TW322492B - Thermal-resistant styrene resin composition modified by rubber - Google Patents

Abstract

A thermal-resistant styrene resin composition comprising a continuous matrix phase of styrene copolymer (A) having imino group, and 5 to 45 wt.% relative to the resin composition of rubber particles dispersed in the continuous matrix phase, the styrene copolymer (A) having imino group being obtained by polymerizing 89 to 20 parts by weight of styrene monomer, 10 to 50 parts by weight of acrylonitrile, 1 to 30 parts by weight of maleimide monomer and 0 to 40 parts by weight of other copolymerizable monomers, and the rubber particles comprising: (1) 98 to 70 wt.% relative to the total amount of the rubber particles of emuslfied rubber particles (B) having weight average diameter of 0.05 to 0.8 (muon)m, and (2) 2 to 30 wt.% relative to the total amount of the rubber particles of bulk (or solution) rubber particles (C) having weight average diameter of 0.1 to 10 (muon)m.

Description

^ 224d2 A7 B7 5. Description of the invention (丨) The present invention is damaged by a rubber-modified heat-resistant styrene resin composition, which refers to a type with good impact strength, tensile strength, fluidity and heat resistance Resin composition with good physical properties such as good balance, and difficult to produce chess pollution during molding. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) It is mainly because of its good moldability, physical properties and mechanical properties, especially the good appearance and gloss of the molded products is a big wait; but as users continue to improve the quality requirements In general, there is still a need for improvement in impact strength and heat resistance of general styrene strip resins. At present, in order to improve the gate appearance of injection molded products by processing and molding manufacturers, and adopt fully automated production, pinhole type pouring is gradually adopted. The pin gate is used for injection molding. Because this type of pinhole gate is very small, the viscosity of the resin melt that is relatively difficult to flow through the hole is injection molded. Therefore, the requirements for improving the fluidity of styrene resin are also increasing; On the one hand, although the automatic injection molding can reduce the manpower requirements and rapid mass production, but the styrene strip resin often has oily materials during injection molding Precipitation and sticking to the mold cause pollution of the mold. In order to manage the contaminated chess tools, it is often necessary to interrupt automated production, thereby reducing the efficiency of production; therefore, how to make the styrene strip resin have good impact strength, heat resistance, The balance of tensile strength, fluidity and other physical properties, and it is not easy to produce chess equipment pollution, is a problem that needs to be improved in this field. Love is, the main purpose of the present invention is to provide a rubber-modified heat-resistant styrene strip resin composition that has good balance of physical properties such as impact strength, heat resistance, tensile strength, fluidity, and is less prone to mold contamination. __ 第 03 页 _ This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 322492 A7 A7 B7 Fifth, the description of the invention (2) The rubber-modified heat-resistant styrene resin composition, the main components of which include: the continuous matrix phase of the styrene strip copolymer (A) containing an imidate group, and the continuous matrix phase dispersed in the continuous matrix phase and occupying the resin composition 5 ~ 45 heavy MX rubber particles; the above-mentioned styrene-coated copolymers containing amide imide groups (A) are composed of styrene strip single plaques, acrylonitrile strip monomers, malealdimine strips and others It can be copolymerized by polymerization; and the rubber particles contain (1) 98 ~ 70 weight X of gold rubber particles, and the weight average particle diameter of 0.05 ~ 0.8 emulsified rubber particles (B); and (2) account for all 2 ~ 30 weight X of the rubber particles, and the bulk (or solution) acorn particles (C) with an average particle size of 0.1 ~ 10 mm, which is grafted onto the emulsified rubber particles (B) and consists of The average thickness of the rigid styrene strip copolymer obtained by the polymerization of single-shelled snakehead is 30 ~ 160 A, and the graft is The average thickness of the hard styrene bar copolymer on the bulk (or solution) oak murine particles (C) and polymerized by graft polymerized monomers is 90 ~ 300 A, and the styrene bar monomer contained in the above resin composition The total content of dimers and trimers formed by the skull and / or acrylic eye strip monomers is below 20,000 ppb. The styrene bar copolymer containing aldimine groups of the present invention (A) You consist of 89 to 20 parts by weight of styrene bar, 10 to 50 parts by weight of acrylonitrile bar, 1 to 50 parts by weight of maleimide bar 30 parts by weight, and optionally copolymerizable monomers from 0 to 40 parts by weight, which can be obtained by block, solution, suspension or emulsion polymerization methods, of which block or solution polymerization methods are preferred The weight-average molecular weight of the aforementioned styrene bar copolymer (A) containing awakening imine groups is between 60,000 and 400,000, preferably between 80,000 and 300,000; the paper size of the benzene page 04 of the present invention is applicable to Chinese national standards (CNS) A4 specification (210X297 mm) I ------. 丨 1 -Policy-- (Please read the precautions on the back before filling out this page), -ίτ Printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs簟 SZ2492 Α7 Β7 5. Description of the invention (3) The styrene strip in the ethylene strip copolymer (A) can be: styrene, α_methylstyrene, p-gas styrene, p-third butylbenzene Ethylene, p-methylstyrene, tan-chlorostyrene, m-cyanostyrene, 2,5-difluorostyrene, 3,4_dicyanostyrene , 2,4,6-tribromostyrene, 2,5-dibromostyrene, etc. Among them, styrene or α-methylstyrene is preferred. The acrylonitrile strip monomers used in the present invention may be: acrylonitrile, (1-methacrylic acid, etc., among which propylene is preferred; the copolymerizable monomer used in the styrene strip copolymer (A) of the present invention) Waist can be: (meth) acrylate strip monomer, acrylic acid, methacrylic acid, anhydrous maleic acid, etc., where (meth). Acrylic strip monosac can be: methyl methacrylate, methacrylic acid Ethyl ester, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, hexyl methacrylate, dodecane methacrylate, 2-hydroxyethyl methacrylate Sleep, glycidyl methacrylate, dimethyl cyanoethyl methacrylate, methyl acrylate, butyl acrylate, etc., among which methyl methacrylate, butyl acrylate is preferred. Malay used in the present invention Fermented imine strips can be: maleimine, H_methylmaleimine, N-isopropylmaleimide, N-butylmaleimide, N-hexylimide Laimide, N-octylmaleimide, N-dodecylmaleimide, N-chenhexylidene Clenoximine, Η-phenylmaleimide, Ν-2,3-tolylmaleimide, Η-2,4-tolylmaleimide, Ν-2,3-ethylbenzene Basic maleimine, N-2,4-ethylphenylmaleimide S, N-2,3-butylphenylmaleimide, N-2,4-butylphenylmaleimide Amine, Ν-2,6-tolylmaleimine, H-2 Page 05 This paper size is applicable to China National Standard (CNS) Α4 specification (210X297mm) (Please read the precautions on the back before filling in this Page) Binding · Order_ Printed A7 B7 by Beigong Consumer Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of Invention (Bucket), 3-cyanophenylmaleimine, N-2,4-cyanophenylmaleimide Imine, N-2,3-bromophenylmaleimide, N-2,4-bromophenylmaleimide, etc. Among them, N-phenylmaleimine is the best. The preferred preparation method of the styrene strip copolymer (A) containing aldimine groups of the present invention can be accomplished by a continuous block or solution polymerization reactor. The upper reactor includes: a column flow Reactor, complete metal mixing (CSTR) reactor, or a tube containing static mixing elements. Etc., among which the gold-mixed reactor is preferred; the number of upper reactors can be one, or two or more than two can be used in combination to crack the iminium group-containing styrene-based copolymer of the present invention. (A), thermal polymerization or polymerization initiator can be added to the reaction, the polymerization initiator includes pervaporated acetyls, pervaporated esters, peroxyketals, and gasified esters , As well as azo compounds with nitro and hexane, etc., the addition amount of the aforementioned polymerization initiator is usually based on 100 parts by weight of 0.01 to 1.0 parts by weight of a single compound! H. The reaction temperature of the above reactor is controlled at 80 ~ 200 TC, the best control is in the range of 90 ~ 160C, and the pressure of the reactor is controlled between 1 ~ 5 kg / cma, as for the time that the raw material solution stays in the reactor, it should be 1 ~ 5 hours In addition, in order to control the molecular weight of the polymer, a transfer agent such as n-dodecyl mercaptan, third-dodecyl alcohol, terpinolene, etc. can be used. After the conversion rate of the polymer monomer is 40 ~ 80 reset! I; After that, usually the obtained copolymer solution is heated to the highest temperature with a preheater, and then the unreacted monomer and volatile matter are removed by the devolatization step In general, the devolatilization step can use the device of decompression degassing tank or the degassing device of the extruder to remove volatiles, then __page 06_; _ This paper size is applicable to China National Standard (CNS) A4 specification ( 210X297mm) (Please read the precautions on the back before filling in this page) Order the A7 ____ B7 printed by the Beigong Consumer Cooperative of the Central Escalation Bureau of the Ministry of Economic Affairs. 5. Description of the invention (5) Collect it into the recovered liquid with a condenser, After removing the water in the recovery liquid, it is used as the raw material solution again; the volatile volatile polymer melt is extruded into the kiln to obtain the aldimine group-containing styrene strip copolymer (A) of the present invention. The rubber particles dispersed in the continuous matrix phase of the styrene bar copolymer (A) containing an imide group account for 5 to 45 weights of the resin composition! 1, and the rubber dispersed in the matrix phase ® particles are in the form of graft copolymers of rubber husks, that is, they contain graft copolymers of emulsified rubber particles (B) and graft copolymers of block (or solution) rubber husk particles (C). The graft copolymer made of emulsified rubber mash particles (B) of the present invention is in the presence of 45 ~ 85 parts by weight of diene strip rubber mash emulsion, and 90 ~ 50 parts by weight of styrene strips; propylene 丨ϋ Shito monomer 10 ~ 50 weight S5, and other copolymerizable monomer M 0 ~ 40 weight X single skull mixture 55 ~ 15 parts by weight, graft polymerization to obtain emulsified rubber particles with a weight average particle size of 0.05 ~ 0.8 Ze (B) graft copolymer emulsion, or a graft copolymer emulsion made of rubber particles (B) with a bimodal distribution of particles with different weight-average particle diameters, and then coagulated, dehydrated, dried, etc. Step, and cracked into a powdered granular emulsified rubber particles (B) graft copolymer; the above diene Shi rubber emulsion refers to a conjugated diene monomer containing 100 ~ 60 weight SX, and 0 ~ 40 weight X The homopolymer * formed by the copolymerization of unsaturated monomers, or its copolymer, the aforementioned conjugated diene monomer can be expressed by the following formula:

RI CHa = C-CH = CH »where R can be a hydrogen group, a methyl group or an atmosphere group, etc., and the copolymerizable unsaturated monomer can be a single styrene strip, a propylene strip monomer, methacrylic acid ____Page 07__ The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297mm) (please read the precautions on the back before filling out this page) Binding · Order 322492 A7 B7 Central Ministry of Economic Affairs Printed by Beigong Consumer Cooperative V. Description of Invention (G) Zong Shan Yu, Acrylic Ester Shan Yu or a mixture thereof. The diene strip oak emulsion used in the present invention may be polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-methyl methacrylate copolymer, isoprene M-diene-butyl acrylate copolymer, etc .; the above diene strip rubber emulsion can be directly polymerized into the form of weight average particle diameter 0.05 ~ 0.8 by the aforementioned single bun, or it can be polymerized into small particle size of 0.05 ~ 0.18 / m first After the rubber emulsion, the small rubber with a particle size of 0.05 ~ 0.18_ is enlarged into a rubber emulsion of 0.2 ~ 0.8 by the traditional method of rubber enlargement. The aforementioned rubber enlargement method can be the addition of organic acids or gold salts or carboxylic acids. The chemical magnification method based on the polymer agglomerate, the mechanical magnification method using mechanical mixing or the frozen E method, etc .; the high molecular aggregating agent used in the aforementioned chemical magnification method may be, for example, butyl acrylate-methacrylic acid copolymer. The preparation of the graft copolymer made of the above-mentioned emulsified oak murine particles (B) usually uses the conventional graft polymerization technique in the presence of a rubber-like polymer, together with styrene strip monomers, acrylonitrile strip monomers, and The copolymerizable monomer mixture added as needed for graft polymerization, using chemical bonding or grafting of at least one of the aforementioned graft monomers to form a rigid styrene strip copolymer on the diene strip rubber; according to the order The ratio of the skull to the diene rubber and the polymerization conditions can simultaneously obtain the polymer grafted on the diene rubber and the desired graft thickness; usually the polymerization temperature of the graft polymerization reaction, the type of the initial rubber, the rubber The physical and chemical properties of the polymer (such as rubber swelling library, copolymerization components and content of rubber), particle size, monomer addition rate, pre-impregnation degree of monomer and rubber, chain transfer, emulsifier Various factors such as dosage and type will affect the graft thickness of the hard styrene strip copolymer. Page 08 (please read the precautions on the back before filling in this page). Clothing · Order 'This paper standard is applicable to China National Standard (CNS) A4 specification (210X297mm) A7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs _B7__ V. Description of the invention (7) Part of the hard styrene copolymer obtained by emulsification graft polymerization «polymerization is partially chemically bonded to the diene rubber, and the other part forms a free copolymerization (Free copolymer); it is also observed with the "photograph of sub-display mirror" of the rubber graft copolymer. The hard styrene copolymer (Occlusion) can be encapsulated in the rubber yoke particles, or not encapsulated at all. The encapsulation degree of the hard styrene copolymer depends on the physical properties; another part of the hard styrene strip copolymer is grafted on the surface of the rubber particles. This part of the hard styrene strip copolymer is to constitute the emulsification of the present invention The grafted thickness layer of the rubber particle (B) graft copolymer. The initial cocoon or catalyst added in the previous graft polymerization reaction can usually be in the range of 0.01 ~ 5.0 replacement parts of the polymerization monomer, preferably 0.1 ~ 3.0 parts by weight; the amount of addition depends on the single bun and the required Depending on the polymerization conditions, the aforementioned initiator can be added in increments, which facilitates the progress of the graft polymerization reaction. Furthermore, the molecular weight of the aforementioned graft polymer can be controlled by the temperature of the graft polymerization reaction, and / or it can be adjusted with a relatively small proportion of conventional molecular weight agents such as mercaptans, halogenating agents, or postenes. Examples of this molecular weight compound are more specific: n-dodecyl mercaptan, third-dodecyl thiol, and α-methylstyrene dimer. The above-mentioned graft polymerization can use the monomer mixture to continuously or incrementally add to the polymerization system, and it is best to simultaneously or incrementally add the starting thin I; the former initiator can use various conventional Emulsion free radical polymerization reaction start. For example: peroxide (peroxy), azo compound or persulfate compound; suitable starting point for pervaporation example: cumene meet gasification (di-cumyl peroxide) 、 Tert-butyl-per- _page 09___ The paper size is applicable to China National Standard (CNS) A4 specification (210X297mm j ~ (please read the precautions on the back before filling in this page)

A7 B7_ printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Development of the Ministry of Economic Affairs V. Description of the invention (『) oxide, benzoyl peroxide, cumene hydroperoxide, third Tert-butyl hydroperoxide (tert-butyl hydroperoxide), etc. The polymerization reaction of the aforementioned diene-to-hydroperoxide emulsion and the single-mixture is stirred under an inert gas skeleton of 20 to 100 t: it can also be pressurized to 0. ~ 100P.SIG; 90% of the monomers are polymerized in the reaction, the polymerization time usually takes 2 ~ 10 hours, and preferably 3 ~ 8 hours. The styrene strip monomers, acrylonitrile strip monomers and copolymerizable monomers used in the graft copolymer made of emulsified ladder particles (B), in addition to the copolymerizable monomers, may further include maleimine Except for the strip monomers, the rest are the same as the monomers in the styrene strip copolymer (A) containing aldimine groups, which will not be repeated here. Through the aforementioned graft polymerization reaction, a weight average particle diameter of 0.05 to 0.8% of the rubber graft copolymer emulsion, and the average of the hard styrene bar copolymer grafted on the emulsified rubber mash particles (B) The thickness is 30 ~ 160 A, the preferred weight average particle diameter is 0.06 ~ 0.6 埤, the graft thickness is 40 ~ 140A, more preferably 40 ~ 100 A; when the graft thickness is less than 30A, the impact strength of the resin and The fluidity becomes worse. If the graft thickness is higher than 160 A, not only does the resin's fluidity become poor, but its impact strength improvement effect is not good. The graft copolymer emulsion of the upper emulsified rubber particles (B) must be added with an appropriate coagulant for coagulation. Generally, the coagulation used includes sulphuric acid, acetic acid, and age-earth Jinjin salt, such as calcium chloride Calcium salt, Magnesium oxychloride, Magnesium salt of magnesia, and Aluminum salt of aluminum sulfate. Among them, IS Tu Jinyou salt is the best. The polymer slurry after coagulation is dehydrated by dehydration process, and then _____ 第10 pages __ This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) _ (Please read the precautions on the back before filling this page)

A7 _B7_ Employee Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 _B7_ V. Description of the invention (?) After drying, the graft copolymer of powdered and granular emulsified oak grain (B) can be prepared. The graft copolymer made of the block (or solution) rubber particles (C) of the present invention is composed of 5 to 30 parts by weight of rubber mash polymer and a mixture of 100 parts by weight of single stern, to It can be obtained by block polymerization and / or solution polymerization. The above-mentioned mono-mixture contains 90 to 50 parts by weight of styrene moieties, 10 to 50 parts by weight of acrylonitrile strips, and 0 to 40 parts by weight of copolymerizable monomers. When the conversion rate of the polymerization reaction reaches 40 ~ 90 reset! K, the copolymer solution is then subjected to a devolatilization step to remove unreversed monomers and volatiles, and the weight average particle size can be prepared from 0.1 to 10. Graft copolymers of classical block or solution rubber particles (C). The graft copolymer of block (or solution) rubber particles (C) of the present invention can be completed by a tandem block or solution polymerization reactor. The upper reactor includes: a column flow reactor, Completely mixed (CSTR) reactors, or tube reactors with static mixing elements, etc., which is preferably a gold-mixed reactor; the number of the above reactors can be one value, or two or more values can be used in combination ; In the production of the graft copolymer of the block (or solution) rubber particles (C) of the present invention, a polymerization initiator may be added to the reaction, and the polymerization initiator includes pergasification enzymes and pergasification esters , Over-vaporized ketals, gasified phosphoric acid esters, and azo compounds with nitro and cyclohexane rings, etc. The amount of pre-polymerization initiator added is usually 0.01 based on 100 parts by weight of monomer ~ 1.0 weight χ. The reaction temperature of the above-mentioned anti-molecular pseudo-control is in the range of 80 ~ 200 t :, preferably in the range of 90 ~ 16010, and the pressure of the reactor is controlled in the range of 1 ~ 5 __ 第 11 页 _ This paper size is suitable for Chinese countries Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling in this page) Order A7 B7 printed by the Consumer Labor Cooperative of the Central Standards Bureau of the Ministry of Economy V. Description of invention (丨 〇) kg / cia In the meantime, the time for the raw material solution to stay in the reactor should preferably be 1 to 5 hours; in addition, in order to control the molecular placement of the polymer, for example, n-dodecyl alcohol and third-dodecyl sulfur can be used. Transference of alcohol, terpineolene, etc. After the polymerization of the polymer is completed, the resulting copolymer solution is usually heated to the highest temperature in a preheater, and then the non-inverted monk and volatiles are removed in the devolatization step. Generally, the devolatization step can use decompression The device of the gas tank or the degassing device of the extruder removes the volatile matter, and then collects it into the recovery liquid by the condenser, and removes the water in the recovery liquid, and then uses it as the raw material solution again; The polymer melt is extruded and granulated to obtain a block (or solution) graft copolymer of rubber particles (C). The rubber polymer suitable for the graft copolymer of the block (or solution) rubber mash particles (C) of the present invention is conjugated diene rubber®, preferably such as butadiene rubber, isoprene rubber, Chloroprene rubber, etc .; among them, the types of butadiene rubber include high cis (Hi-cis) content and low cis (Low-Cis) content; among high cis rubber, the cis (Cis ) / Vinyl (Vinyl) has a typical weight composition of 94 ~ 985S / 1 ~ 531, and the rest of the composition is a trans (Trans) structure, its Mooney viscosity is between 20 ~ 120, and the molecular weight range is 100,000 ~ 800,000; low order In the type of rubber mash, the typical weight composition of cis / vinyl is 20 ~ 40JK / 1 ~ 20: «, the rest is a trans structure, and its Mooney viscosity is between 20 ~ 120; other suitable glue materials are: propylene Guess / butadiene rubber, styrene / butadiene rubber, or a mixture of the above-mentioned different rubbers; the styrene / butadiene copolymerized rubber suitable for the present invention can be a two-stage type (di- block) copolymerization, three-stage (tri-block) page 12 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) Policy · Order A7 __B7 printed by the Central Consortium Bureau of the Ministry of Economic Affairs Beigong Consumer Cooperative V. Invention Description (I 丨) Copolymerization, Random Copolymerization (rando ·) or Star type copolymerization (star type); the styrene / butadiene copolymer rubber has a styrene / butadiene weight ratio range of preferably 5/95 to 80/20, and a molecular weight range of preferably 50,000 ~ 600,000; the rubber sleep suitable for the present invention is preferably a butadiene rubber waist and styrene / butadiene rubber, among which butadiene rubber is better. In the graft copolymer of the block (or solution) rubber particles (C) of the present invention, a part of the hard styrene strip copolymer polymerized by the graft monomers is chemically bonded to the rubber polymer, The other part is formed as a free copolymer (free copolyner); and the rubber particles (C) can encapsulate the above-mentioned hard-coated styrene strip copolymer, and its particle size is mostly between 0.01 ~ 0.5%. The number of encapsulation inside the waist particles can be one (single encapsulation) or more than a few degrees; another part of the hard styrene copolymer is grafted on the surface of the rubber particles (C), and this part of the hard styrene strip is copolymerized The substance is a grafted thickness layer of the graft copolymer carrying the block (or solution) rubber particles (C) of the invention. The aforementioned control of the graft thickness can depend on the temperature, residence time, rubber properties [such as molecular weight, polymerization composition, and the 1,2-vinyl content of the microstructure], bond transfer agent and The type, amount, type of starting agent, reactor design, stirring speed, and specific operating conditions before and after reverse rotation are achieved. The graft copolymers made of block (or solution) rubber particles (C) of the present invention are used in styrene strip monomers, acrylic eye strip monomers and copolymerizable monomers, in addition to copolymerizable monomers. It further contains maleimine strips, and the rest are the same as the monomers in the styrene strip copolymer (A) containing fermentimines. Page 13 This paper scale is applicable to the Chinese National Standard (CNS) Μ specifications (210 X297 public daughter) ~ '(please read the precautions on the back before filling this page)

A7 B7 S22482 ---------V. Description of the invention (丨 stand) (please read the precautions on the back and then fill out this page) The particles (C) obtained by the polymerization reaction of block (or solution) ) Graft copolymer, the weight average particle size of the prepared rubber mash is 0.1 ~ 10 / «, and the average thickness of the hard styrene-based copolymer grafted on the rubber should be 90 ~ 300 A, preferably the weight average The particle size is 0.2 to 7 μm, and the graft thickness is 100 to 300 A; when the graft thickness is less than 90 A, the impact strength of the resin becomes poor. The heat-resistant styrene strip resin composition modified by the rubber waist of the present invention consists of a graft copolymer containing a imidate-containing styrene strip copolymer (A), emulsified rubber particles (B), and a block (or solution ) The rubber particles (C) are obtained by mixing and extruding the graft copolymer; the emulsified rubber plaque particles (B) account for 98 ~ 70 weight iX of all the rubber koji particles, and the block (or solution) rubber fall particles (C) account for all 2 ~ 30 weight X of the rubber grain particles, preferably the emulsified rubber particles (B) account for 97 ~ 75 weight of all the rubber sleeping particles 3 ;, block (or solution) rubber particles (C) account for 3 of all rubber particles ~ 25 weight X, when the block (or solution) rubber particles (C) is contained less than 2 weight ίΚ, the impact strength of the resin is not good, this content is higher than 30 weight 3 !, the resin's tensile strength and Poor heat resistance. Printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs. In addition, the present invention has learned that the total content of dimers and trimers of styrene strip monomers and / or propylene strip monomers contained in the resin composition should be within Below 20,0 00 PPi, when the aforementioned content is higher than 20,000 ρρβ, the resin will visually deposit oil on the surface of the chess tool during processing (Plate out phenomenon), so it is not suitable for long-term processing and injection; as for the invention in this invention Among the dimers and trimers of styrene strip monomers and / or propylene strip monomers, dimers include: AS, AA and SS, and terpolymers include: AAA, SSS, AeS, SaA, where A Stands for acrylonitrile strip monomer, S stands for styrene plaque. Page 14 This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm). The A7 B7 is printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention () The average of the rubber particles in this invention Particle size, Su refers to the application of ultra-thin cut resin or emulsion, after dyeing, photographed with a transmission electron microscope at a magnification of 10,000 times, and about 200 to 1000 acorn dispersion particles photographed in phase H, measured separately The particle size is determined by the following formula: weight average particle size Di Σ ni D i 4 rubber weight average particle size =-Σ η IDI 3 ηι = rubber particle diameter is D, the number of rubber particles grafted by the present invention The average thickness of the hard styrene-based copolymer on the rubber particles. Dissolve the resin in acetone and separate the soluble components in a careful manner. Then disperse the resulting gel in acetone to form a dispersion, and then drop a few drops Disperse the droplets into the main agent of the resin adhesive of the Chen gas resin, and fully mix the main resin and the condensate, and then dry in a vacuum to remove the acrylic acid. Harden it, Di can get it A test piece in which mash is well dispersed in Jing gas resin. The ring gas resin stripping agent used here is a commercially available S under the trade name Ara Id ite Rapid (manufactured by Ciba-Geigy Corporation). The prepared test Η was dyed with four gasifications (0s0 «), cut with a microtome, and then photographed with a 60,000 times penetrating dipper microchain: after dyeing with four gasification osmium, the oak hull The resin and the ring gas resin are dyed black, and the grafted layer of the hard-coated styrene strip copolymer is not dyed but white. The rubber dispersion particles photographed in the phase Η are more than 25 halls. Paper J describes the rubber and the shape of the grafted layer, then cut and weighed, and the grafted layer can be converted according to the equivalent area of the unit weight, and then the area is divided by the circumference of the sleeping particle to obtain the particle diameter of the rubber particle ( D,) Thickness layer (t,), and find the average thickness according to the following formula: Page 15 This paper size is applicable to China National Standard (CNS) 84 specifications (210X297 mm) ------ ^- -^ I Pack-- (please read the precautions on the back before filling in this page) Order A7 _B7_ Printed by the Consumer Cooperative of the Central Bureau of Economics and Trade of the Ministry of Economic Affairs Ⅴ. Invention Description (丨 Dou) η η Σ Diti / Σ Di3 1 »1 i = 1 The present invention can further add a phenol strip or thiopropionate oxidation inhibitor as needed to obtain a resin composition with predetermined characteristics , The present invention can also appropriately add light stabilizers, ultraviolet absorbers, fillers, colorants, slip agents, plasticizers, and electrification inhibitors to improve the moldability of the styrene strip resin; in addition, the present invention can also be mixed and polymerized Resins for metal alloys, such as: polyacrylic acid ester, polyacrylic acid, polyester (PET, PBT), polyphenylene ether, polyvinyl radon, polymethyl methacrylate, ethylene-methyl methacrylate copolymer , Polypropylene, styrene-butadiene block copolymer, hydrogenated acrylonitrile-butadiene copolymer, argonated styrene-butadiene block copolymer, etc., its amount is generally relative to the resin 5 to 200 parts by weight of 100 parts by weight of the composition. In order to obtain the resin composition of the present invention, the typical mixing method is: dry-mixing with a commonly used Hannell mixer, followed by, for example, an extruder mixer, kneading Machine or Banbury mixer. The resin composition of the present invention is suitable for injection molding, extrusion molding, compression molding, blow molding, thermoforming, vacuum molding, and hollow molding Wait In order to explain the present invention in more detail, the following examples and physical properties are used to explain the following. Unless otherwise stated, the ingredients of the following composition are based on parts and percentages of the weight of the gold component in weight percentages. The following examples are given to illustrate the present invention in detail, but the scope of the present invention is not limited to these examples. &Lt; Preparation Examples &gt; (Please read the precautions on the back before filling out this page) _ The 16th hundredth paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) ^ 22492 B7 5. Description of the invention (丨 5) &lt; Preparation Example I-1 &gt; copolymerization of styrene strips containing imino groups Preparation of compound (A-1): Mix 68 parts of styrene X and 22 parts of acrylonitrile! And 10 parts of N-phenylmaleimide 10 parts by weight of X, and then weigh 0.02g of stearyl aldehyde The ", third-dodecyl mercaptan, and the volatiles removed by the reaction described below are condensed and the recovery liquid formed after condensation is combined as a" feeding liquid to supply the internal temperature maintained at 145 t: and the volume of 45 liters. A continuous kettle reactor with agitator, and Ratio of toluene the reaction mixture is maintained at 15¾, while the polymerization ratio is maintained at 56S5. When the reaction liquid is removed by a devolatilization device, particles of styrene strip copolymers containing amide imide groups can be obtained; on the other hand, the removed volatile components are condensed by a condenser as a recovery liquid, and the The aforementioned raw material mixed liquid is mixed and used again; the amount of the 31st-dodecyl mercaptan is adjusted to prepare a iminium group-containing styrene bar copolymer (A-1) having a melt flow index of 1.0. <Preparation Example I-2> Preparation of Aldimine Group-Containing Styrene Strip Copolymer (A-2): Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Styrene 68 weight J :, acrylonitrile 22 weight 5K and phenylmalealdimine 10 weight; S raw materials are mixed, and then ethylene distearate aldolamine 0.025 weight! Ί, third-dodecyl Mercaptan and the recovered liquid formed by condensation of the volatiles removed by the reaction described later are combined as a bait feed liquid to be fed into a continuous-type kettle-type reactor with an agitator whose internal temperature is maintained at 108 t and whose volume is 45 liters. , And the proportion of toluene in the reaction solution was kept at 1555, and the polymerization rate was kept at 55¾. After the reaction liquid is removed by the devolatilization device, the aldehyde-containing page 17 can be obtained. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). -_? Z_ V. Description of the invention (丨 ι) Particles of the imine-based styrene strip copolymer; on the other hand, the volatile components removed are condensed by a condenser as a recovery liquid. They are also mixed with the aforementioned raw materials The liquid is mixed and used again; in this way, the reaction rate is adjusted from the amount of benzaldehyde pergasified, or the amount of the 31st-dodecyl thiolease is adjusted to make the imidate group-containing compound with a melt flow index of 0.9. Styrene bar copolymer (A-2). &lt; Preparation Examples 1 to 3 &gt; Preparation of styrene strip copolymer (A-3) containing amide imide groups: 68 weight styrene, 22 weight J of acrylonitrile; and N-phenylmaleimide 10 Re-suspension: Mix the raw materials of S, and then combine the ethylene glycol distearylamine 0.025 weight χ, the third-dodecyl mercaptan, and the volatiles removed by the reaction described below after condensing to form the recovery liquid formed by condensation The bait feed solution was fed into a continuous Burmese reactor with a stirrer maintained at 155 C and a capacity of 45 liters, and the toluene ratio in the reaction solution was maintained at 15X and the polymerization rate was maintained at 57X. When the reaction liquid is removed by the devolatilization device, the particles of the styrene strip copolymer containing aldimine groups can be obtained; on the other hand, the removed volatile components are condensed by the condenser as the recovery liquid, and continuously The raw material mixed liquid is mixed and used again; the amount of the 31st-dodecyl mercaptan is adjusted to make a styrene-toluene copolymer (A-3) containing an imide group containing a melt flow index of 1.3. &lt; Preparation Example 1-1 &gt; Production of graft copolymers of emulsified rubber mash particles (B-1): Cheng weight "pine 1, 3-butadiene 95.0 acrylonitrile 5.0 potassium peroxyacid solution 15.0 page 18 This paper scale is applicable to the Chinese National Standard (CNS> Α4 specification (210X297mm) (please read the precautions on the back before filling in this page). Packing. Order A7 _B7 5. Description of the invention ((7) pyrophosphate m 3.0 oleic acid Potassium 1.5 Steamed water 140.0 Third-dodecyl alcohol 0.2 According to the above formula at 65t: reaction temperature for 12 hours, the conversion rate is 94%, the solid content is about 4 (U, weight average particle size is 0.1 «η Synthetic rubber emulsion milk. In addition, the following ingredients are used to make a polymer coagulant containing carboxylic acid group: sg_ia_ heavy ray (min η-ethyl acrylate 85 acrylic acid 15 Thirteen-dodecyl alcohol 0 Potassium oleate 2 Sodium dioctyl sulfosuccinate 1 Cumene hydrogen peroxide 0 Formaldehyde sodium hypohydrogenate 0 Steamed water 200 (Please read the precautions on the back before filling this page) Order the Ministry of Economy Printed in response to the above formula at 751C by the Central Bureau of Industry and Fisheries Consumer Cooperatives The reaction was carried out at a temperature for 5 hours to obtain a carboxylic acid group-containing ionomer coagulant with a conversion rate of 9555 and a pH of 6.0. Then, 3 parts by weight of a carboxylic acid group-containing polymer agglomerate (dry weight) was used to enlarge 100 parts by weight Synthetic rubber latex (dry weight), the resulting hypertrophic rubber waist emulsion has a pH value of 8.5 and a weight average particle size of 0.30 / um. Finally, the hypertrophic rubber emulsion is used for graft polymerization according to the following formula To produce graft copolymers of emulsified rubber particles (B-1): __Page 19_ This paper size is suitable for China National Standard (CNS & A4 specifications (210X297 mm) 100,0 25.0 20 200 A7 ____B7_ 5 3. Description of the invention (&amp;) Cheng _iiL Tong Matsu Song Enlarged Rubber Emulsion (Dry Weight) Styrene Acrylonitrile Potassium Oleate Thirteen-dodecyl Mercaptan Cumene Pervaporized Ferrous Hydrogen Aromatic Acid Solution (0.2X) Formaldehyde sodium hyposulfite solution (105!) Ethylenediaminetetraacetic acid solution (0.25¾) Distilled water Add stupid ethylene / acrylonitrile in the above formula to the reaction system within 5 hours by continuous ore addition Polymerization to prepare uncondensed 搛 ® graft emulsion followed by calcium chloride (CaCl ) After coagulation, dehydration, and drying to a moisture content of 2 X or less, the emulsified rubber waist particles (B-1) graft copolymer (rubber content 75 weight X) required by the present invention can be prepared. The weight-average particle diameter is 0.30 fJEBi. <Preparation Example 1-2> Production of graft copolymer of emulsified rubber warm particles (B-2>: Synthetic rubber emulsion made with &lt; Preparation Example 1-1> ( The weight average particle size of the rubber is 0.1%), and it is directly combined with the following table to carry out the graft polymerization and anti-plaque to prepare the uncoagulated rubber mash graft emulsion, which is then coagulated with calcium chloride (CaCU), dehydrated and dried to the moisture content 2S; Below, a graft copolymer of emulsified rubber particles with a rubber content of 50 weight X can be prepared. The weight average particle diameter of the gel particles is 0.1 / Λ. Page 20 This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) ^^ 1 'i nn In i In ϋ— — ^ ϋ — ^ ϋ κ J- ^ (Please read the precautions on the back first (Fill in this page again) Printed Bag A7 of the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs B7 Printed the description of the five inventions (Bei) Synthetic Mash Latex (〇.1 / «) (Dry weight) 100.0 Styrene 75.0 Propylene guess 25.0 Oleic acid evaluation 2.0 Third_ 4 • Dialkyl mercaptan 0.6 Cumene over-gasification 氲 1.4 Ferrous sulfate solution (0.2S!) 8.6 Formazan sub-distillate Sodium acid solution (103!) 8.6 Ethylenediaminetetraacetic acid solution (0.25X) 57.0 Distilled water 200.0 The uncondensed rubber emulsion obtained above and the uncondensed rubber emulsion prepared in &lt; Crack Preparation Example 11-1 &gt; Mixing and coagulating in a weight ratio of 1: 1. The obtained rubber graft emulsion is coagulated and dehydrated with calcium chloride (CaCla), and then dried to a moisture content of less than 235 to prepare the emulsion rubber required by the present invention. Graft copolymer of erroneous particles (B-2) (rubber content 63 weight S!), Its rubber particles The weight-average particle size of the seed is 0.1%, 0.3% bimodal distribution pattern. &lt; Preparation Example Π-3 &gt; Production of graft copolymer of emulsified rubber particles (Β-3): The preparation method of &lt; Preparation Example 1-1 &gt; The difference is the formulation of the graft polymerization reaction And the amount of use, the formula of this graft polymerization reaction is as follows: m_ Tonghuan fat hypertrophy rubber emulsion (dry weight) 100.0 Styrene 22.0 Acrylic eye 8.3 Page 21 This paper scale is applicable to China National Standards (CNS) A4 specifications (2丨 0X297mm) I IJ— n ~ ij. Install I n ϋ 11 n ~~ JL Bing (please read the precautions on the back before filling in this page) Printed A7 ___B7_5 by Beigong Consumer Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs Description of the invention (π) Methacrylic acid methacrylic acid 3.0 Potassium oleate 1.2 Thirty-dodecyl alkyl alcohol 0.2 Isopropylated hydrogen peroxide 0.5 Ferrous sulfate solution (0.2X) 3.0 Formaldehyde sodium hyposulfite solution (10 Magic 3.0 ethylenediaminetetraacetic acid solution (0.2550 20.0 steamed water 200.0 The rubber graft graft emulsion prepared according to the above formula is coagulated with CaCla), dehydrated and dried to moisture content below 2 «, The graft copolymer of the emulsified rubber particles (B-3) required by the present invention Amount 75% by weight X), the weight average particle size of the mash particles is 0.30. &Lt; Preparation Example 1-4 &gt; Cracking of the graft copolymer of emulsified wandering particles (B-4): Take &lt; Preparation Example The preparation method of 1-1 &gt;, the difference is the graft polymerization reaction formula and usage. The graft polymerization reaction formula is as follows: Re-play (please read the precautions on the back before filling this page) BE Dahua rubber emulsion (dry weight) 100. 0 Styrene 8. 4 Acrylonitrile 2. 8 Potassium oleate 2. 0 Thirty-dodecyl mercaptan 0. 1 Cumene pervaporized hydrogen 0 . 2 Ferrous Sulphate Solution (0.2X) 1. 1 Formaldehyde-formulated hyposulfuric acid sales solution (10X) 1. 1 Page 22 This paper scale is applicable to the national standard of China (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (Working solution of ethylenediaminetetraacetic acid (0.25X) 7.3 Distilled water 200.0 The styrene / acrylonitrile in the above formula is added to the reaction system for polymerization in 1 hour by continuous addition, and the obtained rubber Mud graft emulsion is coagulated and dehydrated with urethane nitride (CaCU), and then dried to a moisture content of 2S! Or less, the milk required by the present invention can be prepared Graft copolymer of rubber particles (B-4) (rubber content 90 weight X), the weight average particle diameter of the rubber particles is 0.30%. &Lt; Preparation Example 1-5 &gt; Emulsified rubber particles (B-5) The preparation of the graft copolymer of <Preparation Example 1-1>, the difference is the formulation and use of the graft polymerization reaction, the formulation of the graft polymerization reaction is as follows: (please read the notes on the back first Please fill in the details on this page) Pack-Hypertrophic Rubber Emulsion (dry weight) 100.0 Styrene 300.0 Acrylonitrile 100.0 Potassium oleate 0.5 Thirteen-dodecyl sulfuric acid fermentation 2.2 Isopropylene is printed by the Staff Consumer Cooperative of the Central Bureau of Standards Benzene hydrogen peroxide 5.4 Ferrous sulfate solution (0.250 32.5 Formaldehyde sodium hyposulfite solution (10X) 32.5 Ethylenediaminetetraacetic acid solution (0.25S :) 22.0 Distilled water 200.0 Styrene / acrylonitrile in the above formula Add the ore to the reaction system for polymerization within 8 hours. The obtained rubber graft emulsion is evaporated with calcium (CaCM is coagulated and dehydrated, and then dried to a moisture content of 2X or less. The paper standard is applicable to the Chinese National Standard (CN S) A4 specification (210X297mm) Printed by the Ministry of Economic Affairs, Central Standards Bureau, Beigong Consumer Cooperative Association Α7 Β7 V. Description of the invention (y) Graft copolymers of emulsified chrysanthemum particles (B-5) required for the invention (The content of rubber sleep is 20 weight SO, and the weight average particle size of the rubber sleep particles is 0.30 / «. &lt; Preparation Example H-1 &gt; Production of graft copolymers of bulk (or solution) rubber particles (C-1): Using 0.08 parts by weight of over-gasified benzoylase as an initiator, 6.6 parts by weight Polybutadiene (produced by Asahi Kasei Corporation, trade name Asadene 55AS) is completely dissolved in 74.4 parts by weight of styrene, 25.6 parts by weight of acrylonitrile and 30 parts by weight of ethylbenzene to form a feed solution, which will be The feed solution is entangled and fed into the first reactor with a volume of 45 liters, the reaction temperature is 100 t :, a spiral stirrer with a cooling circulation tube is arranged in the anti-plaque device, and the stirring rate is 150 γρβ, in the first The monomer conversion rate of the reactor is 15X, and the mixture after the first reactor reaction is taken out and sent to the second, third, and fourth reactors in sequence, and 0.1 parts by weight is added to the third reactor In the 31st-12th alkyl mercaptan, the reverse rotation phenomenon is generated in the second reactor. The above-mentioned second, third, and fourth reactors have the same device as the first reactor, but the reaction temperature is 105t in sequence: , 110 t, 125 scoops, and the stirring rate is 270 rpn, 150rpra and llOrpie in sequence; Once the conversion rate of the mixture reaches 603 !, the mixture is taken out and sent to the devolatilization device to remove unreacted monomers and volatiles, and then it is extruded and granulated to obtain block (or solution) rubber particles (C-1) The graft copolymer, the weight average particle diameter of the rubber particles is 0.95_, the rubber waist content is 10 weight; ϋ. &lt; Preparation Example M-2 &gt; The production of graft copolymers of bulk (solution) rubber particles (C-2): According to the preparation method of &lt; Preparation Example 1 &gt;, the difference is that it is the size of the paper on page 24 Applicable to China National Standard (CNS) Α4 specification (210Χ297mm) (please read the precautions on the back before filling in this page) Pack. Order A7 B7 printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of Invention (u) The over-gasified benzoyl nitrate of the starter is 0.12 weight χ, the monomer conversion rate of the first anti-plaque device is 16 J; and the rotation speed is 140 rp ·, while the temperature of the second reactor is 110C and the rotation speed is 300 rp · After extruding and granulating, the graft copolymer of block (or solution) oak hull particles (C-2) can be prepared. The weight average particle size of the oak murine particles is 0.75 / ®, while the rubber The mash content is 10 weight χ. &lt; Preparation Example 1E-3 &gt; Production of graft copolymers of bulk (or solution) rubber particles (C-3): according to the preparation method of &lt; Preparation Example HI-1 &gt;, except that it is used as an initiator The over-gasified benzoyl cyanide is 0.05 parts by weight, and 0.2 replacement parts of the 31st-dodecyl mercaptan are added to the second reactor, and the monomer conversion rate of the first reactor is 19 J !, The rotation speed is 270 rpn, and the rotation speed of the second reactor is 250 rpm. The reverse rotation takes place in the first reactor. After the reaction, it is extruded and granulated, and block (or solution) acorn particles (C- 3) For the graft copolymer, the weight average particle diameter of the rubber particles is 1.0%, and the rubber content is 10% by weight X. &lt; Preparation Example Ϊ-4 &gt; Production of graft copolymers of bulk (or solution) rubber particles (C-4): Use of tri-dodecyl mercaptan and benzoyl peroxide as starters , Dissolve 6.6 parts of polybutadiene (produced by Asahi Kasei Corporation, trade name Ba 33 (^ 1 ^ 5545), and dissolve it in 74.4 parts by weight of styrene, 25.6 parts by weight of acrylonitrile, and 30 parts by weight In ethylbenzene to form the feed solution, the feed solution is then entangled and fed into the first reactor with a volume of 45 liters, the reaction temperature is 95C, and the reactor is equipped with a spiral stirrer with cooling circulation tubes , Its stirring rate is 120rp », the conversion rate of monomers in the first reactor page 25 This paper standard is applicable to China National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling in this Page) Order A7 ^ 22492 ____B7_ Fifth, the description of the invention (Μ ·) is 14S !, the mixture after the first reactor reaction is taken out and sent to the second, third, and fourth reactors in sequence, at the same time in the first Add 0.08 parts by weight of 31-dodecyl mercaptan in the second reactor. Produced in two reactors, the equipment of the second, third, and fourth reactors is the same as that of the first reactor, but the inverse temperature part is 1051, 115 t, 130t in sequence, and the stirring rate is 200 rp · , 150 rpn and ΙΙΟγρβ; as soon as the conversion rate of the mixture is 60J: when, the mixture is taken out and sent to the devolatilization device to remove the unreacted monohydrate and volatiles, after which it is extruded and granulated to make a lump (Or solution) the graft copolymer of the rubber particles (C-4), the weight average particle diameter of the rubber warm particles is 3.3%, and the rubber content is 10 weight X. The resins prepared in the examples and comparative examples of the present invention The test criteria for the physical properties of the composition are as follows: 1. Melt flow index (ΜΙ): According to JIS Κ-7210, test at 22〇10〇〇〇kg, and g / 10 π i π table π 〇. Impact strength (IZOD): tested in accordance with ASTM D-256, expressed in Kg · cb / cb. III. Total content test of dimers and trimers of styrene shit and / or acrylonitrile strip monomers Method: Dissolve the heat-resistant styrene strip resin composition modified by rubber bar in acetone, the resin composition is dissolved Then use Hewlett Packard Company No. 5890 A gas chromatograph with flame male detector for analysis and support. 4. Tensile strength: Page 26 This paper scale is applicable to Chinese national standards (CNS & A4 specifications ( 210 &gt; &lt; 297mm) I ---- ^ --.--- ^ ------ order ------ 1 (please read the notes on the back before filling this page) Economy Printed by the Ministry of Standards and Staff Consumer Cooperatives A7 B7_ Printed and printed by the Central Sample Bureau of the Ministry of Economic Affairs A7 B7_ V. Invention description (s) Tested in accordance with ASTM D-638, expressed in Kg / cBe. V. Softening temperature (Vicat Softening Temperature): Tested according to ASTM D-1525, unit is 1C. 6. Falling Dart Impact (FDI): According to ASTM D-3029, it is expressed in Kg ·. 7. Surface precipitation measurement (Plate out): After injection of the styrene strip resin composition through the Zhenxiong SM-90 injection machine, the injection pressure was 1000 kg / cna, the temperature was 250 t :, and the temperature was 501, and the injection was performed 500 times. Observe whether there are attachments on the surface of the mold. When there is very little oil on the surface of the mold, it is indicated by "O". If there is a small amount of oil on the surface of the chess tool, it is indicated by "Oj. When there is too much oil pollution, it is indicated by" X ". &lt; Examples &gt; &lt; Example 1 &gt; The acetimidate group-containing styrene-based copolymer (A-2) prepared in &lt; Preparation Example I_2 &gt; had a weight X of 64.6, and was prepared from <Preparation Example 1 1> Graft copolymer of the prepared emulsified rubber particles (B-1) 25.4 weight S :, and the bulk (or solution) rubber particles (C-1) prepared by &lt; Preparation Example 1-1 &gt; 10% of the graft copolymer ”! Mix, then add 1.5 parts by weight of the slip agent, and mix and granulate at 240TC with a Wer-ne" & Pfleiderer ZSK 35 extruder. The rubber waist content can be 20% by weight. A heat-resistant styrene strip resin composition modified by rubber koji; then, after injection test at 240T with an injection molding machine of SM-90 manufactured by Miloso Corporation, physical properties were measured and surface appearance was observed, and particle distribution of the composition was analyzed , And the absolute content of the dimers and trimers of vinyl monomers and / or acrylic eye strip monomers, the results are shown in Table 1. ___ 第 27 页 _ This paper size is applicable to China National Standards (CNS) Α4 specification (210X297mm) (Please read the precautions on the back before filling in this page) 袈. Ordered by the Ministry of Economic Affairs A7 B7 printed by the Bureau of Standards Consumer Cooperative V. Description of the invention () &lt; Example 2 &gt; Aldimine group-containing styrene strip copolymer (A-2) prepared from &lt; Preparation Example I_2 &gt; 47.3 weight X, 22.7 weight X of the graft copolymer of the emulsified acumin particles (B-1) prepared by <Preparation Example 1-1>, and the block shape prepared by <Preparation Example 1-1> ( (Or solution) the graft copolymer of rubber particles (C-1) 30 weight X mixed, the remaining molding conditions are the same as in Example 1, the results are shown in Table 1. &lt; Example 3 &gt; will be prepared by &lt; Preparation Example I-1 &gt; 56 weight of the prepared styrene bar copolymer (Al) containing aldimine groups! K, grafting of the emulsified rubber particles (B-1) prepared by &lt; Preparation Example I-1 &gt; The copolymer 24 weight X, and the graft copolymer 20 weight X of the bulk (or solution) oak particle (C-1) prepared by &lt; Preparation Example ϋ 1 &gt; are mixed, and then add 1.5 weight parts of slip And Werner & Pfleiderer ZSK 35 extruder at 240t: mixed and extruded the cracked granules to obtain a heat-resistant styrene-tooth resin composition modified with rubber plait and containing 20 weight X of rubber plaque. A test piece was formed under the extrusion conditions of Example 1, and the physical properties were measured, and the results are also shown in Table 1. &lt; Example 4 &gt; After the raw materials were uniformly mixed according to the formula in Table 1, the operating conditions of Example 1 were used, but The emulsified rubber particles (B) were changed to (B-2). The test pieces obtained were also subjected to various physical property tests. The results are also shown in Table 1. &lt; Example 5 &gt; After mixing the raw materials according to the formula in Table 1, the operating conditions of Example 1 were used, but the emulsified rubber particles (B) were changed to (B-2). 28 pages of this paper are applicable to the Chinese National Standard (CNS) A4 format (210X297mm) (please read the precautions on the back before filling out this page). Printed by the Ministry of Economic Affairs, Central Standards Bureau, Employee Consumer Cooperatives ^ 2492 Α7 Β7 V. Description of the Invention (Li 7) Various physical properties tests were carried out with Tong Zhu, and the results are also shown in Table 1. &lt; Example 6 &gt; After mixing the raw materials according to the formula of Table 1, the operating conditions of Example 3 were followed, but the emulsified rubber particles (B) were changed to (B-2). The results of various physical tests are also shown in Table 1. &lt; Example 7 &gt; After mixing the raw materials according to the formula in Table 1, the operating conditions of Example 3 were used, but the emulsified rubber particles (B) were changed to (B-2), and the block (or solution) rubber particles ( C) Switch to (C-2). The obtained test M was also tested for various physical properties. The results are also shown in Table 1. &lt; Example 8 &gt; After mixing the raw materials according to the formula in Table 1, the operating conditions of Example 3 were used, but the emulsified rubber particles (B) were changed to (B-3), and the test pieces made of the particles were the same Various physical properties were tested and the results are also shown in Table 1. &lt; Example 9 &gt; After mixing the raw materials uniformly according to the formula in Table 1, the operating conditions of Example 3 were used, but the emulsified rubber particles (B) were changed to (B-2), block (or solution) rubber particles (C) Switch to (C-4). The prepared test H was also subjected to various physical property tide tests. The results are also shown in Table 1. &lt; Comparative Examples 1 ~ 7 &gt; After mixing the raw materials according to the formula in Table 1, the test specimens obtained were tested for various physical properties in accordance with the operating conditions of Example 1, and the results are also shown in Table 1. The test results of Comparative Examples 1, 4, and 6 show that the size of the paper on page 29 of the resin group of the present invention is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm) (please read the precautions on the back before filling this page) Installed. Ordered ^ 22492 Printed and printed A7 B7 by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of invention (4) The use of styrene strip copolymer (A-3) for the finished product, its styrene knot and / or acrylic eyes When the total content of dimers and trimers of Shidan is higher than 20,000 ppm, although the flowability of the resin is improved, the surface precipitation of the mold surface is visually defective, so it is not suitable for a wide range of long-term processing and molding, and the softening point of the resin The temperature is also reduced; and the results of Comparative Examples 2 and 3 show that when the graft thickness of the hard styrene strip copolymer grafted on the emulsified rubber particles (B) is less than 30A, or grafted in a bulk (or solution ) When the grafted thickness of the hard styrene copolymer on the rubber particles (C) is less than 90 A, the fluidity of the resin decreases and the impact strength also deteriorates. The results of Comparative Example 4 show that the bulk (or solution ) Oak fall particles account for gold When the ratio of the particles is less than 2 weight, the impact strength of the resin is poor; and the test results of Comparative Example 5 show that when the bulk (or solution) rubber particles (C) account for more than 30 weight X of all the mash particles, the resin The tensile strength is not good, the softening viscosity temperature is also reduced, and it is not suitable for extensive processing. The results of Comparative Example 7 also show that when the grafting of the hard styrene strip copolymer grafted on the emulsified rubber particles (B) When the thickness is higher than 160A, the fluidity of the resin is not good. In contrast to Examples 1 to 9, the present invention, through the limitations of the various components and the amount of use, not only can make the resin composition have good impact strength, high tensile strength, good fluidity, but also maintain good heat resistance of the resin As a result, the appearance of the mold surface has also been improved, and it has industrial use value. You have filed an application for an invention patent according to law. However, the above are just a few of the preferred and feasible embodiments of the present invention. Anyone who is familiar with this technology, and any modifications or changes made in accordance with the spirit of the present invention, should be included in the patent application for this case. Page 30 (Please read the precautions on the back before filling out this page) The size of the paper for binding and binding is applicable to the Chinese National Standard (CNS) A4 (210X297mm) B: SNI ^^^ ii ^ e ^ .AN ^ aslii ^ w08. Thin Lu Yi m 1 massive (or solution) thrashing particles (c) account for the weight of all the rubber particles X Banshang Road Ν-mm 屮 昤 m $ Surface precipitation measurement II mk Falling ball impact strength (FDI) softening viscosity temperature tensile strength Ehrlich Impact Strength Melt Flow Plaque Index 梇 β Slumping w Styrene Strip Copolymer (A) n Types of Block (or Solution) Oak Litter Particles (c) Types of Ru Erpai CIN Yi Su 3 Book Oak Rock Particles Weight average particle size 〇 ™) Weight X Type of emulsified rubber granule particles (B) • if eggplant 5SW mm Teddy C (N Yi 3 book weight average particle size of rubber granules ™) Chongtong X m Chongdong X Visual mold surface (ρρ ·) (kg / c * a) (g / 10 iin) Road «5 ♦ ci / c ·) Μ _ Μ 〇4750 1600 1— * PO cn μ g tsi g 〇Η-» Μ 〇 0.95 03 (― * S ο CO 25.4 &gt; 64.6 Example 1 〇4860 1650 122.5 CO σ &gt; Bing 15.1 o tn? Η- * Μ Ο 0.95 CO 上 ο ίο 22.7 &gt; ίό Example 2 〇10200 1600 124.8 μ on AZλ 00 g 〇1— * Ο 0.95 cn H- * g ο CO to ο &gt; -t— * 56.0 Example 3 〇4845 1500 125.0 with cn ΧΠ ςη ςπ g? t-k s ο ο CO cn 1-k CO ώ 0.1 & 0.3 &gt; ro 59.6 Example 4 〇4780 1800 120.5 CO OO OO &lt; D CJl U1 Cl Λ s ο 0.95 σσ PO ο Η- * S ίο 27.2 3 »ώ ; 42.8 Example 5 〇10050 1500 122.9 to CD OO 17.3 in lu ο t— * ο 0.95 CO ώ 0.1 & 0.3 IS5 00 OO 3Β- t- * 51.2 Example 6 〇10080 1500 122.8 CO &lt; 〇CO o cn H- * g ο ώ ΓΟ CO ο 0.75 ςο ro 0.1 & 0.3 Μ OO OO &gt;-1— »51.2 Example 7 〇10550 1590 123.0 tfi o 17.8 &lt; jy 〇g ο g ο 〇CO CJ1 sc〇 CO δ ο N5 〇〇b〇 &gt; 丄 51.2 Example 8 〇10610 1560 122.7 CO CO 00 — cn CO μ- * g C1 λ σ &gt; cn CO yg 09 ΓΟ CO 0.1 & 0.3 ro oe OO &gt; ί— »51.2 Example 9 X 23000 1450 118.5 CO Oi tn 1— * ro o tn OO 3 g ο &gt;-* g ο o CO cn g 09 Λ g ο OJ 24.0 &gt; 56.0 Comparative Example 1 〇4680 1200 125.8 00 σ &gt; o CO cn OO o CJ1 g ο ώ g 1.00 s OS 丄 ο CO 21.1 h- »68.9 Comparative Example 2 〇4920 1320 '125.7 o OO PO tn? 1—» ΓΟ ο 0.95 09 丄 ο C0 21.1 t- * σ &gt;; OO CO ratio Example 3 X 23050 1280 119.0 ro CO · 〇〇 Office tJl H- * g Ο CO g 1.00 IS &gt; σ9 丄 s ο οο 26.4 &gt; 05 Comparative Example 4 〇10140! 1950 110.2 σ &gt; rvj ho b &gt; Office αι 〇〇 ΓΟ tn ο Λ Μ ο O CO cn σ &gt; cn οσ Η · * g ο 18.0 &gt; Η- * o Comparative Example 5! X 23750 1500 117.2 y tn So OO 05 ςίΐ g? Η- »ο o &lt; 〇cn One CD ώ &gt; do tJl CO 05 Comparative Example 6 〇1400 | 108.3 1 g? OO OO ι— &gt; s? Μ-tg C-'' ㈣ oa ^ B CO til g ο CO O Λ 1— · 〇 example? |

Claims (1)

Scope of patent application (I) A8 B8 C8 D8 Amendment to the application of the Patent Application for Invention Patent No. 8511522 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to amend this type of rubber modified heat-resistant styrene strip resin composition The composition includes: the matrix phase of the styrene copolymer (A) containing aldimine groups, and the rubber particles dispersed in the continuous base phase and occupying 5 to 45 weight of the resin composition! K ; The above-mentioned styrene strip copolymers containing sleeping amine groups (A) are composed of styrene strips with a single core of 89 ~ 20 parts by weight, acrylic eye strips with a single weight of 10 ~ 50 parts by weight, and maleic sleeping iminium strip monomers 1 ~ 30 parts by weight and other copolymerizable monomers are polymerized from 0 to 40 parts by weight; and the rubber particles include: (1) 98 to 70 weight X of all rubber particles, and the weight average particle diameter of 0.05 to 0.8 _ of emulsified rubber Particles (B); and (2) 2 ~ 30% of all rubber particles, and the mass (or solution) rubber particles (C) with a weight average particle size of 0.1 ~ 10%; wherein, the graft is emulsified Hard styrene on rubber particles (B) and polymerized by graft polymerization monomers The average thickness of the material is 30 ~ 160 Α, and the average thickness of the hard styrene strip copolymer grafted on the block (or solution) rubber particles (C) and polymerized by the graft polymerized monomer is 90 ~ 300 Α, the above-mentioned rigid styrene-copolymer copolymer Ye consists of: styrene strip monomer 90 ~ 50 heavy boy! ", Acrylonitrile strip monomer 10 ~ 50% by weight, and other copolymerizable monomers 0 ~ 40% by weight X, and part of the free hard styrene copolymer is formed part of the continuous matrix phase Parts, the total content of dimers and trimers composed of styrene strips and / or acrylonitrile monomers contained in the resin composition and the paper standard on page 31 is applicable to China National Translation Standard (CNS) A4 size (210X297mm) (Please read the precautions on the back before filling in this page) Binding. Order. 4 ABCD 328492 κ, patent application range is below 20,000 ρρπ. 2. The rubber-modified heat-resistant styrene strip resin composition according to item 1 of the patent application scope, wherein the rubber particle diameter of the emulsified rubber particles (B) is bimodal, and the weight average particle diameter is 0.06 ~ 0.15% and 0.17 ~ 0.6 ± 1, and the weight average particle size of the block (or solution) rubber particles (C) is 0.2 ~ 7 / m. 3. The rubber-modified heat-resistant styrene strip resin composition according to item 1 of the patent application scope, in which the average thickness of the hard styrene-to-copolymer grafted on the emulsified rubber particles (B) is 40 to 140 A, The average thickness of the hard styrene bar copolymer grafted on the block (or solution) rubber particles (C) is 100 to 300A or more. 4. According to the rubber-modified heat-resistant styrene strip resin composition described in item 1 of the patent scope, the malealimide strip monomer is N-phenylmaleimide. 5. The rubber-modified heat-resistant styrene strip resin composition according to item 1 of the scope of the patent application, in which the malealimide-based monomer in the composition is 1 ~ 30 weight 3 !. 6. The rubber-modified heat-resistant styrene strip resin composition according to item 2 of the patent application scope, wherein the mass average particle diameter of the block (or solution) rubber particles (C) is 0.2 ~ 1.5wn. Page 32 The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ........................................ ......... order ................ line (please read the notes on the back before filling this page)