TW294680B - Styrene resin composition having improved impact strength - Google Patents

Abstract

A styrene copolymer comprising:(1) 5 to 90 wt.% of a graft copolymer (C) obtained by bulk and/or solution polymerization of 80 to 45 parts by weight of styrene monomer, 15 to 50 parts by weight of acrylonitrile monomer and 0 to 40 parts by weight of a copolymerizable monomer, based on a total amount of 100 parts by weight and in the existence of 0.1 to 10 parts by weight of a rubber graft copolymer (A) having a weight average diameter of 0.05 to 0.8 (muon)m and 0.1 to 10 parts by weight of a acrylic copolymer (B); (2) 95 to 10 wt.% of a graft copolymer (D) obtained by emulsion polymerization of 50 to 15 parts by weight of a mixture of styrene monomer, acrylonitrile monomer and optional copolymerizable monomer in the existence of 50 to 85 parts by weight of a butadiene rubber having a weight average diameter of 0.05 to 0.8 (muon)m; and(3) 0 to 80 wt.% of a polymer obtained by polymerization of 80 to 50 parts by weight of styrene monomer, 20 to 50 parts by weight of acrylonitrile monomer and 0 to 40 parts by weight of an optional copolymerizable monomer.

Description

A7 B7 i printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs i. Description of the invention (j) The present invention is presumed to be based on a styrene resin composition. More pleasantly speaking, the present invention is related to a type with good impact strength, A styrene strip resin composition with low gloss difference and excellent hygienic plating properties. According to press, styrene resin (such as ABS resin, etc.) has a good evaluation of the processability, physical properties and mechanical properties, so it is widely used in electrical appliances, electronic products and automotive materials, but the general ABS There is still a need to improve the impact strength and gloss of the resin, especially in the processing and molding, it is often in different parts, or the same part due to different observation angles, resulting in great gloss difference, which will have a bad appearance on the product Colorful sound. On the other hand, because ABS resin has the advantages of easy processing and molding, quality shoes and electroplating, it has gradually replaced the status of metal recently, and has been widely developed as automotive parts and other decorative and corrosion-resistant articles. As far as the electroplating of ABS resin is concerned, after the ABS resin is chemically roughened (etching), the butadiene rubber on the surface of the resin is preferentially eluted to form dents, and then the processed product is immersed in the chemical liquid Perform electroless plating to make the plated metal adhere to the surface of the ABS resin and the aforementioned dents. The anchor * effect generated by the dents can make the plated metal layer firmly adhere to the ABS resin . Although the above-mentioned existing technology can make the yellow plating layer adhere to the ABS resin, the general ABS resin often suffers from defects such as poor cooling and heating cycles of the electroplated gold layer, poor adhesion strength, and poor external appearance after the yellow plating; Some of the aforementioned deficiencies, some people try to change the injection conditions of ABS resin, that is, increase the injection temperature, reduce the injection speed and injection ® force, etc. This method is applicable to the Chinese national standard (CNS) A4 specifications (210X297) Mm) (Please read the precautions on the back before filling in this 1) Ordered by the Central Standard Falcon Bureau of the Ministry of Economic Affairs, the consumer cooperation du printing 294680 Α7 Β7 i, the invention description (2) Although the strength improvement is slightly improved, it is still suspected Insufficient, and increasing the injection temperature is easy to cause the deterioration of the resin, and reducing the injection speed and injection force will result in a reduction in production speed, which is not economically beneficial. Obviously, simply improving the injection conditions cannot effectively improve the styrene strip Resin plating characteristics. Therefore, how to make the styrene resin have good impact strength, reduce the gloss difference of the finished product, and improve the hot and cold circulation and adhesion strength of the resin plating are the topics that need to be improved in this field. The main object of the present invention is to provide a styrene resin composition having good impact strength, small gloss difference, and excellent plating characteristics. However, the styrene-shito resin composition of the present invention includes: (1) a rubber graft copolymer (A) with a weight-average particle diameter of 0.05 to 0.8 (A) 0.1 to 10 parts by weight and a propylene-based koto copolymer (B ) In the presence of 0.1 to 10 parts by weight, based on a total of 100 parts by weight of the following monomers: 80 to 45 parts by weight of styrene strip monomers, 15 to 50 parts by weight of propylene dimer monomers and copolymerizable monomers 0 ~ 40 parts by weight of the graft copolymer obtained by block and / or solution polymerization (C) 5 ~ 90 parts by weight; (2) The weight average particle size of 0.05 ~ 0.8 of butadiene rubber 50 ~ 85 parts by weight Graft copolymer (D) 95 obtained by emulsified graft polymerization of styrene strip monomers, propylene strip monomers and optionally copolymerizable monomer mixture 50 ~ 15 weight parts in the presence of parts ~ 10 parts by weight (3) 80 to 50 parts by weight of styrene strip monomer, 20 to 50 parts by weight of acrylic eye strips, and copolymers that can be polymerized by copolymerization of single phases if necessary. (Ε) 0 ~ 80 weight: ". Page 04 This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297mm) (please read the precautions on the back before filling out this page). Packing * * Order Printed by Beigong Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs 294680 Δ7 Α7 Β7 5. Description of the invention (3) The rubber-lime graft copolymer (A) of the present invention is in the presence of 50 to 85 parts by weight of butadiene rubber emulsion, and it is combined with styrene monomers and acrylic monomers. 50 ~ 15 parts by weight of strontium, and 0 ~ 30 parts by weight of other copolymerizable monomers to obtain an emulsion of graft copolymer (A) with a weight average particle size of 0.05 ~ 0.8, and then coagulated and dehydrated , Drying and other steps, and to obtain a powdery granular rubber mash graft copolymer (A); the above-mentioned butadiene rubber emulsion contains 100 ~ 60 weight! I; the conjugated diene monomer, and 0 ~ 40 weight 3 {monopolymer formed by a single unsaturated monomer (honopolyner), or a copolymer thereof (copolymer), the aforementioned conjugated diene monohydrate can be expressed by the following formula:

R CHs = J-CH = CH2 where I {can be a hydrogen group, a methyl group or a cyano group, etc., and the single unsaturated monomer can be a styrene monomer, acrylamide monomer, (meth) acrylic acid Ester strip monomer. The butadiene rubber waist emulsion used in the present invention may be butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-methyl methacrylate copolymer, etc .; the above-mentioned butadiene strips The rubber emulsion can be directly polymerized into the form of a weight average particle diameter of 0.05 ~ 0.8 mm, or it can be polymerized into a small particle diameter rubber emulsion of 0.05 ~ 0.18 mm, and then the traditional rubber hypertrophy method can be used to raise 0.05 ~ 0.18 "The small particle size rubber emulsion emulsion is enlarged to 0.2 ~ 0.8_ rubber emulsion. The aforementioned rubber enlargement method can be an organic acid or metal salt or a carboxylic acid group-containing polymer coagulation thin chemical enlargement method, mechanical stirring machinery The hypertrophy method or the freezing hypertrophy method; the polymer coagulant used in the chemical hypertrophy method can be, for example, butyl acrylate-methacrylic acid copolymer. Page 05 This paper scale is applicable to China National Standard (CNS) A4 (210X297mm) (Please read the notes on the back before filling this page) Binding · Order A7 B7 i printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Description of the invention (4) The graft polymerization of the present invention is used to produce rubber graft copolymers with a weight average particle diameter of 0.05 to 0.8 division. The preparation of the above graft copolymers is usually by using the conventional graft polymerization technology. In the presence of a rubbery polymer, perform a graft polymerization reaction with a styrene strip monomer, an acrylic monomer strip monomer, and a (meth) acrylate strip monomer monomer added as needed, using chemical bonding or grafting At least one polymer on the butadiene rubber strip; according to the ratio of the single skull to the butadiene rubber strip and the polymerization conditions, it is possible to obtain the polymer grafted on the butadiene rubber strip at the same time, which is the desired degree of grafting polymer ; Usually the polymerization conditions in the graft polymerization reaction, the chemical properties of the rubber-like polymer, particle size, the rate of monomer addition, chain transfer agent, emulsifier dosage and type, etc., will affect the connection. Degree. The initial catalyst or catalyst added in the aforementioned graft polymerization reaction is usually within 0.01 ~ 5.0 parts by weight of the polymerizable monomer, preferably 0.1 ~ 3.0 parts by weight; the amount of addition depends on the monomer and the required Depending on the polymerization reaction of the polymerization, 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 grafting reaction, and / or blended with a relatively small proportion of conventional molecular weight regulators, such as thiols, halides, or thiols, etc. More specific examples of molecular weight regulators include n-dodecyl mercaptan and tertiary-dodecyl mercaptan. This graft polymerization reaction can also be controlled by changing the grafting of the polymer on the rubber-like polymer. Generally, this effect can be added to the polymerization reaction by using a single «mixture to continuously or incrementally add, and preferably At the same time, the starter is added continuously or added; the aforementioned starter can use various conventional emulsified free radical polymerization. Page 06 This paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) -'-- --------------- llτ ------ 1 | (please read the notes on the back before filling in this page) Printed A7 ^ _B7__ by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (5) Reaction initiators, such as: peroxy and nitrogen compounds, the way of addition can be one-time addition or continuous addition or incremental addition, etc .; appropriate peroxide initiation Examples: Alkali gold percarbate, metrate, perborate, peroxonate, peroxonate, hydrogen peroxide, etc .; oil-soluble starting compounds can also be used, such as: cumyl Peroxide (dicumyl Pero-xide), tert-butyl peroxide (tert-butyl perox i de), isopropyl Through the gasification of hydrogen (cumene hydroperox i de) and the like. The polymerized mule of the pre-butadiene rubber emulsion and the monomer mixture is stirred under an inert gas of 20 ~ 100C, and it can also be pressurized to 0 ~ 10〇PS 1. G .; 90% during the reaction The monomers are polymerized, and the polymerization time usually takes 2 to 10 hours, and preferably 4 to 8 hours. The styrene strip monomers used in the present invention may be styrene, α-methyl methacrylate, α-chlorobenzene ethyl bromide, p-t-butylbenzene ethyl acetate, ρ-methylstyrene, 〇-ambient Styrene, P-methylstyrene, 2,5-dichlorobenzene ethylbenzene, 3,4 —— 'gas benzene ethylbenzene, 2,4,6-Sanao benzene ethylbenzene, 2, 5-dibromostyrene Among others, styrene or α-methylstyrene is preferred. The acrylic monomers used may be: acrylic, 〇 (_methacrylic, etc .; among them, acrylic eyes are preferred. The copolymerizable monomer used in the rubber graft copolymer (Α) of the present invention may be : (Meth) acrylic acid ester monomer, malealdimine monomer, acrylic acid, anhydrous maleic acid, ethylene glycol nethacrylate, etc .; among them (meth) acrylic acid ester Articles can be: methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl. Page 07 This paper uses the Chinese National Standard (CNS) A4 specification (210X297mm) (please Read the precautions on the back first and then fill out this page) Pack · A7 294680 B7____ 5. Description of the invention (butyl acrylate, benzyl methacrylate, hexyl methacrylate, hexyl methacrylate, twelve methacrylate Ester, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dimethylcyanoethyl methacrylate, etc., among which methyl methacrylate is preferred. The maleimide can be: Maleimide, N-Methylmaleimide Isopropyl maleimide, N-butyl maleimide, N-hexyl maleimide, N-octyl maleimide, dodecyl maleimide, N-ring Hexylmaleimide, N-phenylmaleimide, N-2,3-tolylmaleimide, N-2,4-tolylmaleimide, N-2,3 -Ethylphenylmaleimine, N-2,4-ethylphenylmaleimide, N-2,3-butylphenylmalealdimine, N-2,4-butylphenylimine Malealdimine, N-2,6-tolylmalealdimine, N-2,3-chlorophenylmaleimide, N-2,4-chlorophenylmaleimide, N -2,3-bromophenylmaleimide, N-2,4-bromophenylmaleimide, etc., among which N-methylmaleimide is the best. Through the aforementioned grafting After polymerization, a rubber graft copolymer (A) emulsion with a weight average particle size of 0.05 to 0.8 can be prepared, preferably 0.06 to 0.4 Na; when its weight average particle size is less than 0.05, the impact strength for the resin And the electroplating adhesion strength has no effect of changing the bodhisattva, and the tensile strength and gloss difference also become worse. The emulsion of the above rubber graft copolymer (Α) must be added with an appropriate coagulant For coagulation, the commonly used coagulants include sulfuric acid, sugar acids, alkaline earth metal salts, such as: calcium vaporized calcium salt, vaporized magnesium, magnesium sulfate, magnesium salt of aluminum sulfate, aluminum salt of which Age-earth metal salts are preferred. The polymer slurry after the coagulation is dehydrated through a dehydration process, and then dried to obtain a powdered granular oak waist graft copolymer (A); No. 08 of the present invention The paper size of the page is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297mm) -------- {袈 ------ 訂 定 -------- {(please read the notes on the back first Please fill in this page again) Printed by the Ministry of Economic Affairs, Central Bureau of Samples and Employee's Consumer Cooperatives Printed by the Ministry of Economic Affairs, Central Bureau of Samples and Employee's Consumer Cooperatives A7 B7 V. Description of the invention (7) The grafting rate is called styrene monomer, propylene The weight of the hard copolymer grafted onto the rubber is as follows: "weight with rubber": the ratio; and the molecular weight of the hard copolymer grafted on the rubber mash is between 40,000 and 120,000, preferably grafted When the rate is between 10 and 405K, you can get good impact strength, good plating crock strength and better appearance Plating the molded article. The propylene-based Shito copolymer (B) of the present invention is selected from: (meth) acrylate Shito monomer and acrylic eye strip monomer at least one monomer 10 ~ 100% by weight, styrene Shito list "0 ~ 80 weight And other copolymerizable monomers 0 ~ 30% by weight; and the propylene-based copolymer (B) can be styrene-acrylic eye copolymer, methyl methacrylate-styrene-acrylic blind copolymer, poly Methacrylate methacrylate and styrene-methyl methacrylate copolymer, etc .; The polymerization method can be obtained by various polymerization methods such as solution, block, emulsion or suspension. The styrene strip monomers, acrylic monomers, (meth) acrylate ester monomers and rubber graft copolymers (Α) used in the above propylene-based copolymers (B) are the same as described here, and are not here The detailed description; and other copolymerizable monomers selected according to the requirements may be acrylic acid, anhydrous maleic acid, ethylene glycol methacrylate and maleal imidated monomers. The graft copolymer (C) of the present invention is prepared from 0.1 to 10 parts by weight of the rubber graft copolymer (Α), 0.1 to 10 parts by weight of the propylene-based copolymer (B), and a total of 100 parts by weight The following monomer mixture is obtained by block and / or solution polymerization. The above monomer mixture contains: 80 ~ 45 parts by weight of styrene strip monomer, 15 ~ 50 parts by weight of propylene strip monomer and Copolymerized monomer 0 ~ 40 parts by weight, when the conversion rate of the polymerization reaches 40 ~ 90 weights Page 09 This paper scale is applicable to China National Standard (CNS) Α4 specifications (210X297 mm)

If " 'i —amt f ί ^ — — ^ ϋ In n I In n ^ i ^^^ 1 TJ --- Wear i (please read the notes on the back before filling in this page) Printed by consumer cooperatives Μ Β7 V. Description of invention (fat) S; When the above copolymer solution is devolatized to remove unreacted monomers and volatiles, the graft copolymer (C) can be prepared . The graft copolymer (C) of the present invention can be completed by a continuous block or solution polymerization reactor. The foregoing reactor includes: a column flow reactor, a completely mixed (CSTR) reactor, or contains Tube reactors of static mixing elements, etc., which are preferably complete mixing (CSTR) reactors; the number of the above reactors can be one, or two or more can be used; in the manufacture of the graft copolymer of the present invention (C), a polymerization initiator can be added to the reaction. The polymerization initiator includes pervaporated amides, pervaporated esters, pervaporated ketals, pervaporated silicate esters, and has For azo compounds such as nitro and cyclohexane rings, the addition amount of the aforementioned polymerization initiator is usually 0.01 to 1.0% by weight based on 100 parts of a single skeleton. The reaction temperature of the above reactor is controlled at 80 ~ 20〇υ, preferably within 90 ~ 160C, and the pressure of the reactor is controlled at 1 ~ 5 kg / cin2, as for the raw material solution to stay in the reaction The time in the device should be 1 to 5 hours; in addition, in order to control the molecular weight of the polymer, for example, tertiary-dodecyl mercaptan, n-dodecyl mercaptan, zepinolene, etc. can be used Yun transfer agent. 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 unreacted monomer and volatile matter are removed in the devolatilization step. Generally, the devolatization step can use minus ® 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; Copies of the polymer melt, and press it to make page 10. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling this page).

, TT Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy ^ 94660 --------- V. Description of the invention (?) Grain copolymer can be obtained (c). In the graft copolymer (C), the amount of the rubber graft copolymer (A) used is 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, and if less than 0.1 parts by weight, the impact on the resin composition The strength has no improvement effect, and the gloss difference of the resin is large. At the same time, it is not good in the plating adhesion strength and the resistance to cold and hot cycles. When the amount of the rubber graft copolymer (A) is higher than 10 parts by weight, The dispersibility of the rubber graft copolymer (A) in the resin composition is not good, and the appearance of the molded product of the resin composition and the electroplated finished product may also cause fisheye surface defects. The propylene based copolymer (B) used in the graft copolymer (C) of the present invention is between 0.1 and 10 parts by weight, of which 0.15 to 8 parts by weight is preferred; when the amount of the aforementioned components added is less than 0.1 parts by weight At one part, the rubber graft copolymer (A) tends to coagulate together, and cannot be completely dispersed and dissolved in the solution, which makes the pumping operation difficult. The graft copolymer (C) prepared after the reaction will contain coarse particles , The resin composition and the electroplated finished product will produce fish eye (fish eye) surface flaws, and the effect of improving the gloss difference of the resin composition and the adhesion strength of the electroplated finished product is not great; if the propylene-based polymer (B ) If the added amount is higher than 10 parts by weight, it is not economical to repeat the polymerization and processing of the propylene-based Shito polymer (B). The styrene and monomers and the copolymerizable monomers for producing the graft copolymer (D) of the present invention are the same as the monomers described in the aforementioned rubber graft copolymer (A). When the copolymerizable monomer is a maleimide sulfonate monomer, a resin composition excellent in heat resistance can be obtained. The aforementioned maleimide sulfonate monomer can be, for example, N-phenylmaleimide. Page 11 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) nn I mn ^. Nn I I. II! ^ (Read the precautions on the back before filling in this page) Central Bureau of Standards, Ministry of Economic Affairs Employee Consumer Cooperative Printed Α7 Β7 V. Description of the invention (| 〇) The manufacturing method of the above graft copolymer (D) is the same as that of the rubber copolymer (A), and the graft copolymer (D) is grafted with the rubber copolymer Copolymer (A) can be the same composition or different compositions, but based on «better impact strength and plating adhesion strength, the grafting rate of graft copolymer (D) is 18 ~ 80S; the question is Preferably, the molecular weight of the grafted hard copolymer is between 40,000 and 200,000. In the graft copolymer (D) of the present invention, the weight average particle diameter of the rubber particles is 0.05 ~ 0.8%, preferably 0.15 ~ 0.5. If the weight average particle diameter is less than 0.05im, high impact strength cannot be obtained. For resin and electroplated molded products with better adhesion strength, if the weight average particle diameter is higher than 0.8%, the tensile strength and impact strength will be reduced. The copolymer (E) of the present invention is polymerized from 80 to 50 parts by weight of styrene strip monomers, 20 to 50 parts by weight of acrylic eye strip monomers, and optionally copolymerizable monomers of 0 to 40 parts by weight. It is obtained that the above styrene strip monomers, acrylic monomers and copolymerizable monomers are the same as the monomers in the rubber graft copolymer (A), while the aforementioned copolymer (E) can be in the form of blocks, solutions, suspensions It can be obtained by the emulsion polymerization method, which is preferably block or solution polymerization method, the molecular weight of the aforementioned copolymer (E) is between 60,000 ~ 400,000, especially 80,000 ~ 300,000, the above copolymer (E) The content is 0 ~ 80 weight 3 ;. As for the resin composition prepared by mixing and extruding the graft copolymer (C), the graft copolymer (D) and the copolymer (E) in the present invention, the content of the graft copolymer (C) accounts for 5 to 90% of the total resin The weight is preferably 10 ~ 80 weight X. When the content is less than 5 weight! K, the improvement effect of the impact strength and gloss difference of the resin is not significant, and the adhesion strength of the plated molded product is poor. The 12th page of this paper is suitable for China National Standard (CNS) Α4 specification (210X297mm) (please read the precautions on the back before filling in this page) Stupid · Order 2946d0 A7 Printed by the Employees Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs _B7_ V. Description of the invention (丨 丨) At 90 times S! L !, the rubber content is insufficient and the puncture strength of the resin is poor; the content of the graft copolymer (D) in the present invention accounts for 95 ~ 10 weight 3 of all resins; 'It is preferably 60 to 15% by weight. When its content is greater than 95% by weight 3: due to too much rubber content, the resin has poor processability and the appearance of the molded product is not good. If this content is less than 10 weight S : Impact strength of resin composition and dense crock strength of electroplated molded products Worse. The present invention can further add a phenol or thiopropionate strip gasification inhibitor, weathering agent, etc. as needed to obtain a resin composition having predetermined characteristics; the present invention can also appropriately add a light stabilizer for improving the moldability of styrene resin Agents, fillers, colorants, slip agents, plasticizers and antistatic agents; in addition, the present invention can also be mixed with resins for polymer alloys, such as: polyacrylates, polyaldehyde amines, polyesters (PET, PBT) , Polyphenylene _, polyethylene helium, polymethyl methacrylate, ethylene-methyl methacrylate copolymer, polypropylene, styrene-butadiene block copolymer, hydrogenated acrylonitrile-butadiene copolymer Materials, hydrogenated styrene-butadiene block copolymers, etc., and the compounding amount is generally 5 to 200 parts by weight relative to 100 parts by weight of the resin composition. In order to obtain the resin composition of the present invention, the typical mixing method is: using a mixer such as a Hanbail mixer commonly used in the field of many synthetic resins, and then dry-mixing, such as an extruder mixer, kneader or Mixer such as Banbury mixer. When molding using the resin composition of the present invention, molding methods such as injection molding, extrusion molding, compression molding, and hollow molding are generally applicable. In order to explain the present invention in further detail, the following examples and physical property tests are described as follows. Unless otherwise stated, the composition of the following composition is applicable to the Chinese national standard (CMS> A4 specification) on the paper size of page 13 ( 210X 297mm) (Please read the precautions on the back before filling in this page). Binding. Order A7 B7 5. Description of the invention (p) The weight of the composition of the gold part is represented by the weight percentage # parts and the percentage tb. Example I -1 > Rubber graft copolymer (A-1): Ft «heavy __Ϊ. 1 · 3-butadiene 150. 00 persulfate solution (1%) 15. 00 potassium oleate 2. 00 Distilled water 190. 00 Ethylene glycol dimethacrylate 0.13 According to the above formula, the reaction was carried out at a reaction temperature of 651C for 12 hours. The conversion rate was 94¾, the solid content was about 40¾, and the weight average particle size was 0.1%. Rubber latex. In addition, the following components are used to produce a polymer coagulant containing carboxylic acid groups:

JL a (Please read the precautions on the back before filling in this page) Binding · Order ethyl acrylate and methacrylic acid potassium persulfate solution (U) sodium dodecyl benzoate solution (10S!) N-dodecyl sulfide Fermented distilled water 92 Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 200 0 According to the above formula, it is reacted at 75C inversion temperature for 5 hours to obtain a carboxylic acid group-containing polymer flocculant with a conversion rate of about 95% and a pH of 6.2. After that, 3.5 parts by weight of carboxylate group-containing polymer agglomerate (dry weight) was used to enlarge 100 parts by weight of synthetic latex latex (dry weight), and the pH of the resulting hypertrophic rubber emulsion was 8.7, weight average The particle size is about 0.18 Mm. Page 14 This paper scale is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) Employee consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Du Yinzhen A7 B7 V. Description of the invention (丨 3) Finally, the rubber emulsion is used to enlarge The following formulation is subjected to graft polymerization to produce a rubber mash graft copolymer (A-1). · Heavy weight W Enlarged rubber emulsion (dry weight) 100.0 Styrene 25.0 Acrylonitrile 8.3 Tertiary-dodecyl mercaptan 2.0 Isopropylated hydrogen peroxide 3.0 Ferrous sulfate solution (0.2¾) 3.0 Formaldehyde Sodium hyposulfite solution (10SO 0.9 ethylenediaminetetraacetic acid solution (0.25¾) 3.0 The rubber graft emulsion prepared according to the formula in the table above is coagulated with vaporized calcium (CaClO) to produce the rubber graft required by the present invention Copolymer (A-1) (Oak content 75 weight% SO, grafting ratio 24¾, molecular weight of grafted styrene-propylene copolymer is 78,000. ≪ Preparation Example I-2 > rubber graft copolymer (A -2): Synthetic rubber latex (rubber weight average particle size 0.1 μg) prepared in < Preparation Example I-1 > was directly graft-polymerized with the formula in the table below to obtain a rubber containing 71.4 weight Dong Zhi's rubber graft copolymer (A-2) has a rubber weight average particle size of 0.1%, a grafting rate of 26S, and a styrene-propylene sleeping copolymer grafted on rubber knots with a molecular weight of 65,000. __m_ Striving for heavy portions of synthetic rubber milk (0.1 x 1) (dry weight) 100.0 Styrene 30.0 Page 15 of this paper Applicable to China National Standard (CNS) A4 specification (210X297mm) --------- 1 'pack ------ ordered (please read the precautions on the back before filling this page) Α7 Β7 Economy Printed by the Employee Consumer Cooperative of the Central Bureau of Industry of the Ministry V. Description of the invention (14) Acrylonitrile third-grade twelve-yl alkyl fermentation cumene ferric hydroperoxide ferrous acid solution (0.2%) Formaldehyde times Sodium nitrate solution (1〇! «) Ethylenediaminetetraacetic acid solution (0.25¾) < Preparation Example Π-1 > propylene-based strip copolymer (B-1): the composition will be at a rate of 12 kg / hr Styrene 75 weight 3; Methyl methacrylate 10 weight X and acrylonitrile 15 weight! The raw materials of ϋ are mixed, and then ethylene distearate aldolamine 3.0 s / hr ·, pergasified benzaldehyde and third The grade-dodecyl mercaptan and the recovery liquid described later are combined as a feeding liquid to feed into the continuous tank type reactor with a stirrer and the internal temperature is maintained at 108 t: and the volume is 45 liters, and the reaction liquid The proportion of toluene in the reactor is kept at 15 3 !, and the polymerization rate is kept at 55S !. When the reaction liquid is removed by the devolatilization device, the required of the present invention can be obtained Particles of propylene-based strip copolymer; on the other hand, the volatile components removed are condensed by a condenser as a recovery liquid, and the mixed liquid of Burmese and the aforementioned raw materials is reused; in this way, the amount of benzoyl peroxide is adjusted The reaction rate, or adjust the third level of dodecyl alkyl alcohol; and at a rate of about 12 kg / hr to produce a melt flow index of 1.2 styrene-acrylonitrile-methyl methacrylate copolymer (B-1). < Preparation Example I-2 > propylene-based strip copolymer (B-2): The preparation method is the same as < Preparation Example Π-1 >, except that the composition of the single skeleton is 78 weight styrene χ, and the weight of propylene sleep 22! ϋ , Can be made melt flow refers to page 16

(Please read the precautions on the back and then fill out this page), ·, 1T L- This paper scale is applicable to China National Standards (CNS) Μ specifications (210X29 * 7mm) 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 (ι5) A styrene-propylene copolymer with a number of 1.1 (B-2). <Preparation Example m> Preparation of graft copolymer (c): · With <Preparation Example I -1 &gt; 6 parts by weight of the obtained rubber graft copolymer (A-1), 2 parts by weight of styrene-propylene-proton-methyl methacrylate (B-1) prepared by &lt; Preparation Example Π_1 &gt; , 72.0 parts by weight of styrene, 28 parts by weight of acrylonitrile, 7 parts by weight of ethylbenzene, 0.09 parts by weight of tertiary-dodecyl thiolease, 0.05 parts by weight of over-gasified benzoyl (starter) The raw material solution formed was continuously fed into the first reactor at a rate of 22 1 / hr. The volume of this first reactor was 44 liters, the reaction temperature was 120 t :, the pressure in the reactor was 4 kgs, The residence time of the reaction is 2 hours. The mixing speed of the spiral stirring device set in it is 100 rpin. There is a cooling circulation tube in the * mixing device. After the reaction in the first reactor, the mixture is continuously taken out and sent to the second reactor. The device in this second reactor is the same as that in the first reactor. When the conversion rate of the mixture is 60¾, the mixture is taken out and taken out again. The volatilization device removes unreacted monomers and volatiles, and then presses them out to granulate to prepare the graft copolymer (C-1). According to the aforementioned preparation method and the amount stated in the first table, the graft copolymers (C-2), (C-3), (C-4), (C-5), (C-6), ( C-7). &lt; Preparation Example IV &gt; Preparation of graft copolymer (D): Μ Weight 1,: 3-Butadiene 150.00 Potassium persulfate solution (1%) 15.00 Potassium oleate 2.00 Steamed fin water 190.00 Page 17 of this paper The standard is applicable to China National Standard (CNS) A4 (210X 297mm) (read the precautions on the back and then fill out this page) _ 294680 A7 B7

V. Description of the invention (丨 · =) Glycolic acid dimethacrylate 0.13 According to the above formula and reacted at 65¾ reaction temperature for 12 hours, the conversion rate is 94X, the solid content is about 4 (U, weight average particle size 0.1 Xun's synthetic rubber milk. In addition, the following ingredients are used to make a polymer coagulant containing carboxylic acid groups: Sm m___Q ethyl acrylate 90.0 methacrylic acid 10.0 potassium persulfate solution (U) 0.5 sodium dodecyl sulfate solution (10¾) 0.5 n-dodecyl mercaptan 1.0 distilled water 200.0 According to the above formula, it was reacted at 75¾ reaction temperature for 5 hours to obtain a carboxylic acid group-containing polymer flocculant with a conversion rate of about 95% and a pH value of 6.0. , Using 3 parts by weight of carboxylic acid group-containing polymer coagulant (dry weight) to enlarge 100 parts by weight of synthetic rubber latex latex (dry weight), the pH of the resulting hypertrophic rubber emulsion is 8.5, weight average particle The diameter is about 0.31%. Finally, the grafting polymerization reaction is carried out with the hypertrophic rubber emulsion according to the following formula to produce the rubber graft copolymer (D). (Please read the precautions on the back before filling this page) .

、 1T Ministry of Economic Affairs Central Standards Bureau employee consumption cooperation Du Printed S_ © _ Fenzhong Enlarged Rubber Emulsion (dry weight) 100.0 Styrene 38.8 Acrylonitrile 15.0 Tertiary-dodecyl sulfatase 2.0 Page 18 This paper size Applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297mm) A7 B7 The Ministry of Economic Affairs Central Bureau of Privileges and Employee's consumer cooperation du printed five. Description of the invention (I?) Cumene hydroperoxide 3.0 ferrous adenate solution (0.2¾) 3.0 · Formaldehyde sodium sulfoxylate solution (10¾) 0.9 Ethylenediaminetetraacetic acid solution (0.255O 3.0 The rubber graft emulsion prepared according to the formula in the table above is coagulated and dehydrated with calcium oxychloride (CaC 12) , And then dried to a moisture content of 23; below, you can prepare the required rubber graft copolymer (D) (rubber content 65 heavy Dong χ), the graft rate of 38S ;, grafted styrene The molecular weight of a propylene copolymer is 82,000. <Preparation Example V_1> Preparation of styrene-acrylonitrile copolymer (E-1): 76% by weight of styrene, propylene at a rate of 12 kg / hr Acetate 24 weight 5: The raw materials are mixed, and then ethylene distearate amide 3.0 s / hr , Benzoyl peroxide, tertiary-dodecylbenzyl alcohol, and the volatiles removed by the anti-formaldehyde described below after condensation are combined into a recovery liquid used as a feeding liquid to supply the internal temperature at 108 and A continuous kettle-type reactor with a volume of 45 liters and a mixer, and the proportion of toluene in the reaction liquid is kept at 15 S; and the polymerization rate is kept at 55¾. After the reaction liquid is removed through the devolatilizing device, The particles of styrene-acrylonitrile copolymer can be obtained; on the other hand, the volatile components removed are condensed by a condenser as the recovery liquid, and the mixed liquid of Burmese and the raw materials is reused; Adjust the amount of benzaldehyde to adjust the reaction rate, or adjust the amount of tertiary-dodecyl mercaptan; at a rate of about 12kg / hr, a styrene-acrylonitrile copolymer with a melt flow index of 3.0 (E -1). The paper size on page 19 is applicable to the Chinese National Standard (CNS) A4 (210X297mm) (please read the precautions on the back before filling out this page)

J Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy A7 __B7_ V. Description of Invention (U)

&lt; Preparation Example V_2 &gt; Preparation of styrene-acrylonitrile-maleimide copolymer (E-2): 68 weight of styrene at a rate of 12 kg / hr: 22 weight of acrylonitrile S:, Bu The raw materials of phenylmaleimine 10 weight χ are mixed, and then ethylene distearate 3.0 g / hr, pergasified benzoyl amide, tertiary-dodecyl mercaptan, and the reactions described below The recovered liquid formed after condensation of the removed volatiles is combined as a feed solution to feed into a Burmese kettle-type reactor with an internal temperature maintained at 108 t and a volume of 45 liters with a stirrer, and the reaction liquid The toluene ratio was kept at 15 3 !, while the polymerization rate was kept at 55¾. After the volatile components are removed through the devolatilization device, particles of styrene-acrylonitrile-maleimide copolymer can be obtained; on the other hand, the volatile components removed are condensed by a condenser as a recovery liquid It is mixed with the aforementioned raw materials before use; in this way, the reaction rate is adjusted from the amount of pergasified benzoyl acetone, or the amount of tertiary-dodecyl mercaptan is adjusted; and it is made at a rate of about 12kg / hr Styrene-acrylonitrile-maleimide copolymer (E-2) with a melt flow index of 1.5. The physical properties tests of the following examples and comparative examples are divided into two categories, one is the non-electroplated test H physical properties, which includes gloss difference and Ehrlich impact strength, and the other is the test H physical properties after pre-plating, which includes molding The appearance of the product, the heat and cold cycles, and the adhesion strength. The test standards for the above physical properties are as follows: Gloss difference: tested by Gardner (Gardner 600 Incidence angle) according to ASTM D-523, the unit adopts X, and the test test Η is one For injection products with a length of 300nm, a width of 25mm, and a thickness of 3mn, the fan-shaped winding edge is 15 to 10 inches away from the edge. Page 20 The paper size is applicable to the Chinese National Standard (CNS> A4 specifications (210Χ297 mm) l · ---- --- {^ ------- lsτ ------- ^ (Please read the precautions on the back before filling out this page) Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^^ 4680 αί B7 5 2. Description of the invention (I?) (A) Gloss difference in different parts: the gloss at 5 c · and 25 cn from the gate is measured in the direction perpendicular to the test H, the difference is smaller, the more the gloss difference is Small. (B) The gloss difference of the same part in different directions: perpendicular or parallel to the test Η To measure the gloss at 25c from the gate, the smaller the difference between the gloss measured in the vertical direction and the horizontal direction, the smaller the difference in gloss. IZOD: Test according to ASTM D-256, The unit is expressed in kg · cm / cm. The appearance of the electroplated molded product: the resin raw material is injected into the mechanism to obtain a test Η of 101.6 nn X76.5 π &gt; πιΧ3.2Πβ, and the test piece is plated to observe the plating test. The appearance of Η is indicated by X when there are pinholes or fisheyes on the surface of the electroplating test Μ. If the surface of the electroplating test Η is smooth and there are no pinholes, it is indicated by Ο * Cold / heated (passed / tested): Put the electroplating test H at room temperature for 15 minutes, then at -40T: let it stand for one hour, then put the test H at room temperature for 15 minutes, and finally put it at 80¾-hour, which is a cold and hot cycle; The plating test Μ is placed under the pre-conditions and taken out once, 3 times and 5 times to observe whether there are cracks or protrusions in each electroplating test. If there are cracks or protrusions, it means that the plating test piece failed. Smoothness and no cracks indicate that the electroplating test H has passed. * Depth of coating strength: According to ASTM Β-533, the unit is expressed in kg / cn. The procedures for the pre-plating of the pre-plated test specimens are as follows: —. Degreasing: sodium chloride at 50 ° C, sodium dichloride, and page 21 This paper scale is applicable to China National Standards (CNS) A4 (210X297mm) (Please read the precautions on the back before filling in this page) Packing _ Order A7 B7 ^ ----- 1 'invention description printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ^ ----- 1'Instructions for the invention (addition) Mix of acid sales 5 minutes in the liquid. 2. Roughing (etching): placed in a mixture of 681 chromic acid and sulfuric acid for 7 minutes. 3. Neutralize: Place in 2510 hydrochloric acid solution for 2 minutes. 4. Sensitizing & activating: Place it in the mixed solution of 30Ό, vaporized tin and hydrochloric acid for 4 minutes. 5. Accelator: placed in a 40t sulfuric acid solution for 1 minute Ο 6. Chemical Ni plating: placed in a mixed solution of 351 sulfuric acid, oxalic acid, sodium dihydrogen phosphate and boric acid for 12 minutes. t. Copper plating (Cu plating): placed in 25P copper acid solution for 30 minutes, the film thickness is 10%. 8. Ni plating: placed in a 551: sulfuric acid solution for 30 minutes, and its film thickness is 10 mm. Nine. Plating (Cr plating): placed in a 501C copper sulfate solution for 2 minutes, its film thickness is 0.15 yuan. ^ _m_m &lt; Example 1 &gt; Use 50 weight χ graft copolymer (c-υ (made by Preparation Example m-1), 31 weight graft copolymer (D) (made by Preparation Example IV Obtained) and 19 weight: K styrene-acrylonitrile copolymer (Ε-1) (from the preparation example V-1 cracked) mixed, and then added 2.0 parts by weight of slip agent and 0.05 parts by weight of silane-based polymer, And using Werner & Pfleiderer ZSK 35 extruder at 220 C to mix and granulate, you can get the rubber content of 17 tons Dong S! Styrene Shitou page 22 This paper scale is applicable to China National Standards (CNS) A4 specifications (210X297 Cli) — 11. n J 'Outerwear "(please read the precautions on the back before filling in this page) A7 __B7 _ printed by the Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs V. Description of invention () Resin composition, and then Injection molding under 220t (the injection machine is Zhenxiong company number SM-90), and the physical properties are measured. The injection conditions are as follows: ^ Injection temperature: 22〇t: Injection pressure: l50kg / cm2 (75%) injection speed : 72 cm3 / sec (80%) Test piece specification: 1 〇1.6 ® mx 7 6.5 hi nx 3.2 id di The electroplating procedure is described. After the electroplating, the test H is then evaluated for external pressure, cooling and heating cycles, and adhesion strength. In addition, the test H is injected under the same injection conditions as before, and the Ehrlich impact strength and gloss are tested. The measured results are shown in the attached table. 2. &lt; Example 2 &gt; After the raw materials are mixed uniformly according to the formula in Table 2, the processing method of Example 1 is followed, and the test Η for forming test is performed, and the measured physical properties and plating standby are also shown in Table 2. &lt; Example 3 &gt; After mixing the raw materials according to the formula in Table 2, the treatment method of Example 1 is followed, and the test Η for forming test is carried out. The measured physical properties and electroplating readyness are also shown in Table 2. &lt; Examples 4 &gt; After mixing the raw materials according to the recipe in Table 2 and mixing them according to the treatment method of Example 1, and forming test test H, the measured physical properties and plating performance are also shown in Table 2. &lt; Example 5 &gt; After mixing the ingredients according to the formula in Table 2, mix them according to Example 1 Page 23 The paper size is applicable to China National Standard (CNS> Α4 specification (210Χ29 &quot; 7mm) (please read the notes on the back before filling in this Page)-The Ministry of Economic Affairs Employee consumption cooperation du printed 2 ^ 46d0 at B7 V. Description of the invention (u) method, and test Η for molding test, the measured physical properties and electroplating characteristics are also shown in Table 2. &lt; Example 6 &gt; According to the table The formula of the second is to mix the raw materials uniformly according to the processing method of Example 1, and to test the molding test M. The measured physical properties and electroplating characteristics are also shown in Appendix 2. &lt; Comparative Example 1 &gt; The operating conditions are the same as in Example 1, but the resin composition does not contain the graft copolymer (C). The obtained test H was also tested for various physical properties and plating characteristics. The results are shown in Attached in the second table. &lt; Comparative Example 2 &gt; The operating conditions are the same as in Example 1, except that the graft copolymer (C) is changed to (C-5) in Schedule 1, that is, the graft copolymer ( C) The propylene-based strip copolymer (B) is not included. The obtained test Μ is also tested for various physical properties and electroplatability, and the results are shown in Appendix 2. &lt; Comparative Example 3 &gt; The operating conditions are the same as those in Example 1, but the graft copolymer (C) is changed to (C-6) as shown in Table 1, and the graft copolymer (C) prepared therefrom does not contain For the rubber graft copolymer (Α), the molded test Η also measures its physical properties and electroplating characteristics, and is listed in the second table. &lt; Comparative Example 4 &gt; The operating conditions are the same as in Example 1, but the amount of the graft copolymer (C) used is 2 weight! ί, the molded test H was also tested, and the measured results are also shown in Appendix II in. Page 24 This paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) (please read the precautions on the back before filling in this page) * 1Τ Du7 A7 B7_ Five by the Consumer Consumption Cooperation of the Central Sample Bureau of the Ministry of Economic Affairs 3. Description of the invention (23) &lt; Comparative Example 5 &gt; The operating conditions are the same as in Example 1, except that the amount of the wall adhesive graft copolymer (A) in the graft copolymer (C) is 16 parts by weight, which is molded The test strips were also tested, and the measured results are also shown in Attached Table 2. &lt; Comparative Example 6 &gt; The method and composition are the same as Comparative Example 1, except that the injection force of the resin composition is 420 kg / cm2 (30%) and the injection speed is 31.5 cm3 / sec (35¾). The test results of 1, 4 show that when the addition amount of the graft copolymer (C) in the resin composition of the present invention is less than 5 weight S, not only the impact strength is poor, but the improvement effect of gloss difference is not significant. The adhesion strength is also poor. The test results of Comparative Example 2 show that when the graft copolymer (C) is not added with the propylene-based strip polymer (B), not only the gloss difference of the resin composition and the densities of the electroplated finished product The effect of strength improvement is not large, and the appearance of the molded product of the skid plate will also produce fish eyes; and if the graft copolymer (C) does not contain the rubber graft copolymer (Α), the impact strength improvement effect of the resin composition is not great , The gloss difference of the composition is also large, the adhesion strength of the electroplated finished product and the resistance to cold and hot cycles are also poor, which can be confirmed by the test data of Comparative Example 3; The test of Comparative Example 5 shows that when the graft copolymer ( C) The use of the graft copolymer of rubber (Α) When the amount is higher than 10 weight χ, due to the poor dispersibility of the rubber waist graft copolymer (Α) in the resin, the appearance of the molded product of the resin composition and the finished finished product are not ideal; Although lowering the injection speed and injection pressure can slightly improve the electroplating performance of the composition of Comparative 1, the changes in the aforementioned injection conditions will cause a reduction in the production rate, which is not in line with economic benefits. __Page 25_ This paper scale is applicable to the Chinese National Standard (CNS &gt; Α4 specification (210X297mm) (please read the precautions on the back before filling in this page) Order A7 B7 V. Description of invention (2 4) Examples 1 to 6, the present invention is limited by the aforementioned components and usage amounts, not only can the resin composition have good impact strength, but also the gloss difference is small, when the resin composition is used as a plating molded product, its plating characteristics It can also be broadcast and improved, and can be used in the industry, and the invention patent application is submitted according to the law. However, the above are only the most feasible embodiments of the present invention. For those who are familiar with this technology, they should follow the spirit of the present invention. Modifications or changes made in the category should be included in the scope of the patent application in this case. 1. ^ 1 nn ^ In I 、 一 OJ (Please read the precautions on the back before filling this page)

L. Printed by the Employees' Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economy .fi pages This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm)

Claims (1)

A8 B8 C8 D8 printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs VII. Scope of Patent Application (|) No. 84109052 Application for Patent Application for the Patent Park Amendment 1. A styrene resin composition, including: ( 1) In the presence of a weight average particle diameter of 0.05 to 0.8 egg graft copolymer (A) 0.1 to 10 parts by weight and a propylene-based copolymer (B) 0.1 to 10 parts by weight, based on a total of 100 weight Parts of the following monomers: 80 to 45 parts by weight of styrene monomer, 15 to 50 parts by weight of acrylonitrile strip monomers and 0 to 40 parts by weight of copolymerizable monomers obtained by block and / or solution polymerization Graft copolymer (C) 5 ~ 90 weight S; wherein, the rubber graft. The graft copolymer (A) like in the presence of butadiene strip rubber 50 ~ 85 parts by weight, with styrene strip monomer and acrylonitrile strip 50 to 15 parts by weight of monomers, and 0 to 30 parts by weight of other copolymerizable monomers are obtained by graft polymerization, and the propylene-based strip copolymer (B) is derived from: (meth) acrylate strip monomers and propylene oxide At least one monomer selected from the strip monomers is 10 to 100% by weight, and the styrene bed alone sleeps 0 to 80% by weight S !, and He can copolymerize monomers from 0 to 30 to replace ϋί; (2) In the presence of 50 to 85 weight parts of butadiene rubber with a weight average particle size of 0.05 to 0.8, and styrene monomers and propylene Eye Shio monomer and optionally copolymerizable monomer mixture 50 ~ 15 parts by weight of emulsified graft polymerization graft copolymer (D) 95 ~ 10% by weight; (3) Styrene strip monomer 80 to 50 parts by weight, 20 to 50 parts by weight of the acrylonitrile monomer, and optionally copolymerizable monomers 0 to 40 parts by weight copolymerized (E) 0 to 80 parts by weight χ. 2. According to the styrene strip resin composition described in item 1 of the patent application park, the paper size on page 27 is based on China National Standard (CNS) A4 (210Χ297mm) (please read the precautions on the back first Fill in this page) Order A8 B8 C8 D8 Patent application scope (α) where the rubber graft copolymer (Α) is obtained by emulsion polymerization. 3. The styrene resin composition according to item 1 of the patent application scope, wherein the graft ratio of the rubber graft copolymer (A) is 10 to 40¾, and the molecular weight of the grafted hard copolymer is 40,000 to 120,000 . (Please read the precautions on the back before filling out this page) it sets the 28th page of this paper printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ί) 4680 β 1 -ffl m (N spicy ζ 1 x m braided ma heff-ffl m * -as 31 Su cag m (N spicy ma 唞 rubber graft copolymer (A) m HW p «« —-V o 3 MS Tanning parts by weight _ ΠΠηη township parts by weight πβη ο ο o ro 〇〇o --3 ro o ro o / * — s οσ 1 ►— * Sw ✓ CT &gt; Ο Ν &gt; 1 Η-1 ____- . · »— * V 〇1 1 ~~ ^ ο ο o N5 O〇O -o N5 〇Ol o / ^ S D3 1 1- &quot;» '«s- ^ 05 Ο * ν: &gt; 1 Η- »'W» .-—- V o 1 ro ο ο ot \ 3 O〇o 03 OO o tS5 oy * — σα 1 ro t \ 5 Ο / —Ν 1 ro -—- vo \ Os &gt;' — &lt; · Ο 〇〇ο o ΓΟ oo σ &gt; 〇〇o ΟΊ o cc 1 ro, &gt; __ »&lt; · σ &gt; ο &gt; 1 1 ~~» • w · S Cl 1 '— ^ ο ο o 〇〇 o -J ΓΟ oo 1 05 Ο S &gt; 1 Η- * Cl 1 cn ο ο o to oo &lt; 〇-J ro o ro o σσ 1 »— * '• w * ο 1 o 1 05 s— ^ ο ο o ro 〇〇ot oo N5 o οσ 1 1—1 &gt; — * σ &gt; ο / «— ** s &gt; 1 t—» ^-K o 1-&lt; l, w 4tt si ϋ M 龱 m plating adhesion strength (Kg / cm) c + e; CD 0?% Um CD Φ 5: Identify Λ 11 Tan Er ma〇 豳 Χ m m β 砓 砘 ψ 〇〇 gloss difference S; the total amount of rubber contained in the resin ") copolymer ( Ε) wt% graft copolymer (D) wt% graft copolymer (c) wt% 1 cycle 3 cycles 5 cycles (b) vertical / horizontal (a) 5cro / 25cm ΓΟ 〇〇10 / 10 10 10 / 10 10/10 〇〇〇Ο — Ο ro ro 〇 (Ε-1) 29.0 21.0 (Cl) 50.0 Example 1 ro ς〇10 / 10 10/10 10/10 〇29.5 Ο -0 η- * 〇〇 &gt; — * Ο Ο 17.8 (Cl) 82.2 Example 2 ro ΟΊ 10/10 10/10 8/10 〇27.4 Η- * ro CO Ο (Ε-1) 55.9 24.1 (Cl) 20.0 Example 3 ro- 3 10/10 9/10 9/10 〇CO ΟΙ μ ~ * ro »—1 CO? Ο (Ε-1) 28.7 21.3 (C-2) 50.0 Example 4 ro do 10/10 9/10 .mo 〇 27.5 I ο 〇〇〇H- * ο 1 fO CO σ> (C-3) 76.4 Example 5 to 10/10 10/10 9/10 〇27.2 Η-A ►-* to 17.0 (Ε-2) 28.7 21.3 (C-4) 50.0 Example 6 〇〇 9/10 5/10 2/10 〇25.1 α> 〇〇〇〇05 17.0 1 (Ε-1) 73.9 26.1 1 Comparative Example 1 ro o 1 1 1 1 1 X ro αι οι to σ> Η-1 Ο ( Ε-1) 19.0 co (C-5) 50.0 Comparative Example 2 〇〇9 / 10 6/10 2/10 〇CO σ> oo 〇〇h-1 Ο (Ε-1) 16.0 26.1 (C-6) 50.0 Comparative Example 3 t-1 〇〇10 / 10 5/10 2/10 〇24.8 ΓΟ 〇〇ro Η -0 ο (Ε-1) 72.0 tS3 σ> o (C-3) 2.0 Comparative Example 4 ro 1 1 1 1 1 X 26.8 σ> N5 05 17.0 (Ε-1) 35.7 CO (C-7) 50.0 Comparative Example 5