TW466262B

TW466262B - Styrene-based resin composition

Info

Publication number: TW466262B
Application number: TW86116447A
Authority: TW
Inventors: Chiuan-Ming Lin; Dung-Bi Shiue
Original assignee: Chi Mei Corp
Priority date: 1997-11-05
Filing date: 1997-11-05
Publication date: 2001-12-01

Abstract

This invention provides a styrene-based resin composition which exhibits excellent impact and tensile strength and which can prevent cracking and frosting phenomena due to long time erosion by fluorochlorocarbon. The composition comprises: (1) 100 parts by weight of a styrene-based resin obtained from 95-0% by weight of a styrene copolymer (A) and 5-100% by weight of a rubbery grafted copolymer (B), wherein the styrene copolymer (A) contains 20-40% by weight of an acrylonitrile monomer, and the rubbery grafted copolymer (B) is obtained by graft polymerization of a styrene monomer, an acrylonitrile monomer and an optionally used copolymerizable monomer in the presence of a diolefin rubber; (2) 0.5-40% by weight of a polyester-based thermoplastic elastomer (C); and 0.5-40% by weight of an acrylic rubber (D).

Description

466262 Λ7 Β7 五、發明説明（丨）本發明係有關於一種苯乙烯系樹脂組成物，特別是指一種具有良好对衝擊強度、抗拉強度，並且具有可防止組成物經氟氯碳化合物（簡稱H C F C )曰久侵蝕，而產生龜裂及霧化現象之苯乙烯樹脂組成物。按’熟悉該項技術者皆知，將橡膠狀接枝共聚物分散於苯乙烯系共聚物中’所製得的產品是一種耐衝擊笨乙烯系樹脂組成物’此種樹脂组成物可運用在射出成型、押出成型、真空成型、吹延成型或熱成型等方面；一般而言，電冰箱在製造上其外側用鋼板，内侧則採用苯乙烯系樹脂板材’為了達到隔熱的效果，通常會在鋼板與内層間夾設有一聚氨基甲酸酯（Polyurethane)發泡層，前述聚氨基曱酸酿發泡層係由例如：2-氟-2,2-二氯乙烷（2-：^11〇1"0- 2,2-dichloroethane，簡稱 HCFC-141b)以及 2,2-二氣 _ 經濟部中央標準局^工消费合作.社印聚 (請先閲讀背面之注意事項再填商本頁) 1，1，1-三氟乙烷（2,2-dichloro _l，l,l-trifluoro ethane ，簡稱HCFC-123)等氟氯碳化合物（簡稱iiCFC)發泡劑發泡成型’而此等HCFC發泡劑會殘留在pu發泡層中，隨著時間而漸漸擴散並滲入侵蝕苯乙烯系樹脂板材，而使得電冰箱内側板材之肋骨處發生龜裂及霧化之現象；因此，如何在具有良好耐衝擊性之同時’使樹脂加工之成型品與聚氨基甲酸酯層之殘留發泡劑接觸時不致於發生龜裂及霧化現象’乃為此領域極待改善之課題。而在先前技術中，如曰本發明專利特開平7—242764號 ^中冒揭露，由於聚丙烯酸丁基酯（p〇ly butyl ablate) ί 可吸收聚氨基甲酸醋層之發泡劑，因此，在冰箱的聚氨基巾10 -------： 4 6 626 2 經濟部中央標準局另工消费合作社印製 Λ7 _ B7 五、發明説明（二）曱酸酯層與笨乙烯系樹脂層中間塗抹一層聚丙烯酸丁基酉旨，可防止苯乙烯系樹脂層產生龜裂或霧化的現象，惟若如此會增加施工之複雜度而難稱理想。另外’曰本發明公開專利特開平7-26097號及特開昭 62-1 58747號案中亦曾述及，在苯乙烯系樹脂中直接加入可防止受到聚氨基甲酸酯層之HCFC發泡劑侵蝕的化合物，例如：壓克力系橡膠，以提高樹脂抵抗HCFC發泡劑的侵敍 ’惟在苯乙稀系樹脂中添加壓克力橡勝，會造成对衝擊強度、抗拉強度等物性的降低。為了解決上述先前技術所存在的缺點，本案發明人乃經銳利的研究’開發出一種在具有良好耐衝擊強度、抗拉強度之同時’亦可防止組成物長期和氟氣碳化合物接觸時產生龜裂與霧化現象之苯乙烯系樹脂組成物。爰是’本發明之主要目的係在提供一種具有良好耐衝擊強度、抗拉強度，並具有優異耐HCFC性之苯乙烯系樹脂組成物。而’本發明之苯乙烯系樹脂組成物乃包含： (1) 100重量份之苯乙烯系樹脂，其係由苯乙烯系共聚物（Α) 95〜0重量％以及橡膠狀接枝共聚物（Β) 5〜1〇〇重量％所組成，其中，苯乙烯系共聚物（Α)中含有2〇〜40重量％之丙烯腈系單體，而橡膠狀接枝共聚物（Β)係在二烯系橡膠存在下，和苯乙烯系單體、丙烯腈系單體及視需要而選之可共聚合單體接枝聚合而得； (2) 0. 5〜40重量份之聚酯系熱可塑性彈性體（c); (請先聞讀背面之注意事項再填寫本頁} i.466262 Λ7 Β7 V. Description of the invention (丨) The present invention relates to a styrene resin composition, in particular, it has a good impact strength, tensile strength, and has the ability to prevent the composition HCFC) is a styrene resin composition that has been eroded for a long time and has cracked and atomized phenomena. According to 'A person familiar with this technology knows that the rubber-like graft copolymer is dispersed in a styrene-based copolymer' and the product obtained is an impact-resistant stupid vinyl resin composition. This resin composition can be used in Injection molding, extrusion molding, vacuum molding, stretch molding or thermoforming; generally speaking, refrigerators are manufactured with steel plates on the outside and styrene resin plates on the inside. In order to achieve the effect of heat insulation, A polyurethane foam layer is interposed between the steel sheet and the inner layer. The aforementioned polyurethane foam layer is made of, for example, 2-fluoro-2,2-dichloroethane (2-: ^ 11〇1 " 0- 2,2-dichloroethane (referred to as HCFC-141b) and 2,2-digas _ Central Standards Bureau, Ministry of Economic Affairs ^ Industrial and consumer cooperation. Printed by the society (please read the precautions on the back before filling out the merchant's book Page) 1,1,1-trifluoroethane (2,2-dichloro_1, l, l-trifluoroethane, HCFC-123) and other fluorochlorocarbon compounds (iiCFC) foaming agent foaming molding 'and this Such as HCFC foaming agent will remain in the pu foam layer, gradually diffuse and penetrate into the erosion styrene over time Ethylene resin sheet, which causes cracks and fogging on the ribs of the inner sheet of the refrigerator; therefore, how to 'residue the resin-processed molded product and the residue of the polyurethane layer while having good impact resistance The occurrence of cracking and atomization when the blowing agent is in contact is a subject that needs to be improved in this field. In the prior art, for example, as disclosed in Japanese Patent Application Laid-Open No. 7-242764 ^, because polybutyl butyl acrylate can absorb the foaming agent of the polyurethane layer, therefore, Polyurethane towels in refrigerators 10 -------: 4 6 626 2 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 _ B7 V. Description of the invention (II) The acetate layer and the stupid vinyl resin layer Applying a layer of polybutyl acrylate in the middle can prevent the styrenic resin layer from cracking or fogging. However, it will be difficult to make it ideal if it will increase the complexity of construction. In addition, it was also mentioned in the cases of Japanese Patent Laid-Open No. 7-26097 and Japanese Patent Laid-Open No. 62-1 58747 that the direct addition of styrenic resin can prevent HCFC foaming caused by the polyurethane layer. Compounds that are attacked by agents, such as acrylic rubber, to improve the resistance of the resin to HCFC foaming agents. However, adding acrylic rubber to styrene resins will cause impact strength, tensile strength, etc. Decrease of physical properties. In order to solve the above-mentioned shortcomings of the prior art, the inventor of this case has developed a sharp research 'developed a method that has good impact strength and tensile strength at the same time' and can also prevent the formation of turtles when the composition is in contact with fluorocarbon compounds for a long time Cracking and atomizing styrene resin composition.爰 is the main object of the present invention is to provide a styrene-based resin composition which has good impact strength, tensile strength, and excellent HCFC resistance. The styrenic resin composition of the present invention includes: (1) 100 parts by weight of a styrenic resin, which is composed of 95 to 0% by weight of a styrenic copolymer (A) and a rubber-like graft copolymer ( Β) 5 to 100% by weight, wherein the styrene-based copolymer (A) contains 20 to 40% by weight of an acrylonitrile-based monomer, and the rubbery graft copolymer (B) is composed of two 5 ~ 40 parts by weight of polyester-based heat in the presence of an olefin-based rubber, graft-polymerized with a styrene-based monomer, an acrylonitrile-based monomer, and a copolymerizable monomer selected as needed; Plastic elastomer (c); (Please read the precautions on the back before filling in this page} i.

、1T , 46 626 2 經濟部中央標準局貞工消费合作社印製 A7 B7 五、發明説明㈠） "~~~ -- (3) 0,5〜40重量份之壓克力系橡膠（D)。本發明之苯乙烯系共聚物（A)係由笨乙烯系單體Μ 重量份、丙烯睛系單體18〜45重量份，及視需要而選之可共聚合單體Q〜4Q重量份聚合而得’其可以塊狀、落液、懸濁或乳化聚合法製得，其中又以塊狀或溶液聚合法為佳 ,上述笨乙烯系共聚物（A)之重量平均分子量在6〇,〇〇〇〜 400’0〇0之間，較佳為8〇,〇〇〇〜3〇〇,〇〇〇之間；本發明苯乙烯系共聚物（A)中的苯乙烯系單體可為：苯乙烯、甲基苯乙烯、間-氯苯乙烯、對-第三丁基苯乙烯、對_甲基苯乙烯、鄰-氯苯乙烯、對-氣苯乙烯、2,5 _二氣苯乙烯、 3, 4 - 一氯笨乙婦、2, 4, 6 _三溴笨乙烯以及5 _二溴苯乙烯等，其中，以笨乙烯或α_甲基苯乙烯較佳。使用於本發明之丙缚腈系單體可為··丙婦腈、α —曱基丙烯腈等’其中以丙烯腈較佳；本發明苯乙烯系共聚物（Α) 中使用之可共聚合單體可為：（甲基）丙烯酸酯系單體、馬來酿亞胺系單體、丙烯酸、〒基丙烯酸、無水馬來酸等，其中’ C甲基）丙烯酸酯系單體可為：甲基丙烯酸甲酯、甲基丙稀酸乙S旨、甲基丙婦酸丙g旨、甲基丙埽酸丁酷、甲基丙婦酸苯甲酯、甲基丙婶酸己酯、甲基丙稀酸環己酯、甲基丙烯酸十二烷酯、甲基丙烯酸2 -羥乙醋、甲基丙烯酸縮水甘油酯、甲基丙烯酸二甲氨基乙酯、丙稀酸甲酯及丙烯酸丁酯等，其中以甲基丙烯酸甲酯、甲基丙烯酸丁酯為佳。馬來醯亞胺系單體可為：馬來醯亞胺、N-甲基馬來醯、 1T, 46 626 2 Printed by the Zhengong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention㈠) " ~~~-(3) 0,5 ~ 40 parts by weight of acrylic rubber (D ). The styrene-based copolymer (A) of the present invention is polymerized from stupid vinyl-based monomers M by weight, acryl-based monomers 18 to 45 parts by weight, and optionally copolymerizable monomers Q to 4Q by weight It can be obtained by block, liquid, suspension or emulsification polymerization methods, among which block or solution polymerization methods are preferred. The weight average molecular weight of the stupid ethylene-based copolymer (A) is 60,000. The styrenic monomer in the styrenic copolymer (A) of the present invention may be: 0 to 400'000, preferably 80,000 to 300,000; Styrene, methylstyrene, m-chlorostyrene, p-tert-butylstyrene, p-methylstyrene, o-chlorostyrene, p-aerostyrene, 2,5_aerated styrene , 3, 4-monochlorobenzyl ethene, 2, 4, 6-tribromobenzyl ethylene, and 5-dibromostyrene, etc. Among them, benzyl ethylene or α-methylstyrene is preferred. The acrylonitrile-based monomer used in the present invention may be ... propionitrile, α-fluorenyl acrylonitrile, etc. Among them, acrylonitrile is preferred; the copolymerizable polymer used in the styrenic copolymer (A) of the present invention Monomers can be: (meth) acrylate monomers, maleimide monomers, acrylic acid, methacrylic acid, anhydrous maleic acid, etc., where 'C meth) acrylate monomers can be: Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, formazan Cyclohexyl acrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, methyl acrylate and butyl acrylate Among them, methyl methacrylate and butyl methacrylate are preferred. The maleimide imide monomers can be: maleimide, N-methylmaleimide

X 私纸張尺度適用中國固家楯準（CNS ) Λ4^祐（210X29?公兑） (請先閲讀背面之注意事項再填寫本頁) 訂 % 經濟部中央橾準扃員工消f合作社印製 466262 A7 ________ Β7 五、發明説明（4 ) 亞胺、Ν-異丙基馬來醯亞胺、Ν_ 丁基馬來醯亞胺、Ν_己基馬來醢亞胺、辛基馬來醯亞胺、Ν-十二基馬來醯亞胺、Ν_ 環己基馬來醯亞胺、笨基馬來醯亞胺、ν-2, 3-甲笨基馬來醢亞胺、Ν-2, 4-甲苯基馬來醢亞胺、Ν-2, 3-乙苯基馬來酿亞胺、Ν-2,4-乙苯基馬來醯亞胺、Ν-2,3-丁苯基馬來醯亞胺、Ν-2, 4-丁苯基馬來醯亞胺、Ν—2, 6_甲苯基馬來醯亞胺、Ν-2, 3-氯笨基馬來醯亞胺、ν-2, 4-氣苯基馬來醯亞胺、Ν-2, 3-溴笨基馬來醯亞胺、Ν_2, 4-溴苯基馬來醯亞胺等 ’其又以Ν-苯基馬來醯亞胺為最佳。本發明笨乙烯系樹脂組成物中’苯乙烯系共聚物（Α)組成中’丙烯胯系單體含量一般在18〜42重量％，較佳為2〇〜40重量％，最佳在24〜38重量％，若丙烯腈系單體所佔比率大於42重夏％時’樹脂組成物之成品會變黃，即γ I值 (黃色度）會偏高，且成型品加工性變差，因此，為了得到較為優良之成品，本發明苯乙烯系共聚物（Α)中的丙烯跨系單體所佔之比率須加以控制。本發明之橡勝狀接枝共聚物（Β)係由二稀系橡膠2〜g〇重量份，以及由苯乙烯系單體50〜90重量％、丙稀賸系單體10〜50重量％ ’及視需要而選之可共聚合單體〇〜4〇重量％所組成之單體混合物98〜1〇重量份接枝聚合而得. 其可經由個別的塊狀、溶液、懸浮或乳化聚合作用聚合而製得，亦可經由此等聚合方法之組合製得，如乳化—塊狀或塊狀一懸浮聚合方法；較佳為乳化聚合法、域狀聚合法及溶液聚合法’尤以乳化聚合法為較佳；經乳化聚合而得 ___-頁本纸張尺度適用中國國家標準（CNS ) A4规格i 2i〇X2i)7公益） ----- (請先閱讀背面之注意事項再填寫本頁〕X Private paper size is applicable to China Gujia Standard (CNS) Λ4 ^ You (210X29? Credit) (Please read the precautions on the back before filling this page) Order% Printed by the Central Government of the Ministry of Economic Affairs 466262 A7 ________ B7 V. Description of the invention (4) Imine, N-isopropylmaleimide, N_butylmaleimide, N_hexylmaleimide, octylmaleimide , N-dodecylmaleimide, N_cyclohexylmaleimide, Benzylmaleimide, ν-2, 3-methylbenzylmaleimide, Ν-2, 4- Tolyl maleimide, N-2,3-ethylphenylmaleimide, N-2,4-ethylphenylmaleimide, N-2,3-butylphenylmaleimide Imine, Ν-2, 4-butylphenylmaleimide, N-2, 6-tolylmaleimide, NM-2, 3-chlorobenzylmaleimide, ν-2 , 4-aminophenylmaleimide, N-2, 3-bromobenzylmaleimide, N_2, 4-bromophenylmaleimide, etc. Amidine is the best. The content of the propylene-based monomer in the 'styrene-based copolymer (A) composition of the stupid vinyl-based resin composition of the present invention is generally 18 to 42% by weight, preferably 20 to 40% by weight, and most preferably 24 to 40% by weight. 38% by weight. If the proportion of acrylonitrile-based monomer is greater than 42% by weight, the finished resin composition will turn yellow, that is, the γ I value (yellowness) will be high, and the processability of the molded product will be poor. In order to obtain a relatively good finished product, the ratio of the propylene cross-linked monomer in the styrene-based copolymer (A) of the present invention must be controlled. The rubber-like graft copolymer (B) of the present invention is composed of 2 to g parts by weight of a dilute rubber and 50 to 90% by weight of a styrene-based monomer and 10 to 50% by weight of a propylene-based monomer. 'And the copolymerizable monomers selected from 0 to 40% by weight of the monomer mixture composed of 98 to 10 parts by weight of graft polymerization. It can be obtained by individual block, solution, suspension or emulsion polymerization It can be obtained by polymerization, or it can be made by a combination of these polymerization methods, such as emulsification-block or block-suspension polymerization methods; preferably emulsion polymerization method, domain polymerization method and solution polymerization method, especially emulsification. The polymerization method is better; it is obtained by emulsification polymerization. _- The paper size of this paper applies the Chinese National Standard (CNS) A4 specifications i 2i〇X2i) 7 public welfare) ----- (Please read the precautions on the back before Fill out this page]

、1T, 1T

P 屬： 466262 Μ Β7 五、發明説明（5P belongs to: 466262 Μ B7 V. Description of the invention (5

之橡膠狀接枝共聚物⑻r 乂佳的方式係在丁二缔橡膠乳液 25〜90重量份(乾重)存在下，和苯乙稀系單體5〇〜90重量 %、丙烯u單體〜5Q重量％，以及㈣要而選之可共聚合單體。〜50重量％所組成之單體混合物75〜1〇重量份接枝聚合而得重量平均粒徑在mb之乳液，爾後經政結、脫水、乾料步驟，而製得橡膠狀接枝共聚物⑻ ，上述橡膠狀接枝共聚物⑻之橡膠含量通常在25〜90重里％較佳為45〜80重量％，前述丁二稀系橡勝乳液乃包含100〜60重量%之共軛二烯單體，和〇〜4〇重量％可共聚合不飽和單體所形成的均聚合物(h嶋polymer )，或其八聚物（copolymer )，别述共輛二稀單體可以下式表示： R 請閲讀背之注項再填The preferred method of rubber-like graft copolymer ⑻r is in the presence of 25 to 90 parts by weight (dry weight) of butadiene rubber emulsion, 50 to 90% by weight of styrene monomer, and propylene u monomer to 5Q% by weight, and copolymerizable monomers are preferred. 75 ~ 10 parts by weight of a monomer mixture composed of ~ 50% by weight is graft-polymerized to obtain an emulsion having a weight average particle size of mb, and then undergoing steps of coagulation, dehydration, and drying to obtain a rubber-like graft copolymer ⑻ The rubber content of the rubbery graft copolymer ⑻ is usually 25 to 90% by weight, preferably 45 to 80% by weight. The aforementioned butadiene-based rubber emulsion contains 100 to 60% by weight of a conjugated diene monomer. Polymer, and homopolymer (h〇polymer) formed by copolymerizing unsaturated monomers with 0 to 40% by weight, or octapolymer (copolymer) thereof. In addition, a total of two dilute monomers can be expressed by the following formula: R Please read the back note and fill it out

I I 經濟部中央標準局β工消φ：合作杜印裝 CH2=C-CH=CH2 其中R可為氫基、甲基或氣基等，而可共聚合不飽和單體可為苯乙稀系單體、丙稀腈系單體、甲基丙稀酸酿系單體、丙烯酸酯系單體或其混合物。上述丁二烯系橡膠乳液可為聚丁二烯、丁二烯—笨乙烯共聚物、丁二婦—丙歸腈共聚物、丁二稀—甲基丙婦勝共聚物等，I可以前述單體直接聚合成重量平均粒徑〇的〜〇·8面之形態，亦可先聚合成U5〜〇.18咖之小粒徑橡膠乳液後，再以傳統的橡膠肥大法，冑〇.〇5〜〇18诹之小粒徑橡膠乳液肥大成G.2〜Q.8咖的橡膠乳液，前述橡踢肥大法可為添加有機酿或+風施士 A ΧΛ, Μ佩敗次金屬鹽或含羧酸基之高分子凝集劑本紙張訂 m :) *l46 626 2 經濟部令央標準局男工消贤合作社印製 A7 B7 五、發明説明（的化學肥大法、機械攪拌之機械肥大法或者冷凍肥大法等 ’前述化學肥大法所採用之高分子凝集劑可使用例如丙歸酸丁酯一甲基丙稀酸共聚物。上述乳化聚合而得之橡膠狀接枝共聚物（B)之橡膠粒子具有單峰式粒徑分佈或者雙峰式粒徑分佈，其中，單峰式粒徑分佈的重量平均粒徑為〇.〇5〜〇 8咖，而雙峰式粒握分佈的重量平均粒徑為〇〇5〜〇18咖及〇.2〜〇.8咖。而利用塊狀或溶液聚合而得之橡膠狀接枝共聚物（B)的製造方法’係將例如二烯系橡膠2〜25重量份預先溶於98 〜75重量份之單體混合物及視需要而選之溶劑中’該單體 h合物包括50〜90重量％之苯乙烯系單體、1〇〜50重量％之丙烯腈系單體及〇〜4〇重量％之可共聚合單體，接著將所得/合液泵入反應槽中混合均勻，以進行接枝聚合反應，反應期間可視情況添加適當的鏈移轉劑，例如第三—十二烷基硫％以控制聚合物之分子量，而使用之反應槽可由多槽組合而成，較佳為附有強力攪拌器之釜型反應槽，使用之溶劑可為甲苯、二曱笨、乙苯、曱基一乙基酮、乙基醋酸等。前述使用於塊狀或溶液聚合法之二烯系橡膠較佳係以陰離子聚合法聚合而得者，例如：丁二#橡膠、異戊間二烯橡膠、氣丁二烯橡膠、丁二烯〜丙烯蹌橡膠、丁二烯一苯乙烯橡膠等，其中丁二烯橡膠有高順式（Hi-Cis)含量及低順式（Los-Cis)含量之分；高峒式橡膠中，其順式（Cis) /乙烯基（Vinyl)之典型重量組成為94〜98%/ι〜⑽，其 ( 2!〇Χ 297λ>^; f請先閱^背面之注意事項再填寫本頁} ------.-----^----裝------訂------，ιι-ί---一卜 — l·· 46 626 2 經濟.邱中央橾準扃於工消费合作枉印製 Λ 五、發明説明（γ ) 餘組成為反式（Trans)結構；其Mooney黏度在20〜120間 ’分子量範圍以1 〇〇, 〇〇〇〜8〇〇, 〇〇〇為佳；低順式橡膠中，順式/乙烯基之典型重量紕成為2〇〜40%/1〜20% ，其餘為反式結構；其Mooney黏度在20〜120間；適合於本發明之笨乙烯/丁二烯共聚合橡膠，其聚合型式可為二段式 (di-block)共聚合、三段式（tri-block )共聚合、無規則共5^物（random)或星式共聚合（star type )。而苯乙稀/ 丁二烯橡膠之重量比例範圍較佳為5 /95到80/20，分子量範圍較佳為50, 000〜600, 000 ;本發明之塊狀或溶液接枝共聚物中，適用之橡膠以丁二烯橡膠及苯乙烯/丁二稀橡膠為佳。由塊狀或溶液聚合法聚合而得之橡膠狀接枝共聚物（B) ’其橡膠粒子之重量平均粒徑一般在0.6〜1〇咖之間，較佳為1.0〜7_0 um，前述塊狀或溶液橡膠狀接枝共聚物（β)之橡膠含量通常為4〜25重量％，較佳為8〜15重量％。本發明之橡膠狀接枝共聚物（Β)除了可各别使用前述礼化聚合法之橡膠狀接枝共聚物或塊狀（或溶液）聚合法之橡膠狀接枝共聚物外，亦可將前述二者併用，以形成雙峰或三峰式分佈：雙峰式分佈者如： (1) 重量平均粒徑0.2〜0.8 um(乳化聚合），重量乎均粒徑0.6〜l〇um(塊狀或溶液聚合）；或 (2) 重量平均粒控0.05〜〇_ 18 um(乳化聚合），重量平均粒徑0. 6〜10 um (塊狀或溶液聚合）。衣紙張尺度適用中國國家標荜（CNS )八4規诘（2!0X297^ii (請先閲讀背面之注意事項再填寫本頁) ----·'----^---r---i------訂------束--^---_--.II. Central Bureau of Standards, Ministry of Economic Affairs, β, φ: Cooperative printing, CH2 = C-CH = CH2, where R can be hydrogen, methyl, or gas, and the copolymerizable unsaturated monomer can be styrene-based Monomer, acrylonitrile-based monomer, methacrylic acid-based monomer, acrylate-based monomer, or a mixture thereof. The aforementioned butadiene-based rubber emulsion may be polybutadiene, butadiene-benzyl ethylene copolymer, butadiene-acrylonitrile copolymer, butadiene-methacryl copolymer, etc. The polymer can be directly polymerized into a form with a weight average particle size of 0 ~ 8. It can also be polymerized into a small particle size rubber emulsion of U5 ~ .18 coffee, and then the traditional rubber hypertrophy method is used. The small-diameter rubber emulsion of ~ 〇18 肥 is enlarged into a rubber emulsion of G.2 ~ Q.8, the aforementioned rubber kick hypertrophy method can be the addition of organic brewing or + Win Shi Shi A χΛ, Μ 败 secondary metal salt or containing Carboxylic acid-based polymer agglutinating agent for paper m :) * l46 626 2 Printed by A7 B7, Male Workers' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (Chemical hypertrophy method, mechanical agitation method or mechanical hypertrophy method) As the polymer agglutinating agent used in the aforementioned chemical hypertrophy method such as the freezing hypertrophy method, for example, butyl propionate monomethyl acrylic acid copolymer can be used. Rubber of the rubber-like graft copolymer (B) obtained by the above emulsion polymerization The particles have a unimodal particle size distribution or a bimodal particle size distribution. The weight-average particle diameter of the diameter distribution is from 0.05 to 0.88, and the weight-average particle diameter of the bimodal particle grip distribution is from 0.05 to 〇18 and 0.2 to 0.8. Method for producing a rubber-like graft copolymer (B) obtained by polymer polymerization in a state or in solution, for example, 2 to 25 parts by weight of a diene rubber is previously dissolved in 98 to 75 parts by weight of a monomer mixture and is selected as required. In the solvent, the monomer compound includes 50 to 90% by weight of a styrene-based monomer, 10 to 50% by weight of an acrylonitrile-based monomer, and 0 to 40% by weight of a copolymerizable monomer. The obtained / mixed solution is pumped into the reaction tank and mixed uniformly to carry out the graft polymerization reaction. During the reaction, an appropriate chain transfer agent such as tertiary dodecyl sulfide may be added to control the molecular weight of the polymer. The reaction tank can be composed of multiple tanks, preferably a kettle-type reaction tank with a powerful stirrer, and the solvent used can be toluene, dioxin, ethylbenzene, fluorenyl monoethyl ketone, ethylacetic acid, and the like. The diene rubber used in the block or solution polymerization method is preferably polymerized by an anion polymerization method. The winners include, for example, butadiene rubber, isoprene rubber, air butadiene rubber, butadiene to propylene rubber, butadiene monostyrene rubber, etc., of which butadiene rubber has a high cis ( Hi-Cis) content and low cis (Los-Cis) content; high-type rubber, the typical weight composition of cis (Cis) / vinyl (Vinyl) is 94 ~ 98% / ι ~ ⑽, Its (2! 〇 × 297λ >^; f Please read the precautions on the back of ^ before filling out this page} ------.----- ^ ---- 装 -------- Order- -----, ιι-ί --- 一卜 — l · · 46 626 2 Economy. Qiu Zhonghuan 橾 quasi-industrial-industrial-consumption cooperation printed Λ 5. Invention Description (γ) The remaining composition is trans (Trans ) Structure; its Mooney viscosity is between 20 ~ 120 'molecular weight range is preferably 100,000, 8000 ~ 800, 〇00; in the low cis rubber, the typical weight of cis / vinyl is 2 2 〇 ~ 40% / 1 ~ 20%, the rest are trans structure; its Mooney viscosity is between 20 ~ 120; suitable for the stupid ethylene / butadiene copolymer rubber of the present invention, and its polymerization type can be two-stage (di -block) copolymerization, tri-block copolymerization, random A total of 5 random (star) or star type (star type). 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. In the block or solution graft copolymer of the present invention, Suitable rubbers are butadiene rubber and styrene / butadiene rubber. 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 0.6 and 10, preferably 1.0 to 7_0 um. The rubber content of the solution-like rubber-like graft copolymer (β) 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, in addition to the rubber-like graft copolymer or the block (or solution) polymerization method of the above-mentioned etiquette polymerization method, the rubber-like graft copolymer can also be used separately. The foregoing two are used together to form a bimodal or trimodal distribution: A bimodal distribution is, for example: (1) a weight average particle size of 0.2 to 0.8 um (emulsion polymerization), and a weight average particle size of 0.6 to 10 um (lumpy) Or solution polymerization); or (2) weight average particle control 0.05 ~ 〇_ 18 um (emulsion polymerization), weight average particle size 0.6 to 10 um (lumpy or solution polymerization). Applicable to China National Standards (CNS) Regulation 8 (2! 0X297 ^ ii (Please read the precautions on the back before filling this page) ---- · '---- ^ --- r- --i ------ order ------ bundle-^ ---_--.

I 4 6 62 6 2 A7 B7 經濟部中央標準局負工消"合作社印製五、發明説明（牙）三峰式分佈者如：重量平均粒徑〇,〇5〜0.15 um(乳化聚合），重量平均粒徑〇 _ 17〜0 · 8 um (乳化聚合），重量平均粒徑0.25〜7.0um(塊狀或溶液聚合）。前述橡膠粒子之重量平均粒徑的測試方法，係以四氧化娥（Os〇4)將樹脂染色後，再以穿透式電子顯微鏡照相，將相月中所照得之橡膠分散粒子取1 00〇個左右之粒子測其粒徑’再以下式求其重量平均粒徑：Σ n jD i4 橡膠重量平均粒徑----Σ n i3 其中’ n=橡膠粒子徑為d之橡膠粒子數至於本發明橡膠粒子接枝共聚物（B)所使用的笨乙烯系單體、丙烯晴系單體及其他可共聚合單體之種類，和前述苯乙烯系共聚物（A)中的單體舉例說明相同，在此不贅述。本發明苯乙烯系樹脂組成物中的聚酯系熱可塑性彈性體（C)，疋由分子結構中具有硬質段之聚酯及具有低玻璃轉移溫度(Tg)之聚醚或聚酯軟質段構成之塊狀共聚物，依其分子結構不同，主要有下述兩種型式： (1) 聚酯一聚醚型之聚酯系熱可塑性彈性體：般硬質段為芳香族系結晶性聚醋，軟質段為聚趟類。 (2) 聚酯—聚酯型之聚酯系熱可塑性彈性體：一般硬質段為芳香旄糸&θ π & P ^骨族系結晶性聚酯，軟質段為脂肪族 (請先閲讀背面之注意事項再填寫本頁) 厂裝' 訂I 4 6 62 6 2 A7 B7 Work load of the Central Standards Bureau of the Ministry of Economic Affairs " Printed by the cooperative V. Description of invention (teeth) Those with a trimodal distribution such as: Weight average particle size 0, 05 ~ 0.15 um (emulsion polymerization), The weight-average particle diameter is 0-17 ~ 0 · 8 um (emulsion polymerization), and the weight-average particle diameter is 0.25-7.0 um (block or solution polymerization). The aforementioned method for measuring the weight average particle diameter of rubber particles is that after dyeing the resin with osmium tetroxide (Os04), and then photographing it with a transmission electron microscope, the rubber dispersed particles obtained in the moon phase are taken as 100 The particle size of about 0 particles is measured, and the weight average particle diameter is calculated by the following formula: Σ n jD i4 Rubber weight average particle size ---- Σ n i3 where 'n = the number of rubber particles whose rubber particle diameter is d. Types of stupid vinyl monomers, acrylic monomers, and other copolymerizable monomers used in the rubber particle graft copolymer (B) of the present invention, and examples of the monomers in the aforementioned styrene-based copolymer (A) The description is the same, and is not repeated here. The polyester-based thermoplastic elastomer (C) in the styrene-based resin composition of the present invention is composed of a polyester having a hard segment in a molecular structure and a polyether or polyester soft segment having a low glass transition temperature (Tg). According to their molecular structure, the block copolymer mainly has the following two types: (1) Polyester-polyether type polyester thermoplastic elastomer: The general hard segment is aromatic crystalline polyacetate, The soft segment is a poly-trip type. (2) Polyester-polyester type thermoplastic elastomers: Generally the hard segment is aromatic 旄糸 & θ π & P ^ bone family crystalline polyester, the soft segment is aliphatic (please read first Note on the back then fill out this page) Factory installed

:E 經濟部中央標準局負Η消贤合作让印製 *46626 2 五、發明説明（1 ) 系之聚酯類。般而s ，大都使用聚醋一聚醚型的聚醋系熱可塑性彈性體’其中，聚酯的代表是聚對笨二甲酸丁烯酯（pl〇y— butylene terephthalate，簡稱PBT)，而聚醚的代表為聚四亞甲基醚二醇（p〇ly tetra methylene ether glyC〇i)。本發明之聚酯系熱可塑性彈性體（C)佔全部苯乙烯系樹脂組成物的0.5〜4〇重量份，最佳為2〜2〇重量份，前述成份之添加量若低於0.5重量份時樹脂的耐衝擊強度會降低，但添加量若大於4 Q重量份，則抗拉強度會大幅滑落，樹脂之物性亦不佳。本發明苯乙埽系樹脂缸成物中的壓克力系橡膠（D)，係由具有軟質橡膠性質的核部（C〇re)與硬質聚合物之殼層 (shell)組合而成，有關壓克力系橡膠（D)之製造方法在曰本特開平1-103657、1-103568、2-129266號及美國發明專利第3983296、4150005、4564653號案中均有記载。一般而言’本發明之壓克力系橡膠（D)中具有軟質橡膠性質的核部可為·.聚丙烯酸乙酯、聚丙烯酸丙酯、聚丙稀駿正丁醋、聚丙烯酸異丁酯、聚丙烯酸己酯、聚丙烯酸辛S旨、聚丙烯酸—2 —乙基己酯、聚甲基丙烯酸甲酯、聚曱基丙烯酸乙酯、聚甲基丙烯酸丙酯、聚甲基丙烯酸異丙酿、聚甲基丙烯酸第三丁酯、聚甲基丙烯酸異丁酯等橡膠性質的彈性體；而硬質聚合物之殼層可為：聚曱基丙烯酸甲醋、聚苯乙烯、丙烯賸—苯乙烯共聚物、曱基丙晞酸甲醋一苯乙烯共聚物等硬質聚合物。 -—_____ 第 11 頁本紙張尺度適用中國國鮮（-------------- ----->--Γ----i------IT------->- ; ' ..-,.. (請先閱讀背面之注意事項再棋苟本頁} i 經濟部中央標準局負工消费合作社印製 4 6 626 2 A7 —------------ B? 五、發明説明（丨0 ) ~~~ —' 本發月使用之壓克力系橡膠（D)的使用量重量…乙稀系樹脂的〇·…量份，：Π、2〜2。重量伤+田添加量少於〇. 5重量份時不具有耐腳C性之效果准右添加里大於4〇重量份，則樹脂之耐衝擊強度及抗拉強度會大幅降低，造成樹脂物性的變差，亦會產生龜裂之現象。另卜本發明本乙婦系樹脂組成物以丙酮/甲苯溶劑測疋之膨潤指數為4. 2〜7· 5，當膨潤指數小於4. 2時會造成抗拉強度不佳’而膨潤指數若大於7, 5 _，樹脂,组成物之物性如抗拉強度及耐衝擊強度均會大幅降低。、本發明之苯乙烯系樹脂組成物可依需要添加使用其他的添加齊1 ’例如：抗氧化劑、可塑劑、加工助劑、紫外線女疋劑、紫外線吸收劑、填充劑、強化劑、著色劑、滑劑、帶電防止劑、難燃劑、難燃助劑、熱安定劑、偶合劑或其他添加劑等，上述添加劑可在聚合反應中、聚合反應後 '凝結前或押出混練的過程中添加。其中’抗氧化劑宜使用如酚系抗氧化劑、硫醚系抗氧化劑、磷系抗氧化劑、螯劑等物質’而酚系抗氧化劑的添加量以0.005〜2.0重量％為佳，具代表性者有：十八烷基 (3,5 -雙第二丁基__4_羥笨基）_丙酸酯、三乙二醇雙[3_(3_ 第一丁基-5-甲基-4-經苯基）丙酸酯]、四[甲樓基_3_(3,5-雙第二丁基-4-羥笨基）丙酸酯]甲烧、2_第三丁基_6_(3 一第二丁基-2-經基-6-甲基苯甲基）-4-甲基苯基丙烯酸酯、 2,2’-甲撐基-雙（4-甲基-6-第三丁基酚）、2, 2，-硫雙（4-甲 -~;——— __第 12 頁本纸張尺度賴中國群標準（CNS),‘、峨格（2似297公兑） (請先閱讀背面之注意事項苒填寫本買): E Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and cooperation. * 46626 2 V. Description of the invention (1) Polyesters. In general, polyacetate-polyether-based thermoplastic elastomers are mostly used. Among them, polyester is represented by polybutene terephthalate (PBT), and polymer The representative of the ether is polytetramethylene ether glycol. The polyester-based thermoplastic elastomer (C) of the present invention accounts for 0.5 to 40 parts by weight, preferably 2 to 20 parts by weight, of the entire styrene resin composition, and if the amount of the foregoing components is less than 0.5 parts by weight When the impact resistance of the resin is reduced, if the added amount is more than 4 Q parts by weight, the tensile strength will fall off greatly, and the physical properties of the resin will not be good. The acrylic rubber (D) in the acetofluorene-based resin cylinder composition of the present invention is a combination of a core (Core) having a soft rubber property and a shell of a hard polymer. The manufacturing method of the acrylic rubber (D) is described in Japanese Patent Application Laid-Open Nos. 1-103657, 1-103568, and 2-129266, as well as in US Patent Nos. 3983296, 4150005, and 4465653. Generally speaking, the core portion of the acrylic rubber (D) of the present invention having soft rubber properties may be: polyethyl acrylate, polypropyl acrylate, polypropylene n-butyl vinegar, polyisobutyl acrylate, Polyhexyl acrylate, polyacrylic acid, polyethyl 2-hexyl acrylate, polymethyl methacrylate, polyethyl acrylate, polypropyl methacrylate, polyisopropyl methacrylate, Polyisobutyl methacrylate, polyisobutyl methacrylate and other rubber-like elastomers; and the shell layer of the hard polymer can be: polymethyl acrylic acrylate, polystyrene, propylene residual-styrene copolymerization Polymers, rigid polymers such as methyl ethyl acetonate-styrene copolymer. -—_____ Page 11 This paper size applies to China's national fresh (-------------- ----- >-Γ ---- i ------ IT ------- >-; '..-, .. (Please read the notes on the back before playing this page} i Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 4 6 626 2 A7 — ------------ B? V. Description of the invention (丨 0) ~~~ — 'The amount of acrylic rubber (D) used in this month. Weight ... Ethylene resin 〇 ... Parts by weight: Π, 2 ~ 2. Weight injury + field addition amount less than 0.5 parts by weight does not have the effect of resistance to foot C. quasi-right addition is greater than 40 parts by weight, the impact resistance of the resin 2〜 The strength and tensile strength will be greatly reduced, causing the deterioration of the physical properties of the resin, but also the phenomenon of cracking. In addition, the present invention is a bismuth resin composition with acetone / toluene solvent measured swelling index of 4. 2 ~ 7.5, when the swelling index is less than 4.2, the tensile strength will be poor, and if the swelling index is greater than 7, 5 _, the physical properties of the resin and composition such as tensile strength and impact strength will be greatly reduced. The styrene-based resin composition of the present invention may be added and used as needed. Add Qi 1 'for example: antioxidants, plasticizers, processing aids, UV female tincture, UV absorbers, fillers, strengthening agents, colorants, slip agents, antistatic agents, flame retardants, flame retardant additives, Heat stabilizers, coupling agents or other additives, the above additives can be added during the polymerization reaction, after the polymerization reaction 'before coagulation or extruding and kneading process. Among them, antioxidants such as phenolic antioxidants and thioether antioxidants should be used. , Phosphorus-based antioxidants, chelants, etc., and the phenol-based antioxidant is preferably added in an amount of 0.005 to 2.0% by weight. Representative examples are: octadecyl (3,5 -bis second butyl __4 _Hydroxybenzyl) _propionate, triethylene glycol bis [3_ (3_ first butyl-5-methyl-4-transphenyl) propionate], tetrakis [methloyl_3_ (3, 5-bis-second butyl-4-hydroxybenzyl) propionate] methylbenzene, 2-third butyl-6- (3-second butyl-2-meryl-6-methylbenzyl) 4-methylphenyl acrylate, 2,2'-methylidene-bis (4-methyl-6-tert-butylphenol), 2, 2, -thiobis (4-methyl- ~;- —— __Page 12 This paper size is based on China Group Standard (CNS) , ’, Ege (2 similar to 297 exchange) (Please read the notes on the back first and fill in this purchase)

4.66262 Λ7 B7 五、發明説明（1” 基_6_第三丁基酚）、2, 2, _硫代-二乙撐基-雙[3-(3, 5-雙第二丁基_4—經笨基）丙酸酯]、2, 2，-乙二醯胺-雙[乙基-3-(3,5-雙-第三丁基__4_羥苯基）丙酸酯]等。硫鍵系抗氧化劑的添加量以0.005〜2.0重量％為佳，具代表性者有：二硬脂醯硫二丙酸酯、二棕櫚醯硫二丙酸脂、五赤蘇醇-四-(召-十二甲基-硫丙酸酯）、雙十八烷基硫&等。 0系、技< 氧化劑為亞磷酸酯系抗氧化劑或磷酸酯抗氧化劑’其添加量以〇.〇15〜2.〇重量％為佳，具代表性者有：三（壬基苯基）亞磷酸酯、十二烷基亞磷酸酯、環狀新戊烷四氫蒸基雙（十八烷基亞磷酸酯）、4,4’-亞丁基雙（3-甲基-6_第三丁基苯基-雙十三烷基亞磷酸酯）、三（2,4-第三丁基苯基）亞磷酸酯、四（2,4-第三丁基笨基）-4, 4，-伸聯苯基磷酸醋、9, 10-二氫-9-氧_10_磷酸菲-ίο-氧撐等。螯劑的添加量以0.001〜2.0重量％為佳，具代表性者有：二苯甲醯基甲烷、二乙胺四醋酸的鈉鹽等。前述抗氧化劑的添加量通常相對於苯乙烯系樹脂組成物合計量的0.03〜2.0重量％。滑劑具代表性者有··硬脂酸鈣、硬脂酸鎂、硬脂酸鋰等之金屬肥皂、乙撐二硬脂醯胺、曱撐二硬脂醯胺、棕櫚酸醯胺、硬脂酸丁酯、硬脂酸棕櫊酯、聚丙酸醇三硬脂酸酯、正二十二烷酸、硬脂酸等之化合物、聚乙烯蠟、二十八娱;酸壤、巴西掠網壤（Carnuba wax )、石油躐等；滑劑的添加量相對於苯乙烯系樹脂組成物通常合計的0. 0 3〜 _______第 13 頁________________ 本紙張尺度通用中國國家標率（CMS〉从规格（210X：297公浼） (請先閱讀背面之注意寧項再填寫本頁} 經濟部中央標隼局Η工消费合作社印製 --------·Ί·---i------IT------,.^1^----rI: 466262 Λ7 B7 五、發明説明（Ι· 經濟部中央榡卒局負工消许合作社印製 5.0重量％ ;為了改善押出成型性、熱成型性，也可以加入如甲基丙稀酸甲醋系的加工助齊丨；紫外線吸收劑具代表性者有.苯並三唑系化合物、二苯甲輞系化合物、氰丙烯酸系化合物，而紫外線安定逾丨且七八文疋Μ具代表性者有：阻滯胺系化 CT物’前述物質之添加量以相耕於贫^咕$此里从相對於本乙烯系樹脂組成物通常合計量的0.02〜2,0重量％。在改善樹脂之耐候性、耐紫外線照射產生變色或樹脂之物性劣化方m滞胺系紫外線安定劑/氰丙婦酸系之紫外線吸收劑二者組合併用柄，例如：b a s f公司之 UVinUl wm.◦重4%)/uvinul 3G35(〇〇2〜 1. 0重量％)。帶電防止劑具代表性者有：三級胺系化合物、四級錄鹽系化合物等之低分子系化合物，或聚醯胺聚醚，如3 一氣—1，2 -環氧丙料合體之永久帶電防止性的高分子系物質。填充劑具代表性者有：碳酸鈣、矽土、雲母。強化劑具代表性者有：玻續纖维、碳纖維、各種晶絲 (whisker)類。著色劑具代表性者有：氧化欽、氧化鐵、石墨、欧菁染料。難燃劑或難燃助劑具代表性者有：十漠二笨基醚、四漠雙紛A、漠化聚笨乙稀寡聚合體、漠化環氧樹脂、六演環十一烧、氯化聚化烯、三苯基麟酸、紅鱗、氧化錄、氫氧化紹、氫氧化鎮、蝴酸鋅、三聚氰胺、#氰胺鹽、石夕氧第14苜 ^紙張尺度適用中國国家標毕{ CNS〉格（ (請先閱讀背面之注意事項再填寫本頁) ,裝- .1: 訂 466262 Α7 B? 經濟部中央標準局Μ工消贤合作社印製五、發明説明（丨3 ) 粉末、聚四氟乙烯粉末、膨脹性石墨等。熱安定劑具代表性者有：二丁基錫馬來酸鹽、鹽基性鎂鋁羥基碳酸鹽等；而熱變色防止劑可為低分子量的笨乙烯一無水馬來酸共聚物’其添加量乃相對於本發明苯乙烯系樹脂組成物通常合計量的0. 1〜1 . 0重量％。偶合劑具代表性者有：矽烷系、酞酸酯、鍺酸酯系化合物。在本發明之苯乙烯系樹脂組成物中為了改質，可以適當使用聚合體系之添加物’例如··塊狀聚合法、溶液聚合法、塊狀懸濁聚合法等，也就是可採用乳化聚合法以外的方式製造之苯乙烯系樹脂，例如：丙烯睛一丁二烯—苯乙烯樹脂、使用丁二烯系橡膠以外的橡膠，例如：E P D Μ 、以丙烯酸丁酯橡膠來改質的ΑΕ S樹脂、AA S樹脂等苯乙烯系樹脂、無水馬來酸一苯乙烯共聚物、苯乙烯—馬來酿亞胺共聚物、馬來醯亞胺含量超過40重量％的苯乙烯 _丙烯腈一無水馬來酸共聚物、以苯胺馬來醯亞胺化的苯乙烯一丙烯腈一無水馬來酸共聚物，沒有接枝的架橋橡膠例如：丙烯腈一丁二烯橡膠、氯化乙烯樹脂、聚曱基丙烯酸甲酯、聚碳酸酯樹脂、聚醯胺樹脂、聚對酞酸丁烯酯、聚伸笨基醚、聚氯乙烯、苯乙烯系熱可塑性彈性體、各種相溶化劑等，其使用量相對於本發明1 00重量份之苯乙烯系樹脂組成物的3〜200重量份。為得到本發明之樹脂组成物，其混合方法具代表性者是：以一般使用之漢歇爾混合機乾混後再以諸如押出混合第15 本紙浪尺度適用中國國家標隼（CNS ) /\4現恪（2丨0X 297公砬） (請先閱讀背面之注$項再填莴本頁) --------'----^---r---装------訂 k;4.66262 Λ7 B7 V. Description of the invention (1 ”group-6-third butyl phenol), 2, 2, thio-diethylidene-bis [3- (3, 5-bis-second butyl_4 —Bentyl) propionate], 2, 2, ethylenediamine-bis [ethyl-3- (3,5-bis-third butyl__4_hydroxyphenyl) propionate], etc. The added amount of the sulfur-bond antioxidant is preferably 0.005 to 2.0% by weight. Representative examples include: distearyl thiodipropionate, dipalmitine thiodipropionate, pentaerythritol-tetra- (Call-dodecylmethyl-thiopropionate), dioctadecylsulfide & etc. 0 series, technology < The oxidant is a phosphite-based antioxidant or a phosphate-based antioxidant 'and its addition amount is 0. 〇15 ～ 2.0% by weight are preferred, and representative examples include tris (nonylphenyl) phosphite, dodecylphosphite, cyclic neopentanetetrahydrodichlorobis (octadecane) Phosphite), 4,4'-butylene bis (3-methyl-6-tert-butylphenyl-bistridecyl phosphite), tris (2,4-tert-butylbenzene Base) phosphite, tetrakis (2,4-tert-butylbenzyl) -4,4, -biphenylphenyl phosphate, 9, 10-dihydro-9-oxy_10_phenanthrene phosphate-ίο- Oxygen and so on. The chelating agent is preferably added in an amount of 0.001 to 2.0% by weight, and typical examples include dibenzomethylmethane, sodium salt of diethylamine tetraacetic acid, and the like. The amount of the antioxidant added is usually relative to the styrene resin. 0.03 to 2.0% by weight of the total composition. Representative examples of the lubricant include metal soaps such as calcium stearate, magnesium stearate, and lithium stearate, ethylene distearylamine, and fluorescein. Compounds such as stearylamine, palmitate, butyl stearate, palmityl stearate, polytrialcohol tristearate, n-docosalic acid, stearic acid, etc., polyethylene wax, Twenty-eight entertainments; acid soil, Brazilian carnuba wax, petroleum tincture, etc .; the amount of lubricant added is usually 0. 0 3 ~ _______ page 13 _______ Paper Standard General China National Standards (CMS) from the specifications (210X: 297 cm) (Please read the note on the back before filling in this page} Printed by the Central Standards Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives -------- --- · Ί · --- i ------ IT ------ ,. ^ 1 ^ ---- rI: 466262 Λ7 B7 V. Description of the invention (I. Central Ministry of Economic Affairs In order to improve the extruding moldability and thermoformability, you can also add processing such as methyl acrylic acid methyl vinegar, etc .; UV absorbers are representative of . Benzotriazole-based compounds, benzophenone-based compounds, cyanoacrylic-based compounds, and UV-stabilized compounds with more than seventy-eight texts are as follows: blocking amine-based CTs, the amount of the aforementioned substances In terms of relative poverty, the amount is from 0.02 to 2,0% by weight relative to the total amount of the vinyl resin composition. In order to improve the weather resistance of resin, discoloration caused by ultraviolet radiation resistance, or deterioration of the physical properties of resin, the combination of hysteresis amine ultraviolet stabilizer / cyanopropionic acid ultraviolet absorber is used in combination, such as UVinUl wm. By basf company. 4% by weight) / uvinul 3G35 (0.02 to 1.0% by weight). Representative examples of antistatic agents are low-molecular-weight compounds such as tertiary amine compounds, quaternary salt-recording compounds, etc., or polyamine polyethers, such as the permanent one-gas 1,2,2-propylene oxide composites. Antistatic polymer material. Representative fillers are: calcium carbonate, silica, mica. Reinforcing agents are typically represented by glassy continuous fibers, carbon fibers, and various whiskers. Typical colorants are: oxin, iron oxide, graphite, and Eugen dye. Representative examples of flame retardants or flame retardant additives are: Benzyl Dibenzyl Ether, Benzene Di-A, Benzyl Oligomeric Polymer, Benzyl Epoxy, Benzyl Ethylene, Chlorinated polyene, triphenyllinic acid, red scale, oxidation record, hydroxide, zinc hydroxide, zincate, melamine, #cyanamide salt, Shixiu 14th alfalfa ^ Paper standards are applicable to Chinese national standards Completion of {CNS> (please read the notes on the back before filling this page), install-.1: order 466262 Α7 B? Printed by the Ministry of Economic Affairs, Central Standards Bureau, Mong Xiaoxian Cooperative, V. Invention Description (丨 3) Powder, polytetrafluoroethylene powder, expanded graphite, etc. Representative examples of thermal stabilizers are: dibutyltin maleate, basic magnesium aluminum hydroxycarbonate, etc., and the thermal discoloration preventive agent can be a low molecular weight The ethylene-anhydrous maleic acid copolymer 'is added in an amount of 0.1 to 1.0% by weight relative to the usual total amount of the styrene-based resin composition of the present invention. Representative examples of the coupling agent include: silane-based, phthalic acid Ester, germanate-based compounds. In the styrene-based resin composition of the present invention, Appropriate use of additives of the polymerization system, such as a block polymerization method, a solution polymerization method, a block suspension polymerization method, etc., that is, a styrene resin that can be manufactured by a method other than the emulsion polymerization method, such as acrylonitrile Butadiene-styrene resin, using rubbers other than butadiene-based rubber, such as: EPD M, AES resin modified with butyl acrylate rubber, AA S resin and other styrene-based resins, anhydrous maleic acid-1 Styrene copolymer, styrene-maleimide copolymer, styrene-acrylonitrile-anhydrous maleic acid copolymer containing more than 40% by weight of maleimide, aniline maleimide-imidized benzene Ethylene-acrylonitrile-anhydrous maleic acid copolymer, grafting rubber without grafting, for example: acrylonitrile-butadiene rubber, vinyl chloride resin, polymethyl acrylate, polycarbonate resin, polyamide resin, Polybutylene terephthalate, poly (phenylene terephthalate), polyvinyl chloride, styrene-based thermoplastic elastomer, various miscibility agents, etc., the amount used is 100 parts by weight relative to the styrene-based resin composition of the present invention Of 3 200 parts by weight. In order to obtain the resin composition of the present invention, the typical method of mixing is: dry mixing with a general-use Hanschel mixer, and then use the 15th paper scale to apply the Chinese national standard ( CNS) / \ 4 is now (2 丨 0X 297 Gong) (Please read the note on the back before filling in this page) --------'---- ^ --- r-- -Install ------ order k;

P -------^---^---P ------- ^ --- ^ ---

Vt4 6 626 2五、發明説明（丨4 ) 經濟部中央標準局眞工消f合作社印裝機、捏合機或班伯立混練機等之混合機熔融混合。本發明之樹脂組成物適用於射出成型法、押出成型法、壓縮成型法、吹延成型法 '熱成型法、真空成型法及中空成型法等成型方法。為更進一步詳細說明本發明，再以實施例與物性測試說明如下，以下組成物之成份除非特別聲明，否則是以佔全部絚成重量以重量百分計的份數和百分比來表示。以下舉出實施例詳細說明本發明，但本發明之範圍並不以此等實施例為限0 〈製備例> <製備例I _ 1 >苯乙烯系共聚物（Α_υ之製造： θ以12 kg/吐的速度將苯乙烯60重量％、丙烯腈40重量％之原料混合，再將乙撐二硬脂醯胺3 〇 g/hr、過氧化苯甲酿、第三二貌基硫醇，以及後述反應所除去之揮發份經冷凝後所形成之回收液合併作為餵給液，以供給入内溫度保持在108 t：而容積45公升之附有攪拌器的連續式釜型反應器，且使反應液中的甲苯比例保持在，而聚合保.持在5 5 %。當反應液通過脫揮發裝置除去揮發份後，可得到苯乙烯系共聚物的顆粒；另—方面，所除去之揮發份以冷凝器凝縮作為回收液，並連續地與前述原料混合再使用之.此方法係由過氧化笨甲醢的量來調I反應速率，&調整第三醇Λ4」而以約12 kg/hr的速率製成两科 3里為32重篁/之本乙烯系共聚物（Ay)。 (請先閱讀背面之注意事項再填寫本頁)Vt4 6 626 2 V. Description of the Invention (丨 4) The Central Standards Bureau of the Ministry of Economic Affairs, Cooperative Consumers, Cooperative Presses, Kneaders or Banbury mixers are melt-blended. The resin composition of the present invention is applicable to molding methods such as injection molding method, extrusion molding method, compression molding method, and stretch molding method, such as a thermoforming method, a vacuum molding method, and a hollow molding method. In order to further illustrate the present invention in detail, the following examples and physical property tests are used to explain the following. Unless otherwise specified, the components of the following composition are expressed in terms of parts and percentages by weight based on the total weight. The following examples are used to illustrate the present invention in detail, but the scope of the present invention is not limited to these examples. 0 <Preparation example> < Preparation example I _ 1 > Styrene copolymer (Manufacture of Α_υ: θ At a rate of 12 kg / spit, 60% by weight of styrene and 40% by weight of acrylonitrile were mixed, and then ethylene distearylamine 30 g / hr, benzyl peroxide, and third dimeryl sulfur The alcohol and the recovery liquid formed by condensing the volatiles removed by the reaction described below are combined as a feed liquid to supply the internal temperature at 108 t: and a continuous kettle reactor with a stirrer volume of 45 liters, The toluene ratio in the reaction solution was kept at the same time, while the polymerization was kept at 55%. After the reaction solution was removed by the devolatilization device, the styrene-based copolymer particles were obtained; in addition, the styrene-based copolymer particles were removed. The volatile content is condensed by a condenser as a recovery liquid, and is continuously mixed with the aforementioned raw materials for reuse. This method is to adjust the I reaction rate by the amount of benzyl peroxide, and adjust the third alcohol Λ4 ″ to about 12 The rate of kg / hr is made into two families of 3 li for 32 weights / head Ethylene copolymers (Ay). (Note Read then fill the back surface of the page)

466262 A7 B7 五、發明説明（ΐ ΕΓ ) <製備例I — 2 >苯乙烯系共聚物（A-2)之製造：依 < 製備例I — 1 >的製備方法’不同之處在於：以笨乙烯60重量％、丙烯腈34重量％、丙烯酸丁酯6重量％之原料進行反應，並製成丙烯腈含量為30重量％之苯乙烯系共聚物（A-2)。 <製備例I 一 3 >苯乙烯系共聚物（A-3)之製造：依< 製備例I— 1〉的製備方法’不同之處在於：以笨乙烯70重量％、丙烯腈30重量％之原料進行反應，並製成丙烯腈含量為28重量％之苯乙烯系共聚物（A-3)。〈製備例I — 4 >苯乙烯系共聚物（A-4)之製造：以12 kg/hr的速度將苯乙婦35重量％、丙烯腈65重量％之原料混合，再將乙撐二硬脂醯胺3. 0 g/hr、過氧化苯曱醯、第三-十二烷基硫醇’以及後述反應所除去之揮發份經冷凝後所形成之回收液合併作為银給液，以供給入内溫度保持在1 08 °C而容積45公升之附有攪拌器的連續式蒼型反應器’且使反應液中的甲苯比例保持在15% ，而聚合率保持在55% 。466262 A7 B7 V. Description of the invention (ΐΕΓ) < Preparation example I-2 > Production of styrenic copolymer (A-2): According to < Preparation example I-1 > Preparation method'different points The invention consists of reacting 60% by weight of stupid ethylene, 34% by weight of acrylonitrile, and 6% by weight of butyl acrylate, and preparing a styrene-based copolymer (A-2) having an acrylonitrile content of 30% by weight. < Preparation Example I-3 > Production of styrene-based copolymer (A-3): According to < Preparation method of Preparation Example 1-1> 'The difference is that 70% by weight of styrene and 30% of acrylonitrile are used. A weight% of the raw materials were reacted to prepare a styrene-based copolymer (A-3) having an acrylonitrile content of 28 weight%. <Preparation Example I-4> Production of styrene-based copolymer (A-4): A raw material of 35% by weight of acetophenone and 65% by weight of acrylonitrile was mixed at a rate of 12 kg / hr, and then ethylene diethylene glycol Stearylamine 3.0 g / hr, phenylhydrazone, tertiary-dodecyl mercaptan ', and the recovered liquid formed by condensing the volatiles removed by the reaction described below are combined as a silver feed liquid to The continuous temperature reactor with a stirrer with a stirrer volume of 45 liters and an internal temperature of 1 08 ° C was supplied, and the toluene ratio in the reaction solution was maintained at 15%, and the polymerization rate was maintained at 55%.

經濟部中央標準局員工消费合作社印IL 當反應液通過脫揮發裝置除去揮發份後，可得到苯乙烯系共聚物（A)的顆粒；另一方面，所除去之揮發份以冷凝器凝縮作為回收液，並連續地與前述原料混合再使用之 ;此方法係由過氧化苯甲醯的量來調整反應速率，或調整第二 ^二院基疏醇之量，而以約12 kg/hr的速率製成丙烯勝含量為45重量％之笨乙烯系共聚物（A-4) 〇 <製備例π一 1 >橡膠狀接枝共聚物（B-1)的製造：第17頁 #紙银纽刺巾觸家標準（CNS ) Λ❹泣（2丨 46626 2 Λ7 B7 五、發明説明（丨b) Μ 1，3-丁二烯丙烯膾過疏酸鉀溶液焦磷酸鈉油酸鉀蒸餾水第三一-h二恍基硫醇重量伦 95. 0 5. 0 15. 0 3. 0 1. 5 140. 0 0. 2 依以上配方在65°C反應溫度下反應1 2小時，得到轉化率94% 、困體含量約為40% 、重量平均粒徑為〇，ι咖的合成橡膠乳液。另外，以下列成份製造含羧酸基的高分子凝集劑： (請先閱讀背面之注意事項再填寫本頁} 經濟部中央標毕局只工消"合作社印製成 η —丙稀酸乙醋 85. 0 丙烯酸 15.0 第三一十二烷基硫醇 0.3 油酸奸 2. 0 二辛基磺基琥ίά酸鈉 1.0 異丙苯化過氧化氫 0.4 甲醛合次硫酸氫鈉 0. 3 蒸餾水 200. 0 依上述配合在7 5 °C反應溫度下反應5小時，即可製得轉化率95¾ 、pH值6. 0之含羧酸基的高分子凝集劑。之後’利用3重量份含緩酸基之高分子凝集劑（乾重）When the reaction solution is removed by the devolatilizer, the particles of the styrene copolymer (A) can be obtained. On the other hand, the removed volatiles are recovered by condenser condensation. It is continuously mixed with the aforementioned raw materials and then reused; this method is to adjust the reaction rate by the amount of benzamidine peroxide, or adjust the amount of the second ^ 2nd base thiol, and about 12 kg / hr A stupid ethylene-based copolymer (A-4) having a propylene content of 45% by weight was produced at a rate of 〇 < Preparation Example π-1 > Production of a rubber-like graft copolymer (B-1): Page 17 # 纸Silver Button Stinger Touching Home Standard (CNS) Λ❹weeping (2 丨 46626 2 Λ7 B7 V. Description of the invention (丨 b) Μ 1,3-butadiene propylene 脍 potassium persulphate solution sodium pyrophosphate potassium oleate distilled water Trinyl-h difluorenyl mercaptan 95. 0 5. 0 15. 0 3. 0 1. 5 140. 0 0.2 According to the above formula, it is reacted at 65 ° C reaction temperature for 12 hours to obtain the conversion rate. 94%, synthetic rubber emulsion with a content of about 40% and a weight average particle size of 0, ι. In addition, it is manufactured with the following ingredients Carboxylic acid-based polymer agglutinating agent: (Please read the precautions on the back before filling out this page} The Central Bureau of the Ministry of Economic Affairs only prints " cooperative prints made of η-ethyl acetate 85.0 0 acrylic acid 15.0 Tris-dodecyl mercaptan 0.3 Oleic acid 2. 0 Sodium dioctyl sulfosulfate 1.0 Sodium cumene hydroperoxide 0.4 Formaldehyde sodium bisulfite 0.3 Distilled water 200. 0 After reacting for 5 hours at a reaction temperature of 5 ° C, a polymer coagulant containing a carboxylic acid group with a conversion rate of 95¾ and a pH value of 6.0 can be obtained. After that, 3 parts by weight of the polymer coagulant containing a slow acid group is used. (Dry weight)

第 18 一X 本纸張尺度適用中國國家標準（CNS )（210X297公兑） ------------>--'·---------iT----------1, 0 46626 2 經濟部中央標荜局負工消费合作社印製 Λ7 B7 五、發明説明（（ϊ) 來肥大10 0重量份的合成橡膠乳液（乾重），所得到的肥大化橡膠乳液的pH值為8.5，重量平均粒徑為〇.3〇umti 最後，再以肥大化橡膠乳液依下述配方進行接枝聚合反應，以製造橡膠狀接枝共聚物（B-1)» 遙------......-——重量价肥大化橡膠乳液（乾重） 100.0 苯乙烯 25.0 丙婦賸 8, 3 油酸狎 1.2 第三—h二燒基硫醇 0. 2 異丙苯化過氧化氫 0· 5 硫酸亞鐵溶液（0. 2%) 3. 0 曱醛化次硫酸鈉溶液（1 〇 %) 3. 0 乙二胺四醋酸溶液（0, 25%) 20. 0 蒸餾水 200. 0 將上述配方中的苯乙烯/丙烯腈以連續添加方式在小時内加入反應系統中聚合’所製得之橡膠狀接枝乳液以氯化約（CaC 12)凝結、脫水後’再乾燥至水份含量2%以下，就可製得本發明所需要的橡膠狀接枝共聚物）（橡膠含量75重量％) ’其橡膠粒子的重量平均粒徑為〇. 3丨⑽。 <製備例Π - 2 >橡膠狀接枝共聚物（B_2)的製造：以<製備Π—1>所製得之合成橡膠乳液（橡膠粒子重量平均粒徑0_1咖）’直接和下表配方進行接枝聚合反應。第19 本紙張尺度適用中國因尽標华（CNS ) >\彳規格（210X297公势） (請先閱讀背面之注意寧項再填寫本頁) 厂裝. 46 626 2 Μ _____Β7 五、發明説明（θ ) 成~~—----__t 量份合成化橡膠乳液（0.1 um)(乾重） 100.0 笨乙烯 75. 0 丙烯胯 25. 0 油酸钟 2. 0 第三一^h二烷基硫醇 0. 6 異丙苯化過氧化氫 1.4 硫酸亞鐵溶液（0. 2%) 8. 6 甲醛化次硫酸鈉溶液（1 〇%) 8.6 乙二胺四醋酸溶液（〇. 25%) 57. 0 蒸顧水 200. 〇將上述製得之未凝結橡膠乳液與 < 製備例E i >所製得之未凝結橡膠乳液，以重量比1 : 1 方式混合凝結，所製得之橡膠狀接枝乳液以氯化鈣（CaCU)凝結、脫水後，再乾燥至水份含量2%以下，就可製得本發明所需要的橡膠狀接枝共聚物（B-2)(橡膠含量63重量％) ’其橡膠粒子之重量平均粒徑為0. 1通、〇, 3 um之雙峰式分佈.型態。 <製備例Π - 3 >橡耀·狀接枝共聚物（B-3)的製造： (請先閲讀背面之注意事項再填寫本頁) 袭. 訂經濟部中央標毕局只工消f合作社印製以0.08重量份之過氧化苯甲酿作為起始劑，將6.6重量份之聚丁二烯（旭化成公司出品，商品名為Asadene 55as) 完全溶解於74.4重量份之苯乙烯、25_6重量份之丙烯膾及 3 0重量份之乙笨中，以形成進料溶液，之後將進料溶液連續送入體積為45公升之第一反應器中，反應溫度為1〇〇β(：、反應器内配置設有冷卻循環管之螺旋式攪拌器，其攪拌 -__第 20 1；本紙張尺度適用中國國家標準（CNS ) Λ4规格（2!OX297公及）經濟部中央標準局只工消費合作社印製 4 6 626 2 Λ7 _______ B7 五、發明説明（I 1 ) 速率為150 ΓΡΒ1，在第一反應器之單體轉化率為15%，將經過第一反應器反應後之混合物連續取出並依序送入第二、三、四反應器中，同時在第三反應器中加入0.1重量份之第三-十二烷基硫醇，相反轉現象在第二反應器中產生，上述第二、三、四反應器之裝置與第一反應器相同，但其反應溫度依序為1051、litre、125 °C，而攪拌速率依序為270rpm、15 0rpm及110 rpm;俟混合物之轉化率達6〇% 時’將混合物取出送入脫揮發裝置中，移去未反應之單體及揮發份’之後將其押出製粒，即可製得粒狀之橡膠狀接枝共聚物，其橡膠粒子之重量平均粒徑為〇·95咖，橡膠含量為11重量％。將此粒狀之橡膠狀接枝共聚物與前述 < 製備例π — 2 >之橡膠狀的接枝共聚物（β_2)以4: 6的比例混練後，可製得橡膠含量40重量％，而橡膠粒子的重量平均粒徑為〇.1 咖、〇,3 um、ι·〇咖之三峰式分佈型態的橡膠狀接枝共聚物 (Β_3 )。本發明'實施例與比較例所製得樹脂組成物之物性測試標準如下：一、膨潤指數（SI):膨潤膠含量/乾燥膠含量[(Α)/(Β)]，其試驗步驟如下： (1) 精秤樣品樹脂組成物1公克加入30毫升的丙酮振盪至溶解2小時。 (2) 加入第二溶劑甲笨3〇毫升，並置放到隔夜。 (3) 第2天將聚乙烯瓶取出振盪1小時，並以轉速18, 〇〇〇 ________ 第 21 頁 ^紙張尺度適用中國~^^^((；?^)/\4規格（210\ 297公趂) " ^ (請先閱讀背面之注意事碩再填寫本頁} -訂 ,蠢 4 6 626 2 Λ7 B7 經濟部中央標準局貞工消费合作社印製五、發明説明（^) rpm之離心機離心20分鐘。 (4) 倒出澄清液，精秤膨潤膠含量（A)。 (5) 乾燥此 >儿澱物放置在12 5 C之烤箱中烘烤3小時 (6) 精秤乾燥膠含量（B)〇二、艾氏衝擊強度（IZOD): 依ASTM D-256法測試抗拉強度（Tsy)測定：依ASTM D-638法測試耐HCFC-141b性測定：將變形量1.5 %之抗拉強度試片置於 2, 2-二氣乙烧）蒸汽的密閉系統内’其放置溫度為23 t，且放置2小時觀察抗拉強度試片有無龜裂或霧化現象，若試片上有輕度龜裂或霧化現象時以“χ”表示，若試片上有嚴重龜裂或霧化現象時以“XX”表示，若試片無龜裂且無霧化現象時以“ 0 ”表示。 <實施例> <實施例1 > 將由 < 製備例I — 1 >所製得之苯乙烯系共聚物u_n 70重1 % 、由 < 製備例π — 2 >所製得之橡膠狀接枝共聚物（B-2)30重量％，再添加5.0重量份聚酯系熱可塑性彈性體（C) (SUNKYONG 公司製造，商品名為 SKYPEL G14〇D)、5, 〇重量份壓克力系橡膠（D)UUREHA公司製造，商品名為 Paraloid KM355)，以及1.5重量份之滑劑，並以WerneF & Pf leidrer ZSK 35押出機於22〇ec混合押出製粒’即可得以Kg · cm/cm表示以Kg2/C(n表示四 22頁本紙張尺度適用中國國家標準（CNS ) /.W規格（210χ297公及 (請先閱讀背面之注意事項再填寫本頁} 袭The 18th X standard of this paper applies the Chinese National Standard (CNS) (210X297). ------------ >-'· --------- iT-- -------- 1, 0 46626 2 Printed Λ7 B7 printed by the Consumers ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention ((ϊ) 100% by weight of synthetic rubber emulsion (dry weight), The pH value of the obtained masticated rubber emulsion was 8.5, and the weight-average particle diameter was 0.30umti. Finally, the masticated rubber emulsion was subjected to a graft polymerization reaction according to the following formula to produce a rubber-like graft copolymer ( B-1) »Remote ------......----- Weight and price hypertrophic rubber emulsion (dry weight) 100.0 Styrene 25.0 Propylamine left 8, 3 oleic acid 1.2 Third-h 2 Alkyl mercaptan 0.2 Cumene hydroperoxide 0.5 Ferrous sulfate solution (0.2%) 3. 0 Formaldehyde sodium sulfoxylate solution (10%) 3. 0 Ethylenediamine tetraacetic acid Solution (0, 25%) 20. 0 Distilled water 200. 0 The styrene / acrylonitrile in the above formula was continuously added to the reaction system during the hour and polymerized in the reaction system. (CaC 12) After coagulation, dehydration, and then drying A moisture content of 2% or less, can be rubbery graft copolymer of the present invention required to obtain) (rubber content 75 wt%) 'weight average particle diameter of rubber particles is square. 3 Shu ⑽. < Preparation Example Π-2 > Production of rubbery graft copolymer (B_2): The synthetic rubber emulsion (rubber particle weight average particle diameter 0_1 coffee) obtained by < Preparation Π-1 > Table formulations were subjected to graft polymerization. The 19th paper size applies to China's Best Standards (CNS) > \ 彳 specifications (210X297 public power) (Please read the note on the back before filling this page) Factory installed. 46 626 2 Μ _____ Β7 V. Description of the invention (Θ) into ~~ —----__ t parts by weight of synthetic rubber emulsion (0.1 um) (dry weight) 100.0 stupid ethylene 75.0 propylene fluorene 25.0 oleic acid bell 2. 0 third one ^ h dioxane Thiol 0.6 cumene hydroperoxide 1.4 Ferrous sulfate solution (0.2%) 8. 6 Formaldehyde sodium sulfoxylate solution (10%) 8.6 Ethylenediamine tetraacetic acid solution (0.25% ) 57. 0 distilled water 200. 〇 The uncoagulated rubber emulsion prepared above and the uncoagulated rubber emulsion obtained in < Preparation Example E i > were mixed and coagulated at a weight ratio of 1: 1 to obtain After the rubber-like graft emulsion is coagulated with calcium chloride (CaCU), dehydrated, and then dried to a moisture content of less than 2%, the rubber-like graft copolymer (B-2) (rubber required) of the present invention can be prepared. Content 63% by weight) 'The weight average particle diameter of its rubber particles is a bimodal distribution of 0.1 to 0.3 um. < Preparation Example Π-3 > Manufacture of rubber-like graft copolymer (B-3): (Please read the precautions on the back before filling in this page) f Cooperative printed with 0.08 parts by weight of benzyl peroxide as a starter, 6.6 parts by weight of polybutadiene (produced by Asahi Kasei Corporation, trade name Asadene 55as) was completely dissolved in 74.4 parts by weight of styrene, 25-6 Parts by weight of propylene terephthalate and 30 parts by weight of ethylbenzene to form a feed solution, and then the feed solution was continuously fed to a first reactor having a volume of 45 liters, and the reaction temperature was 100 β (:, The reactor is equipped with a spiral stirrer with a cooling circulation tube, which stirs -__ No. 20 1; This paper size applies the Chinese National Standard (CNS) Λ4 specification (2! OX297) and the Central Standards Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative 4 6 626 2 Λ7 _______ B7 V. Description of the invention (I 1) The rate is 150 ΓΡΒ1, the monomer conversion rate in the first reactor is 15%, and the mixture after the reaction in the first reactor is continuously taken out And then into the second, third and fourth reactors in sequence, at the same time The third reactor was charged with 0.1 parts by weight of the third-dodecyl mercaptan, and the reverse rotation phenomenon occurred in the second reactor. The devices of the second, third, and fourth reactors are the same as those of the first reactor, but The reaction temperature is 1051, litre, 125 ° C, and the stirring rate is 270rpm, 150rpm, and 110 rpm. When the conversion rate of the mixture reaches 60%, the mixture is taken out and sent to a devolatilization device. After removing the unreacted monomers and volatiles, it is extruded and pelletized to obtain a granular rubbery graft copolymer. The weight average particle diameter of the rubber particles is 0.95 and the rubber content is 11 weight. %. After mixing this granular rubbery graft copolymer with the rubbery graft copolymer (β_2) of the aforementioned < Preparation Example π-2 > 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 0.1, 0.3, um, and ι · 〇 coffee, and the weight average particle diameter of the rubber particles is 0.1% by weight. The physical property test standards of the resin composition prepared in the examples are as follows: 1. Swelling index (SI): The gel content / dry gel content [(Α) / (Β)], the test steps are as follows: (1) 1 g of resin composition of the fine scale sample is added with 30 ml of acetone and shaken to dissolve for 2 hours. (2) Add the second 30 ml of solvent methylbenzyl and put it overnight. (3) Take out the polyethylene bottle and shake it for 1 hour on the second day, and rotate it at the speed of 18, 〇〇〇 ________ Page 21 ^ Paper size applies to China ~ ^^^ ( (;? ^) / \ 4 specifications (210 \ 297) while quoting ^ (Please read the cautions on the back before filling in this page} -Order, stupid 4 6 626 2 Λ7 B7 Zhengong, Central Bureau of Standards, Ministry of Economic Affairs Printed by the Consumer Cooperative V. Description of the Invention (^) Centrifuge at rpm for 20 minutes. (4) Pour out the clear solution and finely measure the content of the bentonite (A). (5) Dry this product and place it in a 12 5 C oven for 3 hours. (6) Fine dry gel content (B). 02. Izod impact strength (IZOD): According to ASTM D-256 method. Test tensile strength (Tsy) measurement: Test HCFC-141b resistance according to ASTM D-638 method: Put a 1.5% deformation test piece in a closed system of 2, 2-dioxane and steam. 'It is placed at a temperature of 23 t, and it is left for 2 hours to observe the tensile strength of the test piece for cracks or fogging. If there is mild cracking or fogging on the test piece, it is indicated by "χ". When cracking or fogging occurs, it is indicated by "XX". If the test piece is free of cracking and fogging, it is indicated by "0". < Example > < Example 1 > A styrene copolymer u_n 70 obtained from < Preparation Example I-1 > was 1% by weight, and was produced from < Preparation Exampleπ-2 > 30% by weight of the obtained rubber-like graft copolymer (B-2), and then added 5.0 parts by weight of a polyester-based thermoplastic elastomer (C) (manufactured by SUNKYONG Corporation, trade name SKYPEL G14〇D), 5, 0 weight Parts of acrylic rubber (D) manufactured by UUREHA company, trade name is Paraloid KM355), and 1.5 parts by weight of slip agent, and mixed and granulated by WerneF & Pf leidrer ZSK 35 extruder at 22oec. Can Kg · cm / cm be expressed as Kg2 / C (n means four pages of 22 pages. This paper size is applicable to Chinese National Standards (CNS) /.W specifications (210 × 297) and (please read the precautions on the back before filling in this page))

'ST 4 6 626 2 A7 B7 五、發明説明（工丨）'ST 4 6 626 2 A7 B7 V. Description of the invention (work 丨)

到橡膠含量18重量％之苯乙烯系樹脂组成物，然後在220°C 下以射出成型機射出試片後，測量膨潤指數、艾氏衝擊強度、抗拉強度及耐UCFC性等物性，測得結果載於附表一。 <實施例2 > ° 依附表一之配方將原料混合均勻後依實施例1之處理方法’並成型測試用試片，測得之物性亦載於附表—。 <實施例3 > 依附表一之配方將原料混合均勻後依實施例1之處理方法，並成型測試用試片，測得之物性亦載於附表—。 <實施例4 > 依附表一之配方將原料混合均勻後依實施例1之處理方法，並成型測試用試片，測得之物性亦載於附表—。 <實施例5 > 依附表一之配方將原料混合均勻後依實施例1之處理方法，並成型測試用試片，測得之物性亦載於附表一。 <實施例6 > 依附表一之配方將原料混合均勻後依實施例1之處理方法’並成型測試用試片，測得之物性亦載於附表一。 <實施例7 > 依附表一之配方將原料混合均勻後依實施例：之處方法，並成型測試用試片，測得之物性亦載於附表一。理 <比較例1 > 同實施例1之操作條件，不同之處在於：不添加聚酽系熱可塑性彈性體（C)及壓克力系橡膠（D)，所製二/ 巧' < 試 ___—____ 第 23 頁 &紙成尺度適用中國國家標毕（CNS )八4規格（2丨〇X π?公你） -裝 -S6 Μ 經濟部中央標準局貞工消赀合作社印製 4 經濟部中央標準局負工消f合作社印製 6 626 2 Λ7 --~---一 B? 五、發明説明（) 一 --一片同樣進行各項物性測驗，結果載於附表_。 <比較例2 > 同實施例1之操作條件，不同之處在於：不添加聚醋系熱可塑性彈性體（C)，並將壓克力系橡膠（D)的添加量改為8.0重量份，所製得之試片同樣進行各項物性測驗，結果載於附表一。 <比較例3 > 同實施例1之操作條件，不同之處在於：聚酯系熱可塑丨生彈性體（C)之添加量改為4.〇重量份，但不添加壓克力系橡膠（D)，所製得之試片同槔進行各項物性測驗，結果載於附表一。 <比較例4 > 同實施例1之操作條件，不同之處在於：聚酯系熱可塑性彈性體（C)之添加量改為〇 3重量份，而壓克力系橡膠（D)之添加量亦改為〇. 3重量份，所製得之試片同樣進行各項物性測驗，結果載於附表一。 <比較例5 > 同實施例1之操作條件，不间之處在於：聚酯系熱可塑性彈性體（C)之添加量改為3. 〇重量份，而壓克力系橡膠（D)之添加量改為42.0重量份，所製得之試片同樣進行各項物性測驗，結果載於附表一。 <比較例6 > 同實施例1之操作條件，不同之處在於··聚酯系熱可塑性彈性體（〇之添加量改為42 〇重量份，而壓克力系橡 ^— __ ___—_____第 24 頁本紙張尺度國家操準（CNS ) M規格（2丨 (請先閱婧背面之注意事項再填寫本頁}After the styrene resin composition with a rubber content of 18% by weight, and then injecting the test piece with an injection molding machine at 220 ° C, the physical properties such as swelling index, Izod impact strength, tensile strength, and UCFC resistance were measured. The results are set out in Schedule 1. < Example 2 > ° The raw materials were mixed uniformly according to the formula in Table 1 and processed according to Example 1 ', and the test pieces for testing were formed. The measured physical properties are also set out in Table-. < Example 3 > After the raw materials were mixed uniformly according to the formula of the attached table 1, the treatment method of the embodiment 1 was followed, and a test piece for testing was formed. The measured physical properties are also listed in the attached table. < Example 4 > After the raw materials were mixed uniformly according to the formula of the attached table 1, the treatment method of the embodiment 1 was followed, and a test piece for testing was formed. The measured physical properties are also set out in the attached table. < Example 5 > After the raw materials were mixed uniformly according to the formula of the attached table 1, the treatment method of the embodiment 1 was followed, and a test piece for testing was formed. The measured physical properties are also listed in the attached table 1. < Example 6 > After the raw materials were mixed uniformly according to the formula of the attached table 1, the treatment method of the embodiment 1 was used and the test piece for testing was formed. The measured physical properties are also listed in the attached table 1. < Example 7 > After the raw materials were mixed uniformly according to the formula of the attached table 1, the method of the example: where the test piece was formed was formed, and the measured physical properties were also listed in the attached table 1. Principle < Comparative Example 1 > The operating conditions are the same as those in Example 1, except that the polyfluorene-based thermoplastic elastomer (C) and the acrylic rubber (D) are not added. ; Try ___—____ page 23 & paper scale is applicable to China National Standards Complete (CNS) 8-4 specifications (2 丨〇X π? 公你)-installed-S6 Μ Zhengong Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs Printed 4 Printed by the Central Bureau of Standards, Ministry of Economic Affairs, F Cooperative, printed 6 626 2 Λ7-~ --- One B? V. Description of the invention () One--One physical property test is also performed, and the results are shown in the attached table. _. < Comparative Example 2 > The operating conditions were the same as those in Example 1, except that the polyester-based thermoplastic elastomer (C) was not added, and the addition amount of the acrylic rubber (D) was changed to 8.0 weight. The prepared test pieces were also tested for various physical properties, and the results are shown in Table 1. < Comparative Example 3 > The operating conditions were the same as those in Example 1, except that the addition amount of the polyester-based thermoplastic elastomer (C) was changed to 4.0 parts by weight, but no acrylic system was added. For rubber (D), the test pieces prepared were tested for various physical properties at the same time. The results are shown in Table 1. < Comparative Example 4 > The operating conditions were the same as those in Example 1, except that the addition amount of the polyester-based thermoplastic elastomer (C) was changed to 0.3 parts by weight, and that of the acrylic rubber (D). The added amount was also changed to 0.3 parts by weight, and the test pieces prepared were also subjected to various physical property tests, and the results are shown in Table 1. < Comparative Example 5 > The operating conditions of Example 1 are the same, except that the addition amount of the polyester-based thermoplastic elastomer (C) is changed to 3.0% by weight, and the acrylic rubber (D ) Was added to 42.0 parts by weight. The test pieces prepared were also tested for various physical properties. The results are shown in Table 1. < Comparative Example 6 > The operating conditions are the same as in Example 1, except that the polyester-based thermoplastic elastomer (the addition amount of 〇 is changed to 42 〇 parts by weight, and the acrylic is ^ _ _ ___ —_____ Page 24 National Standards (CNS) M Specification for this paper standard (2 丨 (Please read the precautions on the back of Jing before filling this page)

、1T 經濟部中央標_局貝工消费合作社印製 46 626 2 A7 -------- B7 五、發明説明“" — ' 膠(D)之添加量改為3.〇重量份，所製得之試片同樣進行各項物性測驗，結果載於附表一。 <比較例7 > 同實施例1之操作條件’不同之處在於：苯乙烯系共聚物（A-1)改為苯乙烯系共聚物（A_4)，所製得之試片同樣進行各項物性測驗，結果載於附表一。由附表一之比較例1的試驗結果可知，當組成物中未添加聚酯系熱可塑性彈性體（C)及壓克力系橡膠（D)時，樹脂組成物的耐HCFC性不佳，試片上有嚴重龜裂或霧化現象，由比較例2試驗結果顯示，只添加壓克力系橡膠（D)而沒有添加聚酯系熱可塑性彈性體（c)時，組成物之耐衝擊性會下降；再由比較例3之試驗結果顯示，只添加聚酯系熱可塑性彈性體（C)而沒有添加壓克力系橡膠（D)時，試片上有輕度龜裂或霧化現象，樹脂之耐flCFc效果差；由比較例4得知’當聚酯系熱可塑性彈性體及壓克力系橡膠（D)之添加量不足時’其耐jiCFC效果不佳，試片有嚴重龜裂或霧化現象；由比較例5的試驗結果顯示，壓克力樹脂（D)添加過量’且組成物之膨潤指數過高，其抗拉強度及艾氏衝擊強度皆會大幅下降；由比較例6試驗結果顯示 ’聚酯系熱可塑性彈性體（C)添加過量且組成物之膨潤指數過低，其抗拉強度亦降低很多；而由比較例7之試驗結果顯不，若使用丙稀睛含量45重量％之苯乙稀系共聚物 (A-4)時，樹脂組成物之黃色度高色相差，且由於樹脂組成物流動性太差，不易成型。 __ ___第25頁______ ^紙诙尺度適用中國國家操導（CNS ) Λ4規格（210X297公蝥〉 (請先閲讀背面之注意事頊再填寫本頁j、 1T Central Standard of the Ministry of Economic Affairs _ Printed by the Bureau of Shellfish Consumer Cooperatives 46 626 2 A7 -------- B7 V. Description of the invention "" — 'The amount of rubber (D) added was changed to 3.0 parts by weight The obtained test pieces were also tested for various physical properties, and the results are shown in Table 1. < Comparative Example 7 > The operating conditions were the same as those in Example 1 except that the styrenic copolymer (A-1 ) Was changed to styrene copolymer (A_4), and the test pieces prepared were also tested for various physical properties, and the results are shown in Table 1. From the test results of Comparative Example 1 in Table 1, it can be seen that when the composition is not When the polyester-based thermoplastic elastomer (C) and the acrylic rubber (D) were added, the resin composition had poor HCFC resistance and severe cracking or fogging on the test piece. The test results of Comparative Example 2 show that When only acrylic rubber (D) is added and no polyester-based thermoplastic elastomer (c) is added, the impact resistance of the composition is reduced; and the test results of Comparative Example 3 show that only polyester-based rubber is added. When the thermoplastic elastomer (C) is not added with acrylic rubber (D), there is a slight crack or fog on the test piece The resin has poor resistance to flCFc; from Comparative Example 4, it was learned that “when the amount of the polyester-based thermoplastic elastomer and the acrylic rubber (D) is insufficient”, its jiCFC resistance is not good, and the test piece is severely cracked. Or the phenomenon of fogging; the test results of Comparative Example 5 show that the acrylic resin (D) is added excessively and the composition's swelling index is too high, and its tensile strength and Izod impact strength will greatly decrease; from the comparative example 6 The test results show that 'polyester-based thermoplastic elastomer (C) is added excessively and the swelling index of the composition is too low, and its tensile strength is also greatly reduced; the test results of Comparative Example 7 are not significant. When the content of the styrene-based copolymer (A-4) is 45% by weight, the yellowness of the resin composition is high, and the phase difference is poor, and the resin composition is too poor in fluidity, so it is not easy to form. __ ___ page 25 ______ ^ The paper scale is applicable to China National Steering (CNS) Λ4 specification (210X297). (Please read the notes on the back first, and then fill out this page. J

46 626 2 Λ7 Β7 五、發明説明（Λ斗）反觀本發明各實施例，其經由各成份比例及使用量的限制’確實可製造出一種具有良好耐衝擊強度、抗拉強度之樹脂纽成物，且當樹脂組成物製成成型品時，亦具有優異耐HCFC性，而可防止組成物和氟氣碳化合物發泡劑因接觸曰久而產生龜裂及霧化之現象，因此，本發明不僅新穎 ’更具有產業上之利用價值。惟以上所述僅為本發明數較隹可行實施例，舉凡熟悉此項技藝人仕，其依本發明精神範疇所做之修飾或變更，均理應包含在本案申請專利範圍内。附表一：本發明各實施例與比較例之主要成份含量及物性試驗表。 (請先閲讀背面之注意事項再填寫本頁) 厂裝' -訂經濟部中奂標準局負工消費合作社印製準標 ^' 國國中 ;用 |適一度 -尺一 3 4...' Κ 麟第頁一 6 246 626 2 Λ7 Β7 V. Description of the invention (Λdou) In contrast to the embodiments of the present invention, through the limitation of the proportion of each component and the amount of use, it is indeed possible to produce a resin composite with good impact strength and tensile strength. Moreover, when the resin composition is made into a molded product, it also has excellent HCFC resistance, and can prevent the composition and the fluorocarbon compound foaming agent from cracking and atomizing due to long-term contact. Therefore, the present invention Not only novelty, but also industrial utilization value. However, the above are only a few feasible embodiments of the present invention. For those skilled in the art, modifications or changes made according to the spirit scope of the present invention should be included in the scope of patent application in this case. Attached Table 1: Test table of main component contents and physical properties of the examples and comparative examples of the present invention. (Please read the precautions on the back before filling out this page) Factory-installed--Order the standard printed by the Ministry of Economic Affairs, China Standards Bureau Off-line Consumer Cooperatives ^ 'Guo Guozhong; use | moderate degree-ruler 3 4 ...' Κ lin page one 6 2

漦公 7 29 X漦 Male 7 29 X

Claims

fS: 2 ^

&Gt;% Patent Range A8 B8 C8 D8 Supplement I Patent Application Scope Amendment No. 816116447 Patent Application 1. A styrene resin composition comprising: —I tn — I— 1 ^ 1 1. ^ 1 xlr-n.--F T (Please read the notes on the back before filling out this page) (1) .100 parts by weight of styrene resin The copolymer (A) is composed of 95 to 0% by weight and the rubber-like graft copolymer (B) is composed of 5 to 100% by weight. The 'styrene copolymer (A) is composed of styrene ethyl ester monomers 82 to 55. Parts by weight, acrylic monomers η to 45 parts by weight, and copolymerizable monomers 0 to 40 parts by weight to be polymerized to obtain the 'rubber-like graft copolymer (B) based on the diene rubber 2 to 90 Parts by weight, and from 50 to 90 weight by styrene-based monomer? Ί, from 10 to 50 weight by acrylonitrile-based monomer? S, and a copolymerizable monomer of 0 to 40% by weight of a monomer mixture composed of 98 to 10 parts by weight of graft polymerization; I · (2) 2 to 20 parts by weight of a polyester-based thermoplastic elastomer (C ), Which is a block copolymer composed of polyester with a hard segment in the molecular structure and polyether or polyester soft segment with a low glass transition temperature (Tg) of less than 0 ° C; and consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative (3) 2 to 20 parts by weight of acrylic rubber broom (D) 'is a combination of a core with a soft rubber property and a shell with a hard polymer', where the core is selected from: poly Ethyl acrylate, polyacrylate, poly-n-butyl acrylate, polyisobutyl acrylate, polyhexyl acrylate ', polyacrylic acid, polyacrylic acid, 2-ethylhexyl vinegar, polymethyl polyacrylate, Polymethyl acrylic acid, polymethyl polyacrylic acid vinegar, polymethyl polyacrylic acid isopropyl ester, polymethyl polyacrylic acid third butyl ester, polymethyl polyacrylic acid isobutyl vinegar, etc. Ammunition (CNS) (210 $ 297 ^ * AS ^ 466262 I 6. Scope of patent application. — Sexual body; but hard The shell of the polymer is selected from: hard polymers such as polymethyl methacrylate, polystyrene, acrylonitrile-benzyl ethylene copolymers, and methyl methacrylate-styrene copolymers. The stupid vinyl-based resin composition according to item 1, wherein the swelling index of the composition measured with acetone / toluene solvent is 4.2 to 7. 5. (Please read the precautions on the back before filling out this page) Economy Consumer cooperation of the Ministry of Intellectual Property Bureau Du printed paper M V »/ Ns6 (quasi rubbish of home country and middle school use 75 75 21 Announcement of the date of this application, &T; Case No. Category C〇2 L j / 〇ί ( The above blocks are filled out by this Bureau) Therefore »Revision Year " Supplement A4 C4 466262 No. 86116447 Patent Specification Amendment Chinese Name of Invention English Name Nationality Styrene Resin Composition STYRENE-BASED RESIN COMPOSITION (1) Lin Quanming (2 ) Xue Donghuan, residence and residence of the Republic of China (1) No. 46-1, 712 Shanjiaoli, Xinhua Town, Tainan County (2) No. 22, Lane 347, Dongfeng Road 701, Tainan City Pi Name (Name) Chi Mei Industry Co., Ltd. Shenyang Standards Bureau Employee Consumer Cooperative Cooperative Printing Line: Nationality Republic of China Applicant Residence, Residence (Office) Representative Name Xu Wenlong No. 59-1, Sanjiazi, 717 Sanjia Village, Rende Township, Tainan County, Page 1 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) fS: 2 ^

&Gt;% Patent Range A8 B8 C8 D8 Supplement I Patent Application Scope Amendment No. 816116447 Patent Application 1. A styrene resin composition comprising: —I tn — I— 1 ^ 1 1. ^ 1 xlr-n.--F T (Please read the notes on the back before filling out this page) (1) .100 parts by weight of styrene resin The copolymer (A) is composed of 95 to 0% by weight and the rubber-like graft copolymer (B) is composed of 5 to 100% by weight. The 'styrene copolymer (A) is composed of styrene ethyl ester monomers 82 to 55. Parts by weight, acrylic monomers η to 45 parts by weight, and copolymerizable monomers 0 to 40 parts by weight to be polymerized to obtain the 'rubber-like graft copolymer (B) based on the diene rubber 2 to 90 Parts by weight, and from 50 to 90 weight by styrene-based monomer? Ί, from 10 to 50 weight by acrylonitrile-based monomer? S, and a copolymerizable monomer of 0 to 40% by weight of a monomer mixture composed of 98 to 10 parts by weight of graft polymerization; I · (2) 2 to 20 parts by weight of a polyester-based thermoplastic elastomer (C ), Which is a block copolymer composed of polyester with a hard segment in the molecular structure and polyether or polyester soft segment with a low glass transition temperature (Tg) of less than 0 ° C; and consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative (3) 2 to 20 parts by weight of acrylic rubber broom (D) 'is a combination of a core with a soft rubber property and a shell with a hard polymer', where the core is selected from: poly Ethyl acrylate, polyacrylate, poly-n-butyl acrylate, polyisobutyl acrylate, polyhexyl acrylate ', polyacrylic acid, polyacrylic acid, 2-ethylhexyl vinegar, polymethyl polyacrylate, Polymethyl acrylic acid, polymethyl polyacrylic acid vinegar, polymethyl polyacrylic acid isopropyl ester, polymethyl polyacrylic acid third butyl ester, polymethyl polyacrylic acid isobutyl vinegar, etc. Ammunition (CNS) (210 $ 297 ^ *