 fill in this page) The third-dodecyl mercaptan 0.2 was reacted at 6513 temperature for 12 hours according to the above formula, and the conversion rate was 94 X, the solid content was about 40! 1; and the weight average particle size was O.lw. latex. In addition, the following components are used to produce ionic coagulated cocoons containing carboxylic acid groups: -Ordered-Printed by the Employees' Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs η-Butyl acrylate 85 Methacrylic acid 15 Third-dodecyl sulfatase 0.3 oil Potassium acid 2.0 Dioctyl sulfosuccinic acid m 1.0 Isopropyl sulfonated per radon hydrogen 0.4 Formaldehyde hydrogen sulfoxylate 0.3 Steamed water 200 Page 23 into parts by weight 1,3-butadiene 95.0 Propylene 5.0 Potassium oleate solution 15.0 Pyrophosphate m 3.0 Potassium oleate 1.5 Steamed water 140.0 The paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) 322489 A7 B7 V. Description of invention (A) According to the above formula in 75 scoops The reaction was performed for 5 hours to obtain a carboxylate group-containing polymer agglomerate with a conversion rate of about 95 X and a pH of 6.0. Afterwards, 3 parts of the carboxylic acid group-containing ion agglutination _ (dry weight) were used to enlarge 100 parts by weight of synthetic rubber latex (dry weight), and the pH of the resulting hypertrophic rubber emulsion was 8.5, weight average The particle size is 0.30 / α. Finally, the hypertrophic rubber hock emulsion was grafted and reacted according to the following formula to produce the rubber graft copolymer (B-1): Chengzhong Tan hypertrophic rubber emulsion (dry weight) 100.0 Styrene 25.0 Propylene 8.3 Potassium oleate 1.2 Tertiary-dodecyl mercaptan 0.2 Cumene pervaporated hydrogen 0.5 Ferrous sulfate solution (0.2X) 3.0 Formaldehyde sulfoxylate sales solution (10X) 3.0 Ethylenediaminetetraacetic acid Solution (0.25X) 20.0 Steamed water 200.0 (please read the notes on the back ^, 4 fill in this page first)-Packing · Ordering · Rubber grafts made by Duin Printing Co., Ltd. of the Ministry of Economic Affairs, Central Standards Bureau, Shell Industry Consumer Cooperation After the emulsion is condensed and dehydrated with vaporized calcium (CaCl «), and then dried to a moisture content of 2X or less, the rubber graft copolymer (B-1) required by the present invention can be prepared, and its rubber content is 75 weight The most 3 !, the weight average particle size is 0.30 / an. < Preparation Example 1-2 > Manufacture of Oak-Mut Graft Copolymer (B-2): Synthetic rubber syrup prepared by < Preparation Example 1-1 > The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) A7 B7 5. Description of the invention () 3) The average particle size is 0.1 M), directly in conjunction with the following table to carry out the graft polymerization reaction to obtain the rubber waist graft Copolymer (B-2). Ingredient weight * serving 1 please first synthesize rubber milk (0.1 / α) (dry weight) 100.0 read 1 1 styrene 75.0 back. + I of 1 I acrylonitrile 25.0 Note ★ 1 | potassium oleate 2.0 ψ Item 1. 1 I Thirteen-dodecyl thiolase 0.6 Fill in this book 1 Pack I Cumene sulfide meets gasified hydrogen 1.4 pages 1 I Ferrous sulfate solution (0.2%) 8.6 1 1 Formaldehyde sodium sulfoxylate solution (10J!) 8.6 1 1 Tetraacetic acid solution (0.25X) 57.0 Order 1 Distilled water 200.0 The grafted emulsion of oak mash prepared according to the above formula is then coagulated with calcium cyanide (CaCU) to produce the jacket of the present invention The required rubber graft copolymer (B-2) has a rubber sleep content of 50 weight X and a weight average particle size of 0.1 / 0. < Preparation Example 1-3 > Production of Oak-Mut Graft Copolymer (B-3): Printed with 0.1 parts by weight of tertiary-dodecyl sulfatase and 0.07 weight printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs One part of over-gasified benzophenone is used as an initiator, mixed with 6.6 parts by weight of polybutadiene (produced by Asahi Kasei Corporation, trade name Asadene 55AS), and the upper component is completely dissolved in 74.4 parts of styrene , 25.6 parts by weight of acrylonitrile and 30 parts by weight of ethylbenzene, to form a feed solution, and then the feed solution was set into the first reactor of Lizhen 44 liters, the reaction temperature was 100 〇, reaction The device is equipped with a suspected rotary agitator with a cooling Xunchen tube. The standard of the paper on page 25 applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 322489 A7 B7 V. Description of invention U bucket) Economy The printing and mixing rate of the Employees ’Cooperative of the Central Standards Bureau of the Ministry is 300 rp ·. The mixed Yanlian Myanmar after the reaction in the first reactor is taken out and sent to the second reactor in sequence. The equipment and the second reactor One anti-molecular is the same, its reaction temperature is 130 ΊΟ, stirring speed 180 γρβ; when the conversion rate of the mixture is 60X, the mixture is taken out and sent to the devolatilization device to remove unreacted single waist and volatiles, and then it is extruded and granulated to obtain the oak waist graft copolymerization Substance (B-3), the weight average particle diameter of the rubber particles is about 11% X by weight. The physical properties of the resin compositions prepared in the examples and comparative examples of the present invention are tested as follows: 1. Tensile strength: tested according to ASTM D-638, expressed in kg / c · 8. II. Izod impact strength (IZ0D): tested in accordance with ASTM D-256, expressed in kg • CB-CB. 3. Melt flow index: tested in accordance with ASTM D-1238, expressed in g / ΙΟ · ίη .Vicat Softening Tenperature: Tested according to ASTM D-1525, expressed as 1C. V. Falling Dart Impact: Tested according to ASTM D-30 29, unit is kg Χββ (2 kg load). ≪ Fen_ 施 _ # 11 > < Examples 1 ~ 1 1 > According to the formula listed in Table 2, it consists of a combination of 100 parts by weight of sleeping graft copolymer (B) and styrene strip copolymer (Α), and 2.0 parts by weight of two slips. Styrene strip resin composition; the soluble components of the styrene-shi resin composition of Examples 1 to 11 above on page 26. This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm). Please First read the precautions on the back. A binding page is printed A7 _B7_ by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy. V. Invention Description P5). The MJK of the molecular weight distribution and the composition of the molecular weight distribution are measured by the condensate permeation chromatography method. The matrix is analyzed by FTIR (Fourier Transforn-IR) for the polymerization components of each single mule, and the melt is kneaded and extruded into strips according to the examples, and cut into granules and then injection molded to perform various Physical property test, the results are shown in Table 4. < Comparative Examples 1 ~ 6 > The test procedures of Comparative Examples 1 ~ 6 are the same as those of Example 1, except that the formula required for the composition is shown in Table 3, and the aforementioned comparative examples are also as in the examples. The weight of the molecular weight distribution in the tetrahydrofuran soluble fraction of the styrene resin composition is measured by the gel penetration analysis method. U, and the matrix of the composition is analyzed by FTIR (Fourier Transforn-IR) for the polymerization of each monomer, and according to In each of the examples, the melt was kneaded and extruded into strips, cut into pellets, and then injection molded. Various physical property tests were carried out. The results are shown in Table 4. From the experimental results of Comparative Example 1 and Examples 1 to 4 in the attached Table 4, it is shown that when the matrix of the resin composition contains 0.1 to 15 heavy dong! K acrylate monomer polymerization units, the flow index, rigidity When the physical properties such as heat resistance and heat resistance are maintained in a good balance, the impact strength of the resin composition is lifted; and Comparative Example 2 shows that when the content of the polymer unit of the acrylate strip monomer in the matrix of the resin composition is higher than 15 MX , The heat resistance (di softening viscosity) of the resin composition will be greatly reduced; the comparison of Comparative Example 3 and Examples 8, 9, 10, 11 shows that the content of rubber particles at the same value (17 Chong Li X) Under the benchmark, the content of rubber particles in the 0.2 or more period must account for more than 30 weight X of all rubber particles, otherwise the impact strength of the resin composition is not on page 27 (please read the precautions on the back and fill in this page Threading-This paper scale is applicable to China National Standard Falcon (CNS) A4 specification (210X297mm) ^ 22489 A7 B7 5. Description of the invention (bucket) foot; the comparison of Comparative Examples 4, 5, 6 and Example 2 shows, A list of acrylates of the comparative example The content of polymer units, rubber particle content and particle size distribution of the eel are within the scope of the present invention, but when the molecular distribution of the four wondrofuran solubles is employed away from the molecular Λ distribution of the present invention, the physical properties of the composition are not well balanced , That is, it is impossible to obtain good impact strength, tensile strength, and melt flow index at the same time; that is, the present invention can obtain good impact resistance, suitable for processing and molding, and fluidity after being limited by the foregoing components and usage amounts The rubber-modified styrene resin composition with good balance of heat resistance, rigidity and other physical properties can be used in the industry. However, the above is only a few preferred and feasible embodiments of the present invention, which is familiar to those skilled in the art Shi, its modifications or changes made in accordance with the spirit of the present invention should be included in the patent application park of this case. (Please read the notes on the back to fill out this page)-Binding · Binding-Central Bureau of Economics and Trade Printed on the 28th page by the Negative Consumers Cooperative Society. The paper size is in accordance with the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) ^ 22489 Example number in the attached table 1 2 3 4 5 6 7 8 9 10 11 1 2 Types of styrene bar copolymers Α-1 Α-2 Α-3 Α-4 Α-5 Α-6 Α-7 Α-8 Α-9 Α-10 Α-11 Α-12 acrylonitrile (reset% ) 30 30 30 30 30 30 30 29 30 30 30 30 Into styrene (weight ϋί) 70 68 65 62.5 60 50 60 62.8 60 65 65 65 · Material butyl acrylate (weight ϋ;) 1 2 5 7.5 10 20 5 5 5 5 5 5 Group cx-methylstyrene (weight X) 5 into N-phenylmalealdimine (weight X) 3.2 methyl methacrylate (weight X) 5 Melt flow index of styrene bar copolymer 12 11.5 11.7 11.2 11.6 10.8 10.5 7.2 11.3 0.4 20 18 | 3 As 489 Schedule example number 1 2 3 4 5 6 7 8 9 10 11 Group of mash graft copolymer B-1 18.7 18.7 18.7 18.7 18.7 18.7 18.7 22.7 9.1 18.2 20.4 (B) parts by weight B-2 20.5 6.8 B-3 17.0 styrene A-2 81.3 A-3 — 81.3 77.3 70.4 75 62.6 Shito copolymer A-4 81.3 Α · 5 81.3 ⑷ A-7 81.3 A * 8 81.3 parts by weight A-9 81.3 322489 Scheduled comparative example number 1 2 3 4 5 6 Composition Graft rubber copolymer ⑻ parts by weight B-1 18.7 18.7 4.5 18.7 18.7 7.5 B-2 — — 27.3 A — 16.9 B-3 styrene copolymer (A) parts by weight A-1 81.3 — 68.2 One One A-10 — One 81.3 — — A-11 One — One 81.3 — A-12 81.3 A-6 — 81.3 — — —

Claims (1)

322489 ABCD amendment supplement Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 6. Patent application No. 85110868. Patent for applying for invention of gas ^ Application for a patent specification page. 1-1. A styrene strip resin composition, which contains: (a) -A kind of continuous Burmese matrix phase, its styrene strip copolymer is composed of styrene strip monomers, acrylic eye strip monomers, acrylate strip monomers and optionally copolymerized mono-skeleton polymer (A) Substrate, the above styrene shit copolymer (A) contains: 10 ~ 50% by weight of acrylonitrile strip monomer polymerization unit, 45 ~ 89.9 weight S; the styrene strip monomer polymerization unit, 0 ~ 40 weight S: Polymerizable monomer polymerization unit, and 0.1 ~ 15 weight 3; acrylic ester monomer polymerization unit; and (b) dispersed in the matrix phase and based on 100 weight! "Styrene strip tree composition 5 ~ 45 weight Of the rubber particles, the particle size of the upper tumbler rubber particles above 0.20% accounted for more than 30% by weight of all the rubber particles; and the soluble fraction of tetrahydrofuran in the styrene strip resin composition penetrated the color layer with gel The molecular weight distribution measured by the analytical method is: (1) Molecule 1,000 to 40,000, with a molecular weight of 1.000 to 3, 000,000 of 4 to 26 weight "; (2) with a molecular weight of 40,000 to 90,000, with a molecular weight of 1,000 to 3,000 of 18 to 41 weight X; (3) molecular weight of 90,000 ~ 200,000, 2δ weight of molecular weight 1,000 ~ 3,000,000, 5S or more. 2. The styrene strip resin composition according to item 1 of the patent application scope, wherein the content of the acrylate strip monomer polymerization unit is 1 to 10 weight χ. 3. According to the styrene strip resin composition described in Item 1 of the patent application, the acrylate strip monomer is pseudo-butyl acrylate. Page 29 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ..................... ^. ¾ .... ............ Order ............ ^ ^ (Please read the notes on the back before writing this page)