TW548308B - Styrenic resin composition - Google Patents

Abstract

This invention provides a styrenic resin composition which possesses excellent tensile strength, initial color phase, processibility and formability, and chemical resistance, and which shows no lacquer-absorbing phenomenon while coating the shaped product. The composition includes: (1) 100 parts by weight of a styrenic resin which comprising 0-95% by weight of a styrenic copolymer (A) and 5-100% by weight of rubbery graft copolymer (B). Said styrenic copolymer (A) includes 20-40% by weight of acrylonitrile unit, and said rubbery graft copolymer (B) is prepared in the presence of dienic rubber by graft polymerization of 40-90 parts by weight of styrenic monomer and 10-60 parts by weight of acrylonitrile-based monomer, based on 100 parts by weight of monomers, and optionally, 0-40 by weight of copolymerizable monomer. (2) 1-15 parts by weight of a tricomponent copolymer (C) formed of ethylene, acrylate-based compound, and carbon monoxide. (3) 15 parts by weight of a high molecular weight styrenic-acrylonitrile-based copolymer (D) having a weight average molecular weight of greater than 2x10<6> daltons.

Description

548308 A7 '-----— R7 _______ V. Description of the invention (i) [Field of invention] The present invention relates to a kind of stupid vinyl resin composition, especially one (Please read the notes on the back before filling (This page) /. A styrene resin composition with good tensile strength, initial hue, processability, chemical resistance, and injection molding can reduce paint absorption. [Description of Knowing Skills] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, etc.1. All styrenic resin technicians know that rubber-like graft copolymers are dispersed in styrene-based and propionitrile-based copolymers. The product obtained is a kind of impact-resistant acetofluorene-based resin composition. This resin composition can be used in injection molding, extrusion molding, vacuum molding, stretch-forming or thermoforming. In terms of extrusion molding, in order to increase the extrusion output, it is known that the operation temperature increases the extrusion processing temperature, but this will easily cause the phenomenon of steam generation in the molded product. Therefore, how to improve the extrusion extrusion of the extrusion machine during extrusion molding It is difficult to improve the yellowing of the molded product and improve the chemical resistance of the resin, which is one of the issues that need to be improved for this kind of impact-resistant styrene resin composition. In addition, when injection-molded products of impact-resistant styrene resin are applied to outdoor motorcycle parts, it is often necessary to paint to improve their weather resistance. However, in the coating process of styrene-based resin, the molded products are liable to attract paint. The so-called paint absorption phenomenon refers to the phenomenon of uneven distribution of the paint on the surface of the molded product after the painted product is sprayed. 'At this point, how to overcome the phenomenon of paint absorption of this painted product becomes an impact-resistant styrene Another issue for the resin is to be improved. In the prior art, for example, as disclosed in Japanese Patent Application Laid-Open No. 7_3 16390, the addition of a high molecular weight styrene_ acrylic copolymer to a styrene resin can make a vacuum molded product during the extrusion process. The thickness of the meat is on page 3. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 548308 5. Description of the invention (2 has better uniformity, but the ancient 77 molecular weight styrene-acrylonitrile copolymer Although the addition of materials can improve the uniformity of the molded meat, this will cause the composition of the logistics (please read the note on the back? Matters before filling out this page). Reduced mobility, reduced spitting in the extrusion process, etc. It is lacking, and the phenomenon of yellowing of the molded product cannot be improved. Therefore, the composition disclosed in the aforementioned Japanese patent case is not ideal when used for extrusion molding. [Summary of the Invention] Therefore, The object η of the present invention is to provide a product that has good processability and tensile strength, and has good thermal properties. The injection molding can reduce the phenomenon of paint absorption, and the initial hue is good. + # 仲 &amp; good Of Ethylene resin composition. The styrene resin composition described in this section includes: (1) 100 parts by weight of styrene resin, which is composed of 95 to 0% by weight of styrene ethyl resin co-I (A ), And 5 to 100% by weight of the rubber-like graft copolymer (B), the above-mentioned stupid ethylene-based copolymer (A) contains 20 to 40% by weight of the Crimson-like unit, and the rubbery The graft copolymer (B) is in the presence of a women's rubber, and a total of 100 parts by weight of 40 to 90 parts by weight of a styrene-based monomer, 60 to 10 parts by weight of an acrylonitrile-based monomer, and as necessary The remote copolymerizable monomer is obtained by graft polymerization of 0 to 40 parts by weight; printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (2) 1 to 15 parts by weight of ethylene_acrylate-carbon monoxide three-component copolymerization (C); and (3) 1 to 5 parts by weight of a high-molecular-weight stupid ethylene-acrylonitrile copolymer (D), and the molecular weight of the remote copolymer (D) is more than 200,000. The styrene of the present invention The copolymer (A) is composed of 82 to 55 parts by weight of styrene monomer, 8 to 45 parts by weight of acrylonitrile monomer, and may be selected as required. The polymerized monomer is obtained by polymerizing 0 to 40 parts by weight, and it can be a block paper in the paper size _ home fresh (CNS) A4 size ⑽ 297 mm) 548308 A7 B7 V. Description of the invention (3), solution, suspension Obtained by turbid or emulsification polymerization method, in which a block or solution polymerization method is preferred. The weight average molecular weight of the styrene copolymer (A) is between 60,000-400,000, and preferably between 80,000-300,000. The styrenic monomer in the styrenic copolymer (A) of the invention may be: styrene, α-methylstyrene, p-third butylstyrene, p-methylstyrene, ortho-methylbenzene Ethylene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, α-methyl-p-methylstyrene, and bromostyrene, among which styrene or α-formaldehyde Basic styrene is preferred. The acrylonitrile-based monomer used in the styrene-based copolymer (A) may be acrylonitrile, α-methacrylonitrile, etc., of which acrylonitrile is preferred. The copolymerizable monomer used in the styrene-based copolymer (A) of the present invention may be: (meth) acrylate-based monomer, maleimide-based monomer, acrylic acid, methacrylic acid, anhydrous maleic acid Etc. Among them, the (meth) acrylate-based monomer may be: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, methacrylic acid Hexyl ester, cyclohexyl methacrylate, dodecyl methacrylate, 2-hydrocarbon ethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, methyl acrylate and butyl acrylate Among them, fluorenyl methacrylate and butyl methacrylate are preferred. The maleimide-based monomers can be: maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N -Hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, Ν -2,3-Tolylmaleimide, N-2,4-Tolylmaleimide, N-2,3-Ethylbenzene Page 5 This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the notes on the back before filling out this page) ---------- Order --------- line Λ Consumers' Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, page 548308 A7 __B7 V. Description of the invention (4) Base maleimide, N-2,4-ethylphenylmaleimide, N-2,3_ Butyl phenyl male ass, N-2,4-butyl phenyl maleimide, 6-tolyl hexamethyl imine, N-2,3-chlorophenyl maleimide, N-2,4-chlorophenylmaleimide, N-2,3-bromophenylmaleimide, N-2,4-bromophenylmaleimide, etc. -Phenyl malay Imide for the best. In the styrene-ethyl fluorene resin composition of the present invention, the content of the styrene-ethyl women's copolymer (A, 'acrylonitrile unit in the composition is generally 20 to 40% by weight, preferably 24 to 38% by weight, and most preferably 26%) ~ 36% by weight. The rubbery graft copolymer (B) of the present invention is obtained by graft polymerization of 2 to 90 parts by weight of a diene rubber 'and 98 to 10 parts by weight of a monomer mixture, wherein the 100 parts by weight of the monomer mixture includes: 40 to 90 parts by weight of a styrene-based monomer, 60 to 10 parts by weight of an acrylonitrile-based monomer, and 0 to 40 parts by weight as needed It consists of copolymerizable monomers. It can be prepared by individual block, solution, suspension, or emulsion polymerization, or it can be made by a combination of these polymerization methods, such as emulsification_block or block- The suspension polymerization method is preferably an emulsion polymerization method, a block polymerization method, or a solution polymerization method. Among them, the emulsion polymerization method is more preferred. The rubbery graft copolymer (B) obtained by the emulsion polymerization is a better method. It is combined with 98 ~ 1 () in the presence of 2 ~ 90 parts by weight (dry weight) of butadiene rubber emulsion. Emulsion obtained by graft polymerization with a weight average particle diameter of 〇〇 ″, which has been prepared in the early days of this year, is prepared by coagulation, dehydration, and drying. The above emulsion polymerization The rubber content of the rubber-like graft copolymer (B) prepared by the method is usually 25 to 90% by weight, preferably 45 to 80% by weight. The aforementioned succinct rubber emulsion contains 100 to 60% by weight of the total vehicle. Diene monomer and 0 ~ 40% by weight can be used in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) paper size ---------------- ---- Order --------- line (please read Note 3 on the back before filling this page) Printed by Employee Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economy Page 548308 A7 __B7 V. Description of the Invention (Convergence A homopolymer formed by an unsaturated monomer, or a copolymer thereof. The aforementioned conjugated diene monomer can be represented by the following formula: ch2 = C-CH = CH2 where R can be a hydrogen group , Methyl, or chloro, etc., and the copolymerizable unsaturated monomer may be: styrene-based monomer, acrylonitrile-based monomer, methacrylate-based monomer, acrylate-based monomer, or The above-mentioned butadiene-based rubber emulsion may be: polybutadiene, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer, a butadiene-methacrylonitrile copolymer, and the like, which may be the foregoing The monomers are directly polymerized into a form with a weight average particle diameter of 0.05 to 0.8 / zm, or may be polymerized into a small particle size rubber emulsion of 0.05 to 〇18 // m, and then the traditional rubber hypertrophy method is used. 〇5 ~ 〇l8 # m small-diameter rubber emulsion is enlarged to a rubber emulsion of 0.2 ~ 0.8 // m. The aforementioned rubber enlargement method may be the addition of organic acid or metal salt or carboxylic acid group-containing polymer agglutination. Chemical hypertrophy, mechanical mixing, or cold-rolling hypertrophy. Among them, the chemical agglutination method used 1qW1 &amp; 1I molecular agglutination agent can be used, for example: butyl acrylate-methacrylic acid copolymer . The rubber particles of the rubbery graft copolymer (B) obtained by the above-mentioned emulsion polymerization have a unimodal particle size distribution or a bimodal particle grip distribution, and the weight average particle diameter of the unimodal particle size distribution in 纟 is 0 Q 5 ~ g ~ υ · υ :) ϋ · 8 β m, and the weight average particle diameter of the bimodal particle size distribution is 0.05 ~ 〇18 &quot; mn and 0.2 ~ 0.8 / zm. The production method of the rubber-like graft copolymer (B) obtained by using block or solution polymerization to wrap is made of, for example, 2 to 25 diene-based rubber in Caowu Balili, the first paper size applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ------ 丨-丨! • 丨 I · *-! 丨 Order ----- I I (Please read the note on the back? Matters before filling out this page} 548308 A7

It is soluble in 9 8 ~ 7 5 parts by weight of the monomer mixture and a solvent selected as required. The total amount of the monomer mixture is 100 parts by weight, which includes 40 ~ 9 '^ 1 part by weight (please read the note on the back first)咅? Please fill in this page again.) This vinyl monomer, 10 ~ 60 parts by weight of acrylonitrile monomer, 乂 and * 0 ~ 4 by weight of copolymerizable monomer, and then the resulting solution is pumped into the reaction The graft polymerization reaction is carried out in the tank, and a chain transfer agent of 谪 Α w § may be added during the reaction, such as the third-dodecyl mercaptan to control the amount of the polymer 7 &lt; It can be combined by multi-tank series or parallel combination. The pregnant father is a kettle-shaped reaction tank with a powerful stirrer. The solvent used can be ^ M · methylbenzyl, xylene, ethylbenzene, methyl-ethyl Ethyl ketone, ethyl acetate, etc. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the aforementioned diene rubbers used in block or solution polymerization methods, preferably those obtained by anionic polymerization, such as butadiene rubber, isoprene rubber, Gas butadiene rubber, butadiene-acrylonitrile rubber, butadiene_styrene rubber, etc., of which butadiene rubber has high cis (Hi-Cis) content and low cis (Los-Cis) content . In high cis rubber, the typical weight composition of Cis / Vinyl is 94 ~ 98% / 1 ~ 5%, and the remaining composition is trans structure. Its Mooney viscosity is between 20 ~ 120, molecular weight The range is preferably 100,000 to 800,000. In low-cis rubber, the typical weight composition of cis / vinyl is 20 ~ 40% / 1 ~ 20%, and the rest is trans structure. Its Mooney viscosity is between 20 ~ 120. The styrene / butadiene copolymer rubber suitable for the present invention may be a di-block, tri-block, random copolymer or star type) copolymerization. The weight ratio range of styrene / butadiene rubber is preferably 5/95 to 80/20, and the molecular weight range is preferably 50,000 ~ 600,000. Among the block or solution graft copolymers of the present invention, suitable rubber is butyl. Diene rubber and benzene page 8 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 548308 A7 _ B7 V. Description of the invention (7) Ethylene / Butadiene rubber is preferred. The rubber-like graft copolymer (B) obtained by polymerization in a block or solution polymerization method has a weight average particle diameter of rubber particles generally between 0 · ', preferably 1.0 to 7 // m. The rubber content of the solution rubber-like graft copolymer (B) is usually 4 to 25% by weight, preferably 8 to 15% by weight. In addition to the rubber-like graft copolymer (B) of the present invention, the rubber-like graft copolymer of the aforementioned emulsion polymerization method or the block-like (or solution) polymerization method of the rubber-like graft copolymer can be used separately. The two are used together to form a bimodal or bimodal distribution, where the bimodal distribution is as follows: (1) Weight average particle size 0.2 ~ 0.8 / zm (emulsion polymerization), reset average particle size 0.6 ~ 10 // m (mass or solution polymerization); or (2) weight average particle size 0.05 ~ 〇18 # m (emulsion polymerization), weight average particle size 0 · 6 ~ 10 m (mass or solution polymerization) ). Some examples of trimodal distributions are: weight average particle size 0.05 ~ 0.15 // m (emulsion polymerization), weight average particle size 0.17 ~ 0.8 // 111 (emulsion polymerization), and weight average particle size 0.2 5 ~ 7 · 0 // m (block or solution polymerization). Then, the test method for the weight average particle diameter of the rubber particles is described below. After dyeing the resin with osmium tetroxide (Os04), and then photographing it with a transmission electron microscope, take about 1 of the rubber dispersed particles obtained in the photo. Measure the particle size around 〇〇 'and calculate its weight average particle size by the following formula: Σ n iD i4 Rubber weight average particle size --- Σ n iD i3 Page 9 This paper applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm)

--------- ^ --------- ^ (Please read the note on the back? Matters before filling out this page) A7

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 548308 A. Description of Invention (8) 1 In the above formula, η is the number of rubber particles with a rubber particle diameter of D. As for the types of the styrenic 2-body, acrylonitrile-based monomer, and other copolymerizable monomers used in the rubbery graft copolymer (B) of the present invention, and the monomers in the aforementioned stupid vinyl-based copolymer (A) The examples are the same and will not be described again. The ethylene-acrylic-based-carbon monoxide three-component copolymer (C) in the styrene-based resin composition of the present invention is obtained by polymerizing two components: ethylene, acrylate-based, and mono-monoxide. The acrylate monomers in the ethylene_acrylate-based carbon monoxide three-component copolymer (C) used in the present invention may be: ethyl acetate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid Hexyl ester, octyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, third butyl methacrylate, Isobutyl acrylate, etc., of which n-butyl acrylate is preferred. The amount of the ethylene · acrylate-carbon monoxide three-component copolymer (C) used in the present invention is 1 to 15 parts by weight, and preferably 3 to 10 parts by weight relative to 100 parts by weight of the styrene resin. When the added amount is less than 1 part by weight, the initial hue of the composition is not good, that is, the yellowness is high, the chemical resistance is poor, and the effect of improving the paint absorption phenomenon of the molded product is insufficient. However, if the added amount is more than 15 parts by weight, the resin The tensile strength will be greatly reduced, resulting in poor physical properties of the resin composition. The high-pitch styrene-acrylonitrile copolymer (D) used in the styrene-based resin composition of the present invention is obtained by polymerizing two components of a styrene-based monomer and an acrylonitrile-based monomer. The weight average molecular weight of the styrene-acrylonitrile copolymer (D) is more than 2 million. If the molecular weight is 2 million, page 10 This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please Read the precautions on the back before filling in this page) ▼ 褒 --------- Order --------- line · 548308 A7 B7 V. Description of the invention (9) Below 'The resin composition The paint absorption of the molded product cannot be improved. Generally speaking, 'the specific examples of the styrene-based monomer and the acrylonitrile-based monomer in the high-molecular-weight styrene-acrylonitrile-based copolymer (D) used in the present invention are the same as described above', and will not be repeated here. The amount of the high-molecular-weight styrene-acrylonitrile copolymer (D) used in the present invention is from i to 5 parts by weight with respect to 100 parts by weight of the styrene resin, preferably from 2 to 4 parts by weight. When the added amount is less than 1 part by weight, the effect of improving the paint absorption phenomenon of the molded product of the composition is not great, and the tensile strength of the resin composition is deteriorated. When the added amount is more than 5 parts by weight, its fluidity is reduced and processability is reduced. Deterioration, the initial composition of the resin composition is not good, and yellowing is likely to occur (please read the precautions on the back before filling this page). The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the styrene-based additive of the present invention, for example: Anti-stabilizing agent, ultraviolet absorption, anti-charge agent, flame-retardant other additives, etc., the above, before coagulation or extruded kneading amount is relative to 100 weight, of which the amount of 'antioxidant, squid antioxidant is 0.005 based (3,5 -Bisamidine resin is composed of oxidant, additive, filler, and flame retardant additive. Styrene can be added in the process. It is best to use materials such as phenol and chelating agent. Processing, strengthening agents, agents, and thermal stabilization polymerization reactions are added with the following additive-based resin composition-based antioxidants, and the hope is that the representative 2.0 is based on the 4--4-phenyl group) -propionic acid vinegar, (3- Third butyl-5_methyl_4_hydroxyphenyl) propionate] (3,5-bis third butyl-4-hydroxyphenyl) propionate] methane Page 11 This paper is applicable to China National Standard (CNS) A4 Specification (21 () x 297 mm) Adding and using other auxiliary agents, UV colorants, slip agents, coupling agents, or additives after polymerization, and its additives. Additions of sulfur-based antioxidants and antioxidants are: octadecane diethylene glycol bis [3-tetrakis [methylidene-3-third butyl-548308] Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (10) 6- (3-Third-butyl-2-hydroxy-6-methylbenzyl) -4-methylphenylacrylate, 2,2, -methylidene-bis ( 4-methyl-6-tert-butylphenol), 2,2, thiobis (ren methyl-6-tert-butylphenol), 2,2, _thio-diethylidene-bis [3 -(3,5-bis-tertiarybutyl-4-hydroxyphenyl) propionate], 2,2, -ethylenediamine-bis [ethyl-3- (3,5-and-di-dibutyl _4_ via phenyl) propionate] and so on. The thioether-based antioxidant is preferably added in an amount of 0.005 to 2.0 parts by weight. Representative examples include: distearyl thiodipropionate, dipalmitine thiodipropionate, and pentaerythritol-four one ( Stone_dodecylmethyl-propionate), dioctadecylsulfide 8¾ and so on. Phosphorus-based antioxidants are phosphite-based antioxidants or phosphate-based antioxidants, and the addition amount thereof is preferably from 0.5 to 2.0 parts by weight. Representative examples include bis (nonylphenyl) phosphinic acid g Purpose, Dodecyl Iridine I®,% Pentamyl Tetrahydronaphthylbis (octadecylphosphite), 4,4, Butylenebis (3-methyl-6-tert-butyl) Phenylphenyl-bistridecylphosphite), tris (2,4-thirdbutylphenyl) phosphite, tetras (2,4-thirdbutylphenyl) -4,4 ' -Extended benzyl phosphate, 9,10-dihydro-9-oxy-10 phenanthrene-10-oxophosphate, etc. The chelating agent is preferably added in an amount of 0.001 to 2.0 parts by weight, and typical examples include dibenzylmethyl methane, sodium salt of diethylaminetetracarboxylic acid, and the like. The added amount of the antioxidant is usually from 0.03 to 2.0 parts by weight based on the total amount of the styrene-based resin composition. Representative lubricants are: metal soaps such as calcium stearate, magnesium stearate, and stearic acid clock, ethylene distearylamine, methyldistearylamine, methyl palmitate, hard Butyl stearate, palmityl stearate, polytrialcohol tristearate, n-docosaic acid, stearic acid, etc. compounds, polyethylene wax, page 20 This paper applies Chinese national standards (CNS) A4 specifications (21〇x 297 male t) ------------- --------- tr --------- line in &quot;: (Please read first (Notes on the back, please fill out this page) 548308 A7

/ Alkanoic acid wax, Carnuba wax, petroleum wax, etc .; the amount of slip W added to the styrene resin composition usually totals # 0.03 to 5.0 weight ◦ / ◦; in order to improve extrusion moldability, thermoformability It is also possible to add processing aids such as formazan methacrylate; UV absorbers are represented by: benzodiazolium compounds, benzophenone compounds, cyanopropylamines, and Representative examples of external and external stabilizers include: retarded amine-based compounds: the aforementioned substances are added in an amount of 0.02 to 2.0 parts by weight relative to the styrene-based resin composition. In terms of improving the weather resistance of the resin, discoloration caused by ultraviolet radiation, or the degradation of the resin, it is better to use a combination of amine-based ultraviolet stabilizers and cyanoacrylic acid-based external absorbers, such as BA sf Uvinul 4050Η (0. 02 ~! 0% by weight) / uvinul 3030 (0. 2 ~ 1. 0% by weight). Representative examples of antistatic agents are: tertiary amine compounds, low molecular compounds of quaternary ammonium π-based compounds 4, or polyamine polyethers, such as 3 gas-1,2-propylene oxide polymer It is a polymer-based substance that prevents permanent charging. Representative fillers are: calcium carbonate, silica, mica. Reinforcing agents are typically glass fiber, carbon fiber, and various whiskers. Representative colorants include titanium oxide, iron oxide, graphite, and phthalocyanine dyes. Flame retardants or flame retardant additives are representative: decabromodiphenyl ether, bromo trimethyl phenylindane, desertified polystyrene. Page 13 This paper applies Chinese national standards (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page) -Installation ------- Order ----------- Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 548308

Ethylene bond polymer, brominated epoxy resin, succinic acid, ^ succinodecane, chlorinated polyene alkene% St, red phosphorus, antimony oxide, rhenium, -take-W Tian Lice aluminum, magnesium hydroxide, boron (please read the precautions on the back before filling out this page) 酉 Lack of zinc dimer amine, isocyanamide salt, silicon 4 and expanded graphite. Representative examples of M '^ fluoroethylene powder thermal stabilizers are: dibutyltin maleate, triplomagnesium aluminum hydroxycarbonate, and the like; and thermal discoloration prevention is a low molecular weight, lean 7ene-anhydrous malay For acid copolymers, the added resin composition usually contains a total amount of 0.2%; for the stupid ethylene · U parts by weight of the present invention. The representative of the couple &amp; agent t: Shi Xiyao, citric acid, germanium compounds. In order to improve the styrene resin composition of the present invention, the addition of a polymerization system may be appropriately used, for example: E PDM (printed by 消费 pylene dlene m_er), or propylene_ AES resin modified with butadiene rubber, or A AS resin such as A AS resin, anhydrous maleic acid-styrene copolymer, styrene-maleimide fine, and maleimide content exceeding 4 〇Please styrene-propionitrile-anhydrous maleic acid copolymer, α-aniline maleimide imidized acetofluorene-acrylonitrile-anhydrous maleic acid copolymer, bridging rubber without grafting, for example: Acrylonitrile-butadiene rubber, vinyl chloride resin 1 methyl methacrylate, polycarbonate resin, polyamide resin, polybutylene terephthalate, polystyrene ether, polyvinyl chloride, styrene The thermoplastic elastomer, various miscibility agents, and the like are used in an amount of 3 to 200 parts by weight based on 100 parts by weight of the styrene-based resin composition of the present invention. In order to obtain the resin composition of the present invention, the mixing method is representative. Page 14 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 548308 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 -—__— B7___ V. Description of the invention (13): It is dry-blended with a commonly used Hanschel mixer and then melt-mixed with a mixer such as an extruder mixer, a kneader or a Banbury mixer. The resin composition of the present invention is suitable for molding methods such as injection molding, extrusion molding, compression molding, stretch molding, thermoforming, vacuum molding, and hollow molding. [Detailed description of the implementation examples and comparative examples] In order to further explain the present invention in detail, the examples and physical property tests are described below. [Preparation example] &lt; Preparation example I-1 &gt; Production of styrenic copolymer (A-1): 60% by weight of styrene and 40% by weight of acrylonitrile were mixed at a rate of 12 kg / hr Then, the recovery liquid formed by condensing ethylene distearylamine 30 g / hr, benzamidine peroxide, tertiary-dodecyl mercaptan, and the volatiles removed by the reaction described later is condensed. The feed solution was fed to a continuous kettle-type reactor with a stirrer at an internal temperature of 1 08 ° C and a volume of 45 liters, and the toluene ratio in the reaction solution was kept at 5%, and the combination ratio was maintained. At 5 5%. After the volatiles are removed by the reaction solution through the devolatilization device, the particles of Benkun Copolymer can be obtained; on the other hand, the volatiles of the cloud removed by Xidayoudaotian are condensed by the condenser as the recovery liquid and continuously It is mixed with the aforementioned raw materials and reused. In this σ method, the reaction rate is adjusted by the amount of benzamidine peroxide, or the amount of the second dodecyl mercaptan is adjusted to make a styrene-based copolymer (A-1 with an acrylonitrile content of 32% by weight). ). B &lt; Preparation Example I-2 &gt; Production of styrene-based copolymer (a-2) · (Please read the precautions on the back before filling in this page}

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548308

V. Description of the invention (14) The preparation is the same as &lt; Preparation Example I-1 &gt;, but the raw materials are mixed by 72% by weight and the acrylonitrile is 28% by weight. A fluorene-based copolymer (A-2) having an acrylonitrile content of 28 weights was prepared. &lt; Preparation Example Π — 1 &gt; Production of rubbery graft copolymer (B-1): ° / 〇 ^ min

V Component 1,3-butadiene acrylonitrile potassium persulfate solution sodium pyrophosphate potassium oleate distilled water weight of dodecyl mercaptan 95.0 5.0 15.0 3.0 1.5 140.0 0.2 React at 65 ° C reaction temperature according to the above formula 1 In 2 hours, a synthetic rubber emulsion having a conversion rate of 94%, a solids content of about 40%, and a weight average particle diameter of 0 诹 was obtained. In addition, 'the coagulant containing carboxylic acid group is made with the following ingredients: Ingredient I ^ «--- Γ --- Order · -------- Please read the legal matters on the back before filling in this Page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs η—Butyl acrylate Methacrylic acid Third—h Dialkyl mercaptan Oleic acid unoctyl suffix No. Naphthalene cumene hydroperoxide Weight 85.0 15.0 0.3 2.0 1.0 0.4 Page 16 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21 × 297 mm) 548308 A7 _____B7__ V. Description of the invention (15) Dialdehyde sodium bisulfite distilled water according to the above After reacting at 7 5 t: reaction temperature for 5 hrs + τ, we can obtain a g-8 containing wei acid group with a conversion rate of 95% and a pH value of 6.0 &quot; knife agglutinating agent 〇 &quot; Carboxylic acid-based polymer coagulant (dry weight) to 100% by weight of synthetic rubber emulsion (dry weight). The pH value of the resulting enlarged rubber emulsion is 8 · 5, and the weight average particle size is n QA. • 30um. Finally, the following formula is used to make the rubberized graft copolymer (B-1) based on the following formula. 0.3 20.0 million copies Intellectual Property Bureau of the Ministry of Economic Affairs Employees Cooperatives Printed masticated rubber emulsion (dry weight) Styrene propionitrile potassium oleate Third --h dialkyl mercaptan cumene peroxide Ferrous hydrogen sulfate solution (0.2%) Sodium formaldehyde sulfoxylate solution (10%) Ethylenediamine tetraacetic acid solution (0.25%) Steamed crane water 100.0 25.0 8.3 1.2 0.2 0.5 3.0 3.0 20.0 200.0 #Crack ---- ------ tl --------- ^ _ w.r (Please read the precautions on the back before filling this page) Add the styrene / acrylonitrile in the above formula in a continuous manner for one hour It is added into the reaction system to polymerize, and the rubber-like graft 1 liquid 4 calcium chloride (CaCh) is coagulated, dehydrated, and then dried to moisture content. Page 17 This paper applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 548308 A7 B7 5. In the description of the invention (16), the rubber-like graft copolymer (B-1) (rubber content 75% by weight) required by the present invention can be prepared, and its rubber particles The weight average particle diameter is 0.31um. &Lt; Preparation Example Π-2 &gt; Production of Rubbery Graft Copolymer (B-2): &lt; Preparation Π-1 &gt; The prepared synthetic rubber emulsion (average particle diameter of rubber particles 0 · 1 um) was directly subjected to graft polymerization with the formula below 0 A ___ ^ parts by weight of synthetic rubber emulsion (0.1 um) (dry weight) 100.0 Styrene 75.0 Propionate 25.0 Potassium oleate 2.0 Third-h dialkyl mercaptan 0.6 Cumene hydroperoxide 1.4 Ferrous sulfate solution (0.2%) 8.6 Sodium hyposulfite solution (10%) 8.6 Ethylenediamine tetraacetic acid solution (0.25%) 57.0 Distilled water 200.0 The non-condensed rubber emulsion prepared as described above and &lt; Preparation Example π-1 &gt; Mixing and coagulating in a manner, the rubbery graft emulsion prepared is coagulated with calcium chloride (CaC 12), dehydrated, and then dried to a moisture content of less than 2%, to obtain the rubbery graft required by the present invention The copolymer (B-2) (rubber content 60% by weight) has a bimodal distribution pattern in which the weight average particle diameter of the rubber particles is 0. 1 um and 0.3 um. Page 18 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) ▼ _1 1 I ^ 1 ^ 1 1 · 1 1_1 tmmmmm a ^ i Ball eat I * Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 548308 A7 ------ B7 V. Description of the invention (17) &lt; Preparation example π — 3 &gt; Rubber-like graft copolymer (B_3 ) Production: Using 0.08 parts by weight of benzamidine peroxide as a starter, 6.6 parts by weight of 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, and then the feed solution was continuously fed into a first reactor having a volume of 45 liters, the reaction temperature was 100 ° C, the reactor A spiral stirrer with a cooling circulation tube is arranged inside, the stirring rate is 150 rpm, and the monomer conversion rate in the first reactor is 15%. 'The mixture after the reaction in the first reactor is continuously taken out and sequentially Feed into the second, third and fourth reactors, and simultaneously add in the third reactor Into 0.1 parts by weight of the third-dodecyl mercaptan, the reverse rotation phenomenon occurs in the second reactor. The devices of the second, third, and fourth reactors are the same as the first reactor, but the reaction temperature is the same. Sequentially 105 ° C, 1100c, 125c, and the stirring rate is 270rpm, 150rpm, and 110 rpm in sequence; when the conversion rate of the mixture reaches 60%, the mixture is taken out and sent to a devolatilization device. Unreacted monomers and volatiles are removed, and then extruded and granulated to obtain a granular rubbery graft copolymer. The weight average particle diameter of the rubber particles is 0.95 um and the rubber content is 10 weight. %. After mixing the granular rubbery graft copolymer with the rubbery graft copolymer (B-2) of the aforementioned &lt; Preparation Example π-2 &gt; at a ratio of 4: 6, a rubber content of 40 can be obtained. The rubber-like graft copolymer (B-3) having a trimodal distribution pattern of 0.001 μm, 0.3 μm, and 1.0 μm in weight average particle diameter of the rubber particles. [Physical property test standards] Page 19 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) -Installation -------- Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5483〇8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 i. Description of the invention (18) ~, Measurement of the flow index (MI) : Measured in accordance with ASTM D-1238 and expressed as g / 10. — 、 Measurement of tensile strength (TSy): Tested according to A S T M D-6 38 method, expressed as κ g / cm 2. 3. Determination of the initial hue [yellowness (YI)]: The polymer is pressed into a test piece with a size of 4 kn \ 4111 \ 1/8111 (length \ width X thickness), and the yellowness (yeU) is measured by color difference. 〇w index), which is the YI value. 4. Chemical resistance test: Gauze is placed on the tensile strength test piece with a deformation of 1.5%, and sprayed with liquid detergent, and then at 23. (: Place it for 24 hours to observe the tensile strength of the test piece for cracking or fogging. When there is severe cracking or fogging on the test piece, it is indicated by "XX". And when there is slight cracking or fogging on the test piece The phenomenon is indicated by "X", and when there is no crack or fog on the test piece, it is indicated by "0". V. Paint absorption phenomenon: i5〇x7〇 &gt; &lt; 3 (t ) m / m test piece, after spray painting, observe the distribution of the color depth of the spray paint near the valve of the molded product. [〇] indicates uniform distribution of the paint, [△] indicates slightly different shades, [X] It shows that the distribution of paint is obviously different. [Example] &lt; Example 1 &gt; The styrene-based copolymer (A_1) 75 prepared from &lt; Preparation Example I -1 &gt; National Standard (CNS) A4 Regulations (2_10 x 297 mm) ----------- Installation -------- Order --------- (Please read the back first Please fill in this page again) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 548308 A7 B7 V. Description of the invention (19)% by weight of the rubber produced by <Preparation Example Π-2> 25% by weight of a gel-like graft copolymer (B-2), and 3 parts by weight of an ethylene-butyl acrylate-carbon monoxide three-component copolymer (C) (manufactured by Du Pont, trade name: Elvaloy EP-405 1) ), 2 parts by weight of high molecular weight (weight average molecular weight 6 million) styrene-acrylonitrile copolymer (D-1) (manufactured by GE, trade name

BlendexB-869), and 1.5 parts by weight of lubricant, and Werner &amp;

Pfleidrer ZSK 35 extruder is extruded and granulated at 220 ° C.

A styrene-based resin composition with a rubber content of 15% by weight, and then shot the test piece at 220 ° C with an injection molding machine, and measured the flow index, tensile strength, yellowness, chemical properties, and paint absorption phenomenon. The results are shown in the attached table-* 〇 &lt; Examples 2 to 5 &gt; According to the formula of Table 1, the raw materials are mixed uniformly according to the operating conditions of Example 1, and the test pieces for testing are formed. The measured physical properties are also Contained in Schedule 1. &lt; Example 6 &gt; Same operating conditions as in Example 1, except that the styrene-based copolymer (eight-: ^ was changed to the present ethylene fluorene copolymer (A-2) 'The remaining conditions were unchanged, and the results of various physical properties tests were used. Contained in Table 1. [Comparative Example] <Comparative Example 1> The operating conditions are the same as in Example 1, except that the ethylene-butyl acetic acid-carbon monoxide three-component copolymer (c) is not added, and For the high molecular weight styrene-acrylonitrile copolymer (D-1), the test pieces prepared were also tested for various physical properties, and the results are shown in Appendix 1. Page 21 ---------- -Install -------- Order --------- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297) Love) ^ — 548308 A7 B7 V. Description of the invention (20) &lt; Comparative Example 2 &gt; The operating conditions of Example 1 are the same except that ethylene-butyl acrylate-carbon monoxide three-component copolymer is not added (C), and the amount of stupid ethylene-acrylonitrile copolymer i) in the polymer was changed to 2 parts by weight, and the test piece prepared was also subjected to various physical property tests. Schedule I. &lt; Comparative Example 3 &gt; The operating conditions of Example 1 were the same, except that: the addition amount of ethylene-butyl acrylate | co-carbon monoxide three-component copolymer (c) was changed to 6 parts by weight ', but not added For the high molecular weight styrene-acrylonitrile copolymer (D_ 丨), the test pieces obtained were also tested for various physical properties. The results are shown in Table 1. &lt; Comparative Example 4 &gt; The operating conditions were the same as in Example 1, except that the addition amount of the ethylene-butyl acrylate-carbon monoxide three-component copolymer (C) was changed to 1 part by weight, while the high molecular weight styrene- The added amount of acrylonitrile copolymer (D-1) was changed to 7 parts by weight. 'The test piece prepared was also tested for various physical properties, and the results are shown in the attached table'. &lt; Comparative Example 5 &gt; The operating conditions were the same as those in Example 1, except that the addition amount of the ethylene-butyl acrylate-carbon monoxide three-component copolymer (C) was changed to 17 parts by weight, and the high molecular weight styrene -The added amount of the acrylonitrile copolymer (D-1) was changed to 2 parts by weight, and the test pieces prepared were also subjected to various physical property tests. The results are shown in Table 1. &lt; Comparative Example 6 &gt; The same formulation and operating conditions as in Example 1, except that the paper size of the polymer page 22 applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---- ---- ^ --------- (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 548308 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives A 2. Description of the invention (21) The amount of styrene-acrylonitrile extract (D-1) was changed to a low-quantity styrene-acrylonitrile copolymer (D-2, made by Qiu Yingying HYA). Only company-made, trade name PN-127-15, weight 50,000 yuan)), the test piece produced was also tested for various physical properties. The results are shown in Appendix 1. From the test results of Comparative Example 1 in Schedule 1, it can be seen that when ethylene-acrylic acid is not added to the composition, Tianyeding Ding®-a emulsified carbon three-component copolymer (C) and high molecular weight In the case of the styrene-acrylonitrile copolymer (D), the initial hue of the resin composition is poor, the chemical properties are poor, and the molded product has a phenomenon of paint absorption. The test results of Comparative Example 2 show that when the stupid ethylene-acrylonitrile copolymer (D) was simply added, the initial resin composition was: &amp; Shi Ri Lan, # @ + J had a poor color phase, and the chemical resistance was also poor. The improvement of the paint phenomenon is also insufficient. # 由 Comparative Example 3 测试 结果 显 # When only ethylene · butyl acrylate-carbon monoxide three-component copolymer (c) is added to the composition, the tensile strength is deteriorated and the molded product has a phenomenon of paint absorption. The test results of Comparative Example 4 show that when the high molecular weight stupid ethylene-acrylonitrile copolymer (D) is added in an excessive amount (more than 5 parts by weight), the fluidity of the resin composition is reduced, and the processability is poor. The test results of Comparative Example 5 show that when the ethylene-butyl acrylate-carbon monoxide three-component copolymer (C) is added in excess, the tensile strength of the resin composition is greatly reduced, and the test results of Comparative Example 6 show that the average molecular weight is used. If the styrene-acrylonitrile copolymer (0) is less than 2 million, the molded product may have a phenomenon of paint absorption. The test results of the examples of the present invention show that the present invention simultaneously adds a specific proportion of ethylene-propionate-butyric acid_carbon monoxide three-component copolymer (c) and a high-molecular-weight styrene-propionate copolymer to a styrene-based resin. (D), will make the resin composition have good tensile strength, good initial hue, page 23 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------ ----- Install -------- Order ----------- (Please read the precautions on the back before filling this page)

J ^ 3〇8 Description of the invention (22, moldability, chemical resistance, and improved paint absorption of molded products, and is a novel and advanced styrene resin composition.,

Ab above mentioned is only the preferred embodiment of the present invention, if not: to limit the scope of implementation of the present invention, ~ simple equivalent changes made in accordance with the patent application and the contents of the invention specification All modifications and modifications are still within the scope of the invention patent. Attached Table 1: Composition and physical property test results of the examples and comparative examples of the present invention. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 2 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 548308 ti: A -1: 舛 2 &gt; review &gt; and Xiaodiao (Araiti £ 2t #%. A—2: 舛 6 荼 &gt; and Xiaoshen (AYa animal peak but eat 28 t *%. B-1: Tomb—7514¾ ” _it§ 0 · 31 ΐ ο 1 mouth magnetic phenomenon chemical resistance | initial no eye (yellowness) | 4 male strength (Tsy) | Likou workability (MI) resin reference lion content 3 ^ Μ Ϊχ peak W% W works βΨ and 丨 0 ^ ρ Ψ Graft copolymer in 1 shed Styrene copolymer (Α) 2 Ingredients and physical properties 1 (kg / cnf) (g / lOmin) 0 parts by weight Parts ytnr ym 1% weight yCvrv tm 〇〇13.4 cn CJl 1- ^ JND OO Ι 2 (Μ) oo Ψ to 〇 ι -1 Example 〇 CO 1- * 茭 茭 13.5 〇 Ί 2 (Μ) CJD Ψ to ΟΙ IX) 〇〇OD cn H-1 h— ^ οι 4 (Μ) Ψ to ten 1- * 〇Ί 00 〇〇15.3 GO 13.3 ο 2 (Μ) oo Ψ 〇〇IND 矣 CJD 13.4 οι 2 (Μ) OT Ψ Ψ GO οι 62.5 οι 〇〇13.0 CJD CJ1 CD ΟΊ 2 (Μ) OO A to ten CO οι &gt; &lt; XX 19.4 C £ T CD ΟΊ ο Q A DO X h-1 tb $ Example j &gt; XX 19.2 cn INO ο 13.6 cJl 2 (D- 1) Q IND X cn CO &gt; &lt; 〇15.9 1 16.7 οι ο cn &gt; 〒 IND X ο GO GO 〇 &gt; &lt; 211 cn tND oo 10.2 〇Ί 7 (Μ) 1—a 〒 IND X ΟΊ 〇〇1 &quot; «^ 20.9 ΟΊ 2 (Μ) 〒 IND X οι αι &gt; &lt; 〇11 〇〇CO CZ5 η— ^ • CD οι 2 (D-2) GO 〒 CO X ΟΊ ·, · ¾ ^ 丨 548308 〒 2 二 墨 ^^ Refer to 60l4 * v14t + itEt ^ 0 · 1 / zm ^ a 31 // 3 ^ 1¾. B— 3 &quot;# ^ &gt; 苏 ^^^ 黎-## ^ * 40144% -wl: ^ vhtEf ^ o · l // mo · 31 // m two · 0 // mw ^ 5 every V 1 · · M $ t ^ (^ ¥ a platform peak and _t + ^ $ t &lt; ^ 600M. V2: See $ 4 f-3 plug peak and ^ 15 觚.

Claims (1)

548308 A8 B8 C8 D8 Announcement, patent application scope 1, a styrenic resin composition, which contains: (Please read the precautions on the back before filling this page) (1) 100 parts by weight of styrenic resin, It is composed of 95 to 0% by weight of a styrene-based copolymer (A) and 5 to 100% by weight of a rubber-like graft copolymer (B). The styrene-based copolymer (A) contains 20 to 40% by weight of a propionitrile-based unit, and the rubbery graft copolymer (B) is in the presence of a diene rubber, and a total of 100 parts by weight of 40 to 90 parts by weight of styrene-based monomer, propylene 60 to 10 parts by weight of a nitrile monomer and copolymerizable monomers selected from 0 to 40 parts by weight as needed; (2) 1 to 15 parts by weight of an ethylene-acrylate-carbon monoxide three-component copolymer (C); and (3) 1 to 5 parts by weight of a high molecular weight styrene-acrylonitrile copolymer (D), the copolymer (D) having a weight average molecular weight of more than 2 million. 02 according to the patent application The acetofluorene-based resin composition according to the item 1 in the scope, wherein the ethylene-acrylate-monoxide Ethylene copolymer is a fine three ingredients - propionic acid butyl acetate women - carboniferous oxide copolymer three ingredient. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Page 25 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)