467938 A7 B7 五、發明說明（ 本發明係有關具有優良的耐衝擊性、耐塗性、熔融時 色調安定性及成型加工性之平衡性的熱可塑性樹脂組成物 已知的於橡膠質聚合體接枝共聚合氰化乙烯基化合物 及芳香族乙烯基化合物而形成之樹脂組成物有，丙烯腈· 丁二烯•苯乙烯（ABS樹脂），因其具有優良機械特性 及良好成型加工性，故使用的範圍很廣。特別是於汽車、 機車之用途上，因其具有輕量化之優點，故不僅能作爲內 裝部品，另外還可作爲外裝部品使用，又，此時多半作爲 塗裝用。 已知一般可利用增加A B S樹脂中之丙烯腈含有率的 方式以提升耐塗性，因此，截至目前曾有幾個檢討AB S 樹脂中之丙烯腈比率以改良塗裝性的方法提案。例如，特 開平6 - 1 6 8 9 6號公報中所揭示的，規定含橡膠接枝 共聚合物中之氰化乙烯基含有率及氰化乙烯基系共聚合物 中的氰化乙烯基含有率之差與兩共聚合物之比的方法》但 ，此方法的塗性及熔融時色調安定性並不充足。 又，特開平7- 1 1 0 9 9號公報所揭示的，對含有 橡膠接枝共聚合物中之氰化乙烯基含有率具有特定之氰化 乙烯基含有率的氰化乙烯基系共聚合物係有特定範圍的樹 脂組成物。但，其有熔融時色調安定性差的問題。. 因此，本發明之目的爲，提供一種具有優良的·耐衝擊 性、耐塗性、熔融時色調安定性及成型加工性之平衡性的 耐塗性熱可塑性樹脂組成物。爲了達成此目的，於是經本 ^紙張尺度適用中國國家標準<CNS)A4規格（210 X 297公釐0 閲 讀 背 面 之 注 意 事 項 再 填厂 I、-裝 頁i 訂467938 A7 B7 V. Description of the invention (The present invention relates to a thermoplastic resin composition having excellent balance of impact resistance, coating resistance, hue stability during melting and molding processability. Acrylonitrile · butadiene · styrene (ABS resin) is a resin composition formed by branch copolymerization of a vinyl cyanide compound and an aromatic vinyl compound. It is used because it has excellent mechanical properties and good moldability. The range is very wide. Especially for the applications of automobiles and motorcycles, because it has the advantage of light weight, it can be used not only as interior parts, but also as exterior parts. At this time, it is mostly used for painting. It is known that the acrylonitrile content in the ABS resin can be generally increased to improve the coating resistance. Therefore, there have been several proposals to review the acrylonitrile ratio in the ABS resin to improve the paintability. For example, Japanese Unexamined Patent Publication No. 6-1 6 8 9 6 discloses the content of cyanided vinyl in rubber-containing graft copolymers and the content of cyanided vinyl copolymers. "Method for the difference between the content ratio of vinyl cyanide and the ratio of the two copolymers" However, this method is not sufficient in paintability and hue stability during melting. Also disclosed in Japanese Patent Application Laid-Open No. 7-1109 The cyanide vinyl copolymer having a specific cyanide vinyl content in a rubber-containing graft copolymer has a specific range of resin compositions. However, it has a melting point The problem of poor color tone stability. Therefore, an object of the present invention is to provide a coating-resistant thermoplastic resin composition having excellent balance of impact resistance, paint resistance, color tone stability during melting, and moldability. In order to achieve this purpose, the paper size applies the Chinese National Standard < CNS) A4 specification (210 X 297 mm 0).
經濟部智慧財產局員工消費合作社印製 6 4 經濟部智慧財產局員工消費合作社印製 7 93 8 A7 _____^___B7_______ 五、發明說明（2 ) 發明者們專心檢討的結果發現，組合具有特定之氰化乙烯 基含有率及組成分布的氰化乙烯基系共聚合物與含橡膠接 枝共聚合物，可得到耐衝擊性、耐塗性、熔融時色調安定 性及成型加工性之平衡性優良的樹脂組成物，而完成本發 明。 即，本發明之目的可利用特徵爲，橡膠質聚合體（A )5〜40重量％，橡膠質聚合體以外之共聚合物（B) 9 5〜6 0重量％所形成之樹脂組成物中， (1 )共聚合物（B)之平均氰化乙烯基含有率2 5 〜3 5重量％， (2)共聚合物（B)之氰化乙烯基的組成分布中， 具有平均氰化乙烯基含有率比2重量％高之組成的共聚合 物（B)占共聚合物（B)之3〜20重量％， 的耐塗性熱可塑性樹脂組成物而達成》 本發明之含橡膠接枝共聚合物（I)所使用的橡膠質 聚合體（A)有，二烯系橡膠，丙烯酸系橡膠、乙烯系橡 膠等，其具.體例子如，聚丁二烯，聚（丁二烯一苯乙烯） 、聚（丁二烯一丙烯睛），聚異戊二烯、聚（丁二烯一丙 烯酸丁基）、聚（丁二烯一丙烯酸甲基）、聚（丁二烯一 甲基丙烯酸甲基）、聚（丙烯酸丁基一甲基丙烯酸甲基） 、聚（丁二烯一丙烯酸乙基）、乙烯一丙烯橡膠、乙烯一 丙烯_二烯橡膠、聚（乙烯_異丁烯）、聚（乙烯—丙烯 酸甲基）等。又，可單獨使用或2種以上混合使用。其中 ，就耐衝擊性而言又以使用聚丁二烯、聚（丁二烯一苯乙 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公登) -------------'!裝------J 丨訂_.r (請先閱讀背面之注$項再irt本頁} --線· -5 - 467 93 8 A7 __— B7 五、發明說明（3 ) 烯）、聚（丁二烯一丙烯腈）、乙烯—丙烯橡膠特別好。 本發明之含橡膠接枝共聚合物（I )、氰化乙烯基系 "" 共聚合物（II)及氰化乙烯基系共聚合物（III)所 -使用的氰化乙烯基系單體（a )之具體例子如，丙烯睛、 甲基丙烯腈等，又，可單獨使用2種以上混合使用。其中 ，就耐塗性而言較好爲丙烯腈* 本發明之含橡膠接枝共聚合物（I)、氰化乙烯基系 共聚合物（I I )及氰化乙烯基系共聚合物（I I I )所 使用的芳香族乙烯基單體（b)之具體例子有，苯乙烯、 —甲基苯乙烯、鄰甲基苯乙烯、對甲基苯乙烯、對一 t —丁基苯乙烯、鹵化苯乙烯等，又，可單獨使用或2種以 上混合使用》其中，就成型加工性而言較好爲苯乙烯、α -甲基苯乙烯、又以苯乙烯特別好》 本發明之含橡膠接枝共聚合物（I)所使用的能共聚 合之其他的乙烯基系單體（c )之具體例子有，丙烯酸、 甲基丙烯酸等不飽和羧酸，或丙烯酸甲基、甲基丙稀酸甲 基 '丙烯酸丁基等（甲基）丙烯酸酯類，或丙烯醢胺、甲 基丙烯醯胺、Ν —甲基丙烯醯胺等（甲基）丙烯醯胺類， 或順丁烯二醯、Ν -甲基順丁烯二醯、Ν -苯基順丁烯二 醯等順丁烯二醯類、或馬來酸酐、檸康酸酐、烏頭酸酐等 不飽和酸酐等，其中，就成型加工性而言較好爲甲基丙烯 酸甲基、Ν —苯基順丁烯二醯。 本發明之橡膠質聚合體（Α)必需5〜4 0重量％， 橡膠質聚合體以外之共聚合物（Β )必需爲9 5〜6 0重 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱·〉 --— — — — —------霞 i — f } (請先Μ讀背面之注^?#.項再^^本頁) **J· -線· 經濟部智慧財產局貝工消費合作社印製 —6 — 467 93 ^ A7 ______ B7 五、發明說明（4 ) 量％。若橡膠質聚合體（A)低於5重量％時，所得之耐 塗性熱可塑性樹脂組成物的耐衝擊性不充足，又，超過 4 0重量％時所得之耐塗性熱可塑性樹脂組成物的成型加 工性差。而其中就耐衝擊性及成型加工性之平衡性而言， 較好爲橡膠質聚合體（A) 10〜3 5重量％、橡膠質聚 合體以外之共聚合物（B ) 9 0〜6 5%。 本發明之共聚合物（B )的平均氰化乙烯基含有率必 需爲2 5〜3 5重量％。若平均氰化乙烯基含有率低於 2 5重量％時，所得之耐塗性熱可塑性樹脂組成物的耐塗 性不充足，又，超過3 5重量％之情形下熔融時色調安定 性差。而其中就耐塗性及熔融時色調安定性之平衡性觀點 平均氤化乙儲基含有率較好爲2 8〜3 3重量％ » 本發明之共聚合物（Β )的氰化乙烯基之組成分布中 的具有平均氰化乙烯基含有率比2重量％高之組成的共聚 合物必需占共聚合物（Β)之3〜20重量％。若低於3 重量％時所得之耐塗性熱可塑性樹脂組成物的耐塗性不充 足，又，超，過2 0重量％之情形下熔融時之色調安定性差 。而其中就耐塗性及熔融時色調安定性之平衡性觀點較好 爲5〜18重量％» 本發明之含橡膠接枝共聚合物（I)所使用的橡膠質 聚合體（Α)之含有率並無特別限制，但，就耐衝擊性觀 點較好爲1 0〜8 0重量％，又以4 0〜7 0重量％更佳 。又，含橡膠接枝共聚合物（I )之氤化乙烯基系單體（ a )的含有率並無特別限制，但，就成型加工性觀點較好 本紙張尺度適用中國國.家標準（CNS)A4規格（210 X 297公釐-） --------I - II I - - I 請先閲讀背面之注項再本頁) 訂 :線· 經濟部智慧財產局貝工消費合作社印製 -7 - 467938 A7 B7 五、發明說明（5 ) 爲5〜5 0重量％，又以1 0〜4 0重量％更佳。又，含 橡膠接枝共聚合物（I)之芳香族乙烯基系單體（b)的胃 含有率並無特別限制，但，就成型加工性觀點較好爲1 〇 -〜8 0重量％ ’又以2 0〜7 0重量％更佳。又，含橡膠 接枝共聚合物（I )之能共聚合的其他乙烯基系單體（c )之含有率並無特別限制，但，就成.型加工性觀點較好爲 5〜5 0重量％。 另外，接枝率，接枝成分之共聚合物的還原粘度並無 特別限制，但，就耐衝擊性而言接枝率較好爲1 〇〜8 0 重量％，接枝成分之共聚合物的還原粘度較好0 * 2〜0 * 8 d J? / g。 本發明之氰化乙烯基共聚合物（I I )爲，氰化乙烯 基系單體（a ) 1 5〜3 5重量％、芳香族乙烯基系單體 (b) 85〜65重量％。若氰化乙烯基系單體（a)低 於1 5重量％時，使用所得之氰化乙烯基系共聚合物的耐 塗性熱可塑性樹脂組成物之耐塗性不充足，又，超P3 5 重量％時，，會明顯降低使用所得之氛化乙烯基系共聚合物 之耐塗性熱可塑性樹脂組成物之成‘型加工性及熔融時色調 ‘ 安定性。至於芳香族乙烯基系單體（b )低於6 5重量％ 時，會明顯降低所得之耐塗性熱可塑性樹脂組成物的熔融 時色調安定性，又，超過85重量％時，會明顯降低所得 之耐塗性熱可塑性樹脂組成物的耐塗性。而其中又以氤化 乙烯基系單體（a)爲20〜30重量％、芳香族乙烯基 系單體（b )爲8 0〜7 0重量％特別好β 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 一 8胃 --------------;.嚷— {請先閱讀背面之ii急事項再r"免本頁> .SJ· --線· 經濟部智慧財產局員工消費合作社印製 .467 938 A7 B7 五、發明說明（6 ) 本發明之氰化乙烯基系共聚合物（1 I I )爲，氰化 乙烯系單體（a ) 3 0〜5 0重量％、芳香族乙烯基系單 體（b) 70〜50重量％»若氰化乙烯基系單體（a) 低於3 0重量％時，使用所得之氰化乙烯系共聚合物的耐 塗性熱可塑性樹脂組成物之耐塗性不充足，又，超過5 〇 重量％時會降低色調安定性。而其中又以氰化乙烯基單體 (a) 33〜45重量％、芳香族乙烯基系單體（b) 67〜55重量％特別好。 共聚合物（B )之氰化乙烯基的組成分布中*具有平 均氰化乙烯基含有率比2重量％高之組成的共聚合物必需 占共聚合物（B)之3〜2 0重量％，而其具體的方法有 ，使^成分布中具有平均氰化乙烯基含有率比2重量％高 之組成的比率低於2重量％之氰化乙烯基系共聚合物（ I I ) 5 0〜9 0重量單位及，具有平均氰化乙烯基含有 率比2重量％高之組成的比率爲2 5〜4 0重置％之氰化 乙烯基系共聚合物（I I I ) 5〜4 5重量％單位混合的 方法。 ， 氰化乙烯基之組成分布則可利用•將環己烷加入氟化 乙烯基系共聚合物之甲基乙基酮溶液後，使分別沈澱之氰 化乙烯基系共聚合物乾燥•再測定其重量，接著以紅外分 光光度計求取氰化乙烯基含有率而得到。又，平均氰化乙 烯基含有率非各別地而係全體以紅外分光光度計而求得的 本發明中的含橡膠接枝共聚合物（I)之製造方法並 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐-) -------------—策--- 'j (請先閱讀背面之注意事項再f本頁) 訂.! --線· 經濟部智慧財產局員工消费合作社印製 -9 - „467938 A7 B7 五、發明說明（7 ) (請先閱讀背面之注意事項再本頁) 無特別限制，又，可利用乳化聚合法、塊狀聚合法、溶液 聚合法及其組合而成的聚合法而製得。其中就控制橡膠之 粒徑及接枝率觀點較好爲乳化聚合法。 本發明的氣化乙烯基系共聚合物（II)之聚合方法 並無特別限制，但，就能使氰化乙烯基之組成分布準確觀 點又以塊狀聚合法、溶液聚合法特別好》 本發明之氰化乙烯基系共聚合物（I I I )的聚合方 法並無特別限制，但，就能使氰化乙烯基之組成分布寬度 觀點又以水系懸浮聚合爲佳。 此聚合法所使用的懸浮安定劑有，粘土、硫酸鋇、氫 氧化鎂等無機系懸浮安定劑，或聚乙烯醇、羧基甲基纖維 、聚丙烯醢胺、甲基丙烯酸甲基/丙烯醯胺共聚合物等有 機系懸浮安定劑等，又，可利用偶氮基系引發劑、羥基過 氧化物系引發劑聚合。 經濟部智慧財產局員工消費合作社印製 本發明之耐塗性熱可塑性樹脂組成物的製造方法並無 特別限制，又，配合時可使用螺帶混合機、V型混合機、 雌殼體混合，機等。另外亦可採用，使用單軸擠押機、2軸 擠押機等擠押機，或巴巴里混合機、混合物滾筒、加壓捏 和機等之混煉處理方式》 又以對於連續塊狀聚合氰化乙烯基系共聚合物（I I )之過程中爲熔融狀態的氰化乙烯基系共聚合物（I I ) *連續添加，含橡膠接枝共聚合物（I )及利用懸浮聚合 法而製得之氰化乙烯基共聚合物（I I I )使其混合的方 式能使色調更好而爲佳。 _ 未紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公«0~' -10 - 經濟部智慧財產局員工消費合作社印製 467938 A7 B7 五、發明說明（8 ) 又’就色調觀點較好爲，利用單軸擠押機或2軸擠押 機連續將已預先乾燥得自乳化聚合乳膠之泥漿或含水塊的 含橡膠接枝共聚體（I )及，以懸浮聚合而得到之乾燥的 管狀氰化乙烯基系共聚合物（I I I )連續供應給付出口 之2軸擠押機，使其與氰化乙烯基系共聚合物（I I )之 脫單體過程中的殘存單體爲10重量％以下之氰化乙烯基 系共聚合物（I I )熔融混合並同時脫單體，以製成耐塗 性熱可塑性樹脂組成物。 另外，必要時本發明可配合使用， 2 ’ 6 —二—t — 丁基一4 —甲基苯酣， 4，一亞丁基一雙（3 -甲基一6_t —丁基苯酚） 等苯酚系防氧化劑，或三（混合，單及二苯基）磷脂、二 苯基異癸基磷脂等膦脂系防氧化劑，或二月桂基硫撐二丙 酸酯，甘油二肉豆蔻基硫撑二丙酸酯 '二星狀硫撑二丙酸 酯等硫系防氧化劑，或2 —羥基一 4 一辛氧基二苯甲酮， 2_ (2 —羥基—5 -甲基苯基）苯并三唑等苯并三唑系 紫外線吸收，劑，或雙（2，2，6，6 -四甲基）-4-哌啶基等光安定劑，或羥基烷基胺，磺酸鹽等防靜電劑， 或季戊四醇四硬脂酸酯，乙撐雙硬脂醯胺，金屬皂等滑劑 ，或四溴代雙苯酚A，十溴化苯酚氧化物，TBA環氧低 聚物，TB A聚碳酸酯低聚物，三氧化銻等難燃劑，難助 燃劑等各種添加劑，或著色劑，玻璃纖維，碳纖維.等無機 填充材料》 其中就塗性而言，季戊四-四硬脂酸酯較好爲0·1 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐-)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 4 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 7 93 8 A7 _____ ^ ___ B7_______ 5. Description of the Invention (2) As a result of the intensive review by the inventors, the combination has a specific cyanide The vinyl cyanide-based copolymer and the rubber-containing graft copolymer having a vinyl content ratio and composition distribution can be obtained with excellent balance of impact resistance, coating resistance, hue stability during melting, and molding processability. The resin composition completes the present invention. That is, the object of the present invention can be utilized in a resin composition formed by 5 to 40% by weight of a rubbery polymer (A) and 95 to 60% by weight of a copolymer (B) other than the rubbery polymer. (1) The average content of vinyl cyanide of the copolymer (B) is 25 to 35 wt%, and (2) The composition distribution of the vinyl cyanide of the copolymer (B) has an average vinyl cyanide The copolymer (B) having a composition having a higher base content than 2% by weight accounts for 3 to 20% by weight of the copolymer (B), and the coating-resistant thermoplastic resin composition is achieved. The rubber-containing graft of the present invention Examples of the rubbery polymer (A) used in the copolymer (I) include diene rubber, acrylic rubber, and vinyl rubber, and specific examples thereof include polybutadiene, poly (butadiene-1 Styrene), poly (butadiene-acrylonitrile), polyisoprene, poly (butadiene-butyl acrylate), poly (butadiene-methyl acrylate), poly (butadiene-methyl) Acrylic methyl), poly (butyl acrylate-methyl methacrylate), poly (butadiene-ethyl acrylate), ethylene-propylene rubber Rubber, ethylene-propylene-diene rubber, poly (ethylene-isobutylene), poly (ethylene-acrylic acid methyl), etc. Moreover, they can be used individually or in mixture of 2 or more types. Among them, in terms of impact resistance, the use of polybutadiene and poly (butadiene-styrene) paper standards applies to China National Standard (CNS) A4 (210 X 297 GD) ------- ------ '! Equipment ------ J 丨 order _.r (please read the note on the back and then irt this page)-line · -5-467 93 8 A7 __— B7 five Description of the invention (3) olefin), poly (butadiene-acrylonitrile), ethylene-propylene rubber are particularly good. The rubber-containing graft copolymer (I), vinyl cyanide-based " " Specific examples of the polymer (II) and the vinyl cyanide-based copolymer (III)-the vinyl cyanide-based monomer (a) used include acrylonitrile, methacrylonitrile, etc., and they may be used alone Two or more types are used in combination. Among them, acrylonitrile is preferred in terms of coating resistance. * The rubber-containing graft copolymer (I), the cyanide vinyl copolymer (II), and the cyanide vinyl of the present invention Specific examples of the aromatic vinyl monomer (b) used in the system copolymer (III) include styrene, -methylstyrene, o-methylstyrene, p-methylstyrene, and p-t-butyl. Basic styrene, Halogenated styrene, etc. can be used alone or in combination of two or more types. Among them, styrene, α-methylstyrene are preferred in terms of molding processability, and styrene is particularly preferred. The rubber-containing compound of the present invention Specific examples of the copolymerizable other vinyl-based monomer (c) used in the graft copolymer (I) include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, or acrylic acid methyl and methacrylic acid. (Meth) acrylic acid esters such as methacrylic acid butyl, or (meth) acrylamide such as acrylamide, methacrylamide, N-methacrylamide, or maleimide , Maleic anhydride, citraconic anhydride, aconitic anhydride and other unsaturated acid anhydrides, etc., among which, maleic anhydride, such as maleic anhydride, citraconic anhydride, aconitic anhydride and the like In terms of properties, methyl methacrylate and N-phenyl maleic acid are preferred. The rubbery polymer (A) of the present invention must be 5 to 40% by weight. Copolymers other than the rubbery polymer ( Β) Must be 9 5 ~ 60 0 The paper size is applicable to China National Standard (CNS) A4 (210 X 297 Public Love ·〉 --- — — — —------ Xia i — f} (Please read the note on the back ^? #. Item then ^^ this page) ** J · -line · economy Printed by the Shellfish Consumer Cooperative of the Ministry of Intellectual Property Bureau — 6 — 467 93 ^ A7 ______ B7 V. Description of the invention (4) Amount%. If the rubber polymer (A) is less than 5% by weight, the coating resistance obtained is hot The impact resistance of the plastic resin composition is insufficient, and the coating resistance of the thermoplastic resin composition obtained when it exceeds 40% by weight is poor in molding processability. Among them, in terms of the balance between impact resistance and molding processability, a rubber polymer (A) 10 to 35 wt% and a copolymer other than the rubber polymer (B) 9 0 to 6 5 are preferred. %. The average copolymer content of the copolymer (B) of the present invention must be 25 to 35 wt%. When the average vinyl cyanide content is less than 25% by weight, the coating resistance of the obtained coating-resistant thermoplastic resin composition is insufficient, and when it exceeds 35% by weight, the stability of hue upon melting is poor. Among them, from the viewpoint of the balance between the coating resistance and the stability of the hue when melted, the average content of the vinylidene group is preferably 28 to 33% by weight. »The vinyl cyanide of the copolymer (B) of the present invention The copolymer having a composition having an average vinyl cyanide content higher than 2% by weight in the composition distribution must account for 3 to 20% by weight of the copolymer (B). If it is less than 3% by weight, the coating resistance of the obtained thermoplastic resin composition is insufficient, and when it exceeds 20% by weight, the hue stability during melting is poor. Among them, 5 to 18% by weight is preferable from the viewpoint of the balance between coating resistance and hue stability during melting. »The rubber polymer (A) used in the rubber-containing graft copolymer (I) of the present invention contains The rate is not particularly limited, but from the viewpoint of impact resistance, it is preferably 10 to 80% by weight, and more preferably 40 to 70% by weight. In addition, there is no particular limitation on the content of the halogenated vinyl-based monomer (a) containing the rubber-grafted copolymer (I). However, from the standpoint of molding processability, the paper standard is applicable to the Chinese standard. ( CNS) A4 specification (210 X 297 mm-) -------- I-II I--I Please read the note on the back before this page) Order: Line · Consumer of Intellectual Property Bureau of Ministry of Economic Affairs Printed by the cooperative -7-467938 A7 B7 5. Description of the invention (5) is 5 to 50% by weight, and more preferably 10 to 40% by weight. The stomach content of the aromatic vinyl-based monomer (b) containing the rubber graft copolymer (I) is not particularly limited, but it is preferably from 10 to 80% by weight from the viewpoint of molding processability. 'It is more preferably 20 to 70% by weight. In addition, the content of the other vinyl-based monomer (c) which can be copolymerized with the rubber-grafted copolymer (I) is not particularly limited, but it is preferably 5 to 50 from the viewpoint of moldability. weight%. In addition, the graft ratio and the reduced viscosity of the copolymer of the graft component are not particularly limited, but in terms of impact resistance, the graft ratio is preferably 10 to 80% by weight. The copolymer of the graft component The reduced viscosity is preferably 0 * 2 ~ 0 * 8 d J? / G. The vinyl cyanide copolymer (I I) of the present invention is a vinyl cyanide-based monomer (a) of 15 to 35 wt% and an aromatic vinyl-based monomer (b) of 85 to 65 wt%. When the vinyl cyanide-based monomer (a) is less than 15% by weight, the coating resistance of the thermoplastic resin composition using the obtained vinyl cyanide-based copolymer is insufficient, and the super-P3 When it is 5 wt%, the coating resistance of the obtained thermoplastic vinyl copolymer using the obtained thermoplastic resin composition is significantly reduced, and the stability of the molding processability and the hue upon melting is reduced. When the aromatic vinyl-based monomer (b) is less than 65% by weight, the color stability of the obtained coating-resistant thermoplastic resin composition when melted is significantly reduced, and when it exceeds 85% by weight, it is significantly reduced. Coating resistance of the obtained coating thermoplastic resin composition. Among them, the halogenated vinyl monomer (a) is 20 to 30% by weight, and the aromatic vinyl monomer (b) is 80 to 70% by weight. Particularly good. CNS) A4 specifications (210 X 297 mm)-8 stomachs -------------- ;. 嚷 — {Please read the urgent matters on the back before r " free this page >. SJ · --printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs.467 938 A7 B7 V. Description of the invention (6) The cyanidated vinyl copolymer (1 II) of the present invention is (A) 30 to 50% by weight, aromatic vinyl monomer (b) 70 to 50% by weight »If the cyanated vinyl monomer (a) is less than 30% by weight, use the obtained Coating resistance of the vinyl cyanide-based copolymer The coating resistance of the thermoplastic resin composition is insufficient, and when it exceeds 50% by weight, the hue stability is lowered. Among them, the cyanide vinyl monomer (a) 33 to 45% by weight, and particularly preferably 67 to 55% by weight of the aromatic vinyl-based monomer (b). The composition distribution of the cyanidated vinyl group of the copolymer (B) has an average content of the cyanated vinyl group. The copolymer with a composition of 2% by weight must account for 3 to 20% by weight of the copolymer (B), and the specific method is to have an average content ratio of vinyl cyanide in the distribution of 2% by weight The ratio of the composition having a high composition ratio of less than 2% by weight is less than 2% by weight of the cyanide vinyl copolymer (II) 50 to 90, and the ratio of the composition having an average content of the cyanide vinyl content higher than 2% by weight is 2 5 ~ 40 0% reset of the cyanide vinyl copolymer (III) 5 ~ 4 55% by weight unit mixing method. The composition distribution of vinyl cyanide can be used • Cyclohexane is added to fluorinated ethylene After the methyl ethyl ketone solution of the base copolymer is dried, the precipitated vinyl cyanide copolymer is dried and the weight thereof is measured, and then the content of the vinyl cyanide is determined by an infrared spectrophotometer. In addition, the average content of vinyl cyanide is determined by infrared spectrophotometry, and the method for producing the rubber-containing graft copolymer (I) in the present invention is obtained by infrared spectrophotometry. (CNS) A4 specification (210 X 297 mm-) ------------- — 策 --- 'j (Please read the precautions on the back before f this page) Order.! --Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-9-467467 A7 B7 V. Description of Invention (7 ) (Please read the precautions on the back of this page before this page) There is no particular limitation, and it can be produced by emulsion polymerization, block polymerization, solution polymerization, and a combination of polymerization methods. Among them, the control of rubber From the viewpoint of particle size and graft ratio, the emulsification polymerization method is preferred. The polymerization method of the vaporized vinyl-based copolymer (II) of the present invention is not particularly limited, but the viewpoint that the composition distribution of the vinyl cyanide group can be accurately determined is particularly good by the block polymerization method and the solution polymerization method. The polymerization method of the cyanidated vinyl-based copolymer (III) of the invention is not particularly limited, but it is preferable to use a water-based suspension polymerization in terms of the width of the composition distribution of the cyanided vinyl. Suspension stabilizers used in this polymerization method include inorganic suspension stabilizers such as clay, barium sulfate, and magnesium hydroxide, or polyvinyl alcohol, carboxymethyl fiber, polypropylene amidamine, and methacrylic acid acrylamide. Copolymers, such as organic suspension stabilizers, can also be polymerized using azo-based initiators and hydroxy peroxide-based initiators. The manufacturing method for printing the coating-resistant thermoplastic resin composition of the present invention by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics is not particularly limited, and a ribbon mixer, a V-type mixer, and a female shell can be used for mixing. Machine and so on. In addition, it is also possible to use a single-shaft extruder, a 2-shaft extruder, or a mixing treatment method such as a Barbary mixer, a mixture drum, a pressure kneader, etc. The cyanide vinyl copolymer (II) is molten in the process of the cyanide vinyl copolymer (II) * continuously added, containing a rubber graft copolymer (I) and prepared by suspension polymerization The obtained cyanide vinyl copolymer (III) is mixed in such a manner that the color tone is better and better. _ The paper size is in accordance with China National Standard (CNS) A4 (210 X 297) «0 ~ '-10-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 467938 A7 B7 V. Description of the invention (8) and' On the perspective of color Preferably, a uniaxial extruder or a two-axis extruder is used to continuously dry the rubber-containing graft copolymer (I) which has been previously dried from the emulsion polymerized latex slurry or water block, and dried by suspension polymerization. The tubular cyanide vinyl copolymer (III) was continuously supplied to the 2-axis extruder at the outlet, so that the residual monomer in the demonomerization process with the cyanide vinyl copolymer (II) was 10 The cyanidated vinyl copolymer (II) below wt% is melt-mixed and demonomerized at the same time to prepare a coating-resistant thermoplastic resin composition. In addition, the present invention can be used in combination when necessary, 2 '6-2 —T — Butyl-4-methylphenylhydrazone, 4, butylene-bis (3-methyl-6-t —butylphenol) and other phenolic antioxidants, or tris (mixed, mono and diphenyl) phospholipids Phospholipid-based antioxidants such as diphenyl isodecyl phospholipids, or Sulfur-based antioxidants such as lauryl thiodipropionate, glycerol dimyristyl thiodipropionate ', two star-shaped thiodipropionate, or 2-hydroxy-4 4-octyloxybenzophenone, 2_ (2-hydroxy-5-methylphenyl) benzotriazole and other benzotriazole UV absorbers, agents, or bis (2,2,6,6-tetramethyl) -4-piperidinyl etc. Light stabilizers, or antistatic agents such as hydroxyalkylamines, sulfonates, or slip agents such as pentaerythritol tetrastearate, ethylenebisstearylamine, metal soaps, or tetrabromobisphenol A, decabromo Various additives such as phenol oxide, TBA epoxy oligomer, TBA polycarbonate oligomer, antimony trioxide and other flame retardants, flame retardants and other additives, or colorants, glass fibers, carbon fibers, etc. Among them, in terms of paintability, pentaerythritol-tetrastearate is preferably 0.1. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm-)
_ 11 - 4 6 7 9 3 8 A7 B7 五、發明說明（9 ) 〜5重量單位。若其低於0 * 1重量單位時，其提升耐塗 性之效果會不足，又，超過5重量單位時成型性差。 (請先閲讀背面之注意事項再w'r本頁) 因本發明之耐塗性熱可塑性樹脂組成物具有優良的耐 衝撃性、耐塗性、熔融時色調安定性及成型成2性之平衡 性，故可供應給射出成型、片成型、擠押成型、吹煉成型 、壓縮成型、真空成型等各種加工成型之用途，又，這些 加工品適用於塗裝、真空蒸鍍 '電鍍等。 本發明之耐塗谁熱可塑性樹脂組成物尤其適用於丙烯 基系塗料及尿烷系塗料，又，丙烯基系塗料係指，以丙烯 酸及其酯類與，甲基芮烯酸及其酯類或其他乙烯基化合物 之共聚合樹脂爲形成塗膜之主成分的塗料。而尿烷系塗料 係指*樹脂骨架中具有尿烷鍵結或形成塗膜之過程中生成 尿烷鍵結之塗料。 經濟部智慧財產局員工消費合作社印製 爲了更具體說明本發明，下面將以實施例及比較例說 明，但非限於此例。又，參考例、實施例、比較例中的單 位係指重量單位，％係指重量％ »至於所得之含橡膠接枝 共聚合物（.1 )、氰化乙烯基系共聚合物（I I )、氰化 乙烯基系共聚合物（I I I)、共聚合物（B)及耐塗性 熱可塑性樹脂組成物之各物性值係利用下列試驗方法而求 得的》 接枝率：將丙酮加入含橡膠接枝共聚合物（〗）（重量Μ )中回流3小時，再離心分離此溶液4 0分鐘後 過濾不溶成分，接著以6 0 eC真空乾燥此不溶成 分5小時，測定重量（_ N )。其後，利用下列式 本姑張尺度適用中國國家標準<CNS>A4親格（210 X 297公g ) ~ _ 12 - 46 7 93 8 A7 _ B7 五、發明說明（10) 求取接枝率。又，式中L爲含橡膠接枝共聚合物 (I )中橡膠質聚合體含有率（％)。 (請先閱讀背面之注§項再f本頁)_ 11-4 6 7 9 3 8 A7 B7 5. Description of the invention (9) ~ 5 weight units. If it is less than 0 * 1 weight unit, the effect of improving the coating resistance will be insufficient, and if it exceeds 5 weight units, the moldability will be poor. (Please read the precautions on the back before w'r this page) Because of the coating resistance of the present invention, the thermoplastic resin composition has excellent impact resistance, coating resistance, hue stability when melted, and balance of molding properties. It can be used for injection molding, sheet molding, extrusion molding, blow molding, compression molding, vacuum molding and other processing and molding applications, and these processed products are suitable for painting, vacuum evaporation, plating, etc. The thermoplastic resin composition of the present invention is particularly suitable for propylene-based coatings and urethane-based coatings. In addition, propylene-based coatings refer to acrylic acid and its esters, and methylrenoic acid and its esters. Or a copolymer resin of other vinyl compounds is a coating material that forms a main component of a coating film. The urethane-based coating refers to a coating that has a urethane bond in the resin skeleton or forms a urethane bond during the formation of a coating film. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs In order to explain the present invention in more detail, the following examples and comparative examples will be used to illustrate, but not limited to this example. In the reference examples, examples, and comparative examples, the units refer to weight units, and the% refers to% by weight. As for the rubber-containing graft copolymer (.1) and the cyanide-based vinyl copolymer (II) obtained, The physical properties of the vinyl cyanide-based copolymer (III), the copolymer (B), and the coating-resistant thermoplastic resin composition were determined by the following test method. Graft ratio: Acetone was added to Reflux in rubber graft copolymer (〗) (weight M) for 3 hours, then centrifuge the solution for 40 minutes and filter the insoluble component, then dry the insoluble component under vacuum at 60 eC for 5 hours, and determine the weight (_N) . After that, the following formula was used to apply the Chinese National Standard < CNS > A4 Personality (210 X 297 g) ~ _ 12-46 7 93 8 A7 _ B7 V. Description of the invention (10) To obtain the graft rate. In the formula, L is the rubber polymer content (%) in the rubber-containing graft copolymer (I). (Please read the note § on the back before f this page)
接枝率（％) =l〇〇X (N— MxL/100)/(M x L / 1 〇 〇 ) 還原粘度：利用烏貝勒鐵粘度計，於測定溫度3 Ο °C下以 試料濃度0 · 4g/dj?之甲基乙基酮溶液測定 〇 平均氰化乙烯基含有率：以加熱壓力機將試料壓成4 0 以m之薄膜，再以紅外分光光度計求取。 經濟部智慧財產局貝工消費合作社印製 氰化乙烯基組成分布：將試料2 g溶解於8 Omi?之甲基 乙基酮中*再加入環己烷，其後，真空乾燥沈澱 的氰化乙烯基系共聚合物並測定重量，又，以紅 外^分光分析之吸光度比求取此氰化乙烯基系共聚 合物的氰化乙烯基含有率。 其後，標繪累積重量％及氤化乙烯基含有率，再 求取平均氰化乙烯基含有率比2重量％高之比率 艾佐德衝擊強度：將耐塗性熱可塑性樹脂組成物射出成型 後，依據ASTM D256測定附有1/2 本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公發） -13 ™ 467938 A7 B7 五、發明說明（11) inch X切口的艾佐德衝撃強度》 熔融時之色調安定性：將耐塗性熱可塑性樹脂組成物射出 成型時，使其滯留於2 3 0 °C之成型機內3 0分 鐘後，依據JIS K7103，利用日本電色 工業（股）製之測色色差訐測定所得成型品之黃 變度（Y I )。 經濟部智慧財產局員工消費合作杜印製 耐塗性：將耐塗性熱可塑性樹脂組成物射出成型，再於所 得之成型品上噴塗丙烯基系塗料溶液（藤倉化成 (股）製之塗料亞克里線# 6 6 E’/烯料一亞克 里線I型稀料=50/50重量比），其後以 7 0°C乾燥3 0分鐘後，以外觀評估塗面之表面 性。又，尿烷系塗料則使用日本偏得（股）製布 西白（內層：Pu Blush White Base* 中層：pu Blush White Coctail #1，外層：Pu Pearl dear * 硬化劑:Po 1 yar em i gh t y 1 ac Hardenner ’稀料：Polyuremightylac)，再以 7 〇 °C 乾燥 3 0分鐘後，評估塗面之塗膜粘合性。 流動性.：以I SO 1 1 33爲基準，測定220 °C下荷 重10kg之熔體流動率。 : 參逢例1 (製造含橡膠接枝共聚合物（I )) 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐.) -14 - 467938 A7 B7 五、發明說明（12) I ^ ^ 1 ϋ ^ ^ n n H 1· I i 請先Μ讀背面之注专¥項再Wk本頁) 將純水120單位、葡萄糖0·5單位、焦磷酸鈉 0.5單位、硫酸第一鐵0·005單位、聚丁二烯乳膠 (橡膠粒徑0 · 3 #m、凝膠含有率8 5%) 5 0單位（ 固體成分換算下）放入氮取代之反應器中，攪拌下使反應 器內之溫度升至6 5 °C。當內溫達6 5 °C開始聚合時’以 5小時時間連續滴入單體（苯乙烯4 0單位，丙烯腈1 0 單位）及t 一十二烷硫醇0 · 3單位所形成的混合物。同 時以7小時時間連續滴入氫過氧化枯烯0 _ 2 5單位、油 酸鉀2·5單位及純水25單位所形成的水溶液，結束反 應。其後，以硫酸使所得之接枝共聚合物乳膠凝固，再以 苛性蘇打中和後洗淨、過濾、乾燥，得含橡膠接枝共聚合 物（I) »此含橡膠接枝共聚合物（ .1)之橡膠質聚合體 含有率爲5 0%，接枝率爲4 5%、樹脂成分之還原粘度 爲 0_68d5/g。 參考例2 (製造氰化乙烯基系共聚含物（I I )) 經濟部智慧財產局員工消費合作社印製 使用具，有表1之樣式的2槽及預熱機、脫單體機所形 成的連續塊狀聚合裝置，以1 3 5 k g/時之速度連續將 丙烯睛2 5單位、苯乙烯7 5單位及η _辛基硫醇 0 · 1 5單位所形成的單體混合物供應給第1聚合槽，使 其連續塊狀聚合。又，將第1聚合槽之聚合率控制於5 8 〜6 1%，第2聚合槽出之聚合體的聚合率控制於9 0〜 9 1 % »接著，以單軸擠.押機型脫單體機由出口減壓蒸發 回收未反應之單體，再由脫單_機之前端得到表3所記載 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱> ~ -15 - Α7 Β7 467938 五、發明說明（13) 之氰化乙烯基系共聚合物（I I ) A。又，所得氰化乙嫌 基系共聚合物（I I ) A的平均氰化乙燦基含有率及平均 氰化乙嫌基含有率比2重量％高之比率（％)則記載於表 3 0 參考例3 (製造氰化乙烯基系共聚合物（I I ) B) 使用具有表2之樣式的1槽及預熱機、脫單體機所形 成的連續塊狀聚合裝置，並以1 3 5 k g/時之速度將西 嫌睛2 5單位、苯乙嫌7 5單位、η —辛基硫醇〇 . IQ 單位所形成的單體混合物連續供應給聚合槽，使其連績塊 狀聚合。又，將聚合槽出之聚合物聚合率控制於7 4〜 7 6% ’其後，以單軸擠押機型預熱機使聚合反應混合物 預熱後，利用2軸擠押機型脫單體機由出口減壓蒸發回收 未反應之單體，再由脫單體機之前端得到具有表3所記載 之組成的氰化乙烯基系聚合體（I I ) Β。所得氰化乙烯 基系共聚合物（I I ) Β的平均氛化乙烯基含有率及平均 氰化乙烯基，含有率比2重量％高之比率（％ )則記載於表 3。 參考例4 (製造氰化乙烯基系共聚合物（I I ) C) 使用具有表2之樣式的1槽及預熱機、脫單體機所形 成的連續塊狀聚合裝置，並以1 3 5 k g/時之速度將丙 烯睛28單位、苯乙烯72單位' η -辛基硫醇0 . 18 單位所形成的單體混合物連續巧應給聚合槽，使其連續塊 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐> ------------'-.I裝-------訂_,τ--ι--!線7^· (請先閱讀背面之注意事項再¥本頁) ί. 經濟部智慧財產局員工消費合作社印製 —16 _ A7 467938 ______B7__ 五、發明說明（14) 狀聚合。又，將聚合槽出聚合物聚合率控制於7 4〜7 6 %，其後，以單軸擠押機型預熱機使聚合反應混合物預熱 後，利用2軸擠押機型脫單體機由出口減壓蒸發回收未反 應之單體，再由脫單體機之前端得到具有表3所記載之組 成的氰化乙烯基系共聚合物（I I ) C。所得之氰化乙烯 基系共聚合物（i I ) C的平均氰化乙烯基含有率及平均 氰化乙烯基含有率比2重量％高之比率（％)則記載於表 3。 發考例5 (製造氰化乙烯基系共聚合物（I I I ) a) 於容量2 0 J2之具有折流板及法厄德拉型攪拌翼之不 銹鋼製高壓鍋中，將甲基丙烯酸甲基/丙烯醯胺共聚合物 (記載於特公昭45—24151號公報）0·05單位 溶解於離子交換1 6 5單位中，並以4 0 0 r pm攪拌此 溶液及以氮氣取代系內。其次，將丙烯腈3 1單位、苯乙 烯69單位、t —十二烷硫醇0 · 3單位、2，2 —偶氮 二異丁腈0.· 52單位之混合溶液加入攪拌中的反應系內 ，使其升溫至6 0°C而開始聚合。於開始聚合至1 0 0分 鐘之時間內將溫度升至6 5°C*接著，以5 0分鐘將溫度 升至1 0 0°C，以完成聚合。其後，利用一般的方法使反 應系冷卻、分離聚合物、洗淨、乾燥、得氰化乙烯基系共 聚合物體（I I I ) a。所得氰化乙烯基系共聚合物（I I ) a的平均氤化乙烯基含有率及平均氰化乙烯基含有率 比2重量％高之比率則記載於考3。 本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公釐） !!!!^! — 訂·！ 線 (請先閱讀背面之注意事項再rk本頁) 經濟部智慧財產局員工消費合作社印製 17 - 46793 8 A7 ------- B7 五、發明說明（15) 參-考例6 (製造氰化乙烯基系共聚合物（I I I ) b) 除了將丙嫌腈改爲3 7單位，苯乙烯改6 3單位外， 其他同參考例5 ’得表3所記載之氰化乙烯基系共聚合物 (I I I ) b » 參-考例7 (製造氰化乙烯基系共聚合物（I I I) c) 除了將丙烯睛變更爲2 0單位、苯乙烯變更爲8 0單 位外’其他同參考例5，得表3所記載之氰化乙烯基系共 聚合物（I I I ) c » I考例8 (製造氰化乙烯基系共聚合物（I I I ) d) 除了將丙烯睛改爲3 7單位、苯乙烯改爲6 3單位外 ’其他同參考例5，得表3所記載之氰化乙烯基系共聚合 物（I I I ) d。 實施例1〜.3 利用雌殼體混合機以表4的配合比率混合參考例1所 得之含橡膠接枝共聚合物（I )、參考例2〜4所得之氰 化乙烯基系共聚合物（I I ) A〜C、參考例5〜6所得 之氰化乙烯基系共聚合物（I I I ) a〜b及季戊四醇四 硬脂酸酯後，以4 Omm 0之單擠押機熔融混煉，·得耐塗 性熱可塑性樹脂組成物。再測定所得之樹脂組成物的橡膠 質聚合體含有率、共聚合物（B)之平均氰化乙烯基含有 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公曼〉 -------------.裝--- (請先閲讀背面之注意事項再^^本頁) 訂： --線· 經濟部智慧財產局員工消費合作社印製 -18 - 467938 A7 B7 五、發明說明（16) 率、共聚合物（B )之平均氰化乙烯基含有率比2重量％ 高的比率（％)、附1/2 inch切口之艾佐德衝擊強度、 黃變度（Y I )、塗性及熔體流動率，結果記載於表4。 眢施例4 同參考例3以連續塊狀聚合方式得表3所記載之氰化 乙烯基系共聚合物（I I ) B。再由串聯於脫單體機前端 1 / 3長之桶部的具有加熱裝置2軸擠押機型送料器，將 2 0 k g/時速度的參考例1所製得之含橡膠接枝共聚合 物（I )粉末及’ 7k g/時之速度的參考例6所製得之 氧化乙嫌基系共聚合物（I I I ) b及，1kg/時之速 度的季戊四醇四硬脂酸酯送入脫單體機中，使其與7 3 kg/之速度的氰化乙烯基系共聚合物（I I ) B熔融混 煉後’由出口減壓蒸發回收未反應之單體，並由吐出的單 股狀殘渣中得耐塗性熱可塑性樹脂組成物顆粒。接著，測 定所得樹脂組成物的橡膠質聚合體含有率、共聚合物（B )之平均氰，化乙烯基含有率、共聚合物（B )之平均氰化 乙烯基含有率比2重量％高的比率（％)，附有1 /2 inch切口之艾佐德衝擊強度、黃變度（Y I )、耐塗性及 熔體流動率，結果記載於表4 » 比較例1〜8 : 利用雌殻體混合機以表4的配合比率混合參考例1所 得之含橡膠接枝共聚合物（I)、參考例2〜4所得之氰 本紙張尺度適用中國國家標準<CNS)A4規格（210 X 297公釐-) -------------裝11 t請先閱讀背面之注意事項再本頁) ，-Ί ;線. 經濟部智慧財產局員工消費合作社印製 -19 - 467938 A7 B7 五、發明說明（17) 化乙烯基系共聚合物（I I ) A〜C、參考例5〜8所得 之氰化乙烯基系共聚合物（I I I ) a〜d及季戊四醇四 硬酸酯後，以4 Omm#之擠押機使其熔融混煉，得耐塗 性熱可塑性樹脂組成物。再測定所得之樹脂組成物的橡膠 質聚合體含有率、共聚合物（B )之平均氰化乙烯基含有 率、共聚合物（B )之平均氤化乙烯基含有率比2重童％ 的比率（％)、附有1/2 inch切口之艾佐德衝擊強度 、黃變度（Y I )、塗性及熔體流動率，結果記載於表4 〇 由實施例1〜4得知*符合本發明之規定的耐塗性熱 可塑性樹脂組成物具有優良的耐衝擊性、耐塗性、熔融時 色調安定性及成型加工性之平衡性。 而比較例1〜8因橡膠質聚合體含有率 '共聚合物（ B )之平均氰化乙烯基含有率及共聚合物（B )的平均氰 化乙烯基含有率比2重量％之比率（％)不符合本發明之 規定，故比較例1、7之塗性差、比較例4之色調窣定性 及塗性差，，比較例6之衝擊強度低，又，比較例2，3， 5，8之黃變度大，因此，色調安定性差。 由實施例及比較例可得知，本發明之耐塗性熱可塑性 樹脂組成物具有優良的耐衝擊性、耐塗性、熔融時色調安 定性及成型加工性之平衡性。又，其爲，組合具有特定之 氰化乙烯基含有率及組成分布的氰化乙烯系共聚合物、含 橡膠接枝共聚合物及必要時支援的季戊四醇四硬酯酸酯而 初次實現之發明。 _ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) --------------:裝--- (請先閲讀背面之λί.意事項再f本頁) 、"SJ· :線· 經濟部智慧財產局員工消費合作社印製 -20 - 46 7 93 8 A7 B7 五、發明說明（18) 本發明之耐塗性熱可塑性樹脂組成物係特徵爲，由具 有特定之氰化乙烯基含有率及組成分布的氰化乙烯基系共 聚合物、含橡膠接枝共聚合物及季戊四醇四硬脂酸酯組合 而成，又，其具有優良的耐衝擊性、耐塗性、熔融時色調 安定性及成型加工性之平衡性。 因本發明之耐塗性熱可塑性樹脂組成物具有上述特徵 ，故可供應於各種成型加工用途上，其中，尤其適用爲丙 烯基系塗料及尿烷系塗料用汽車、機車用外裝部品用樹脂 材料。 (請先閱讀背面之;i意事項再^^本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱·） 6 4 8 3 9 A7B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（19) 表 1 聚合裝置之樣式 第1聚合槽 第2聚合槽 攪拌型式 具有螺旋帶翼 之完全混合型 具有多段式多孔板 及記錄翼之栓流型 溫度（°c ) 115 上部1 3 0 中部1 5 5 下部1 9 5 壓力 (kg/cm2G) 0 · 9 1 · 2 冷卻裝置 具有外套及單體蒸氣之蒸發回流用冷凝器 -------I I ---- * I I (請先閱讀背面之注意事項再Ϊ本頁) -'sj. .線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -22 - A7 467938 _____B7 五、發明說明（20) 經濟部智慧財產局員工消費合作社印製 表 2 聚合裝置之樣式 攪拌型式 具有螺旋帶翼之完全混合型 溫度rc) 13 5 壓力（kg/cm2G) 0 · 9 冷卻裝置 具有外套及單體蒸氣之蒸發回流用冷凝器 --------------裝—— (請先閱讀背面之注意事項再Jrk本頁) 訂： -線. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公茇-) -23 - 4 6 7 9 3 8 A7 _ _ B7五、發明說明（21) 表 3氣化乙嫌基系共聚合物U U及ft化乙烯基系共聚合物（I I I) 氣化乙嫌基系 共聚合物(II) 氣化乙烯基系 共聚飾CI I I) 參考例NO 2 3 ' 4 5 6 7 8 NO A , B C a b c d 丙稀腈 % 25 25 28 31 37 20 37 苯乙烯 % 75 75 72 69 63 80 63 平均氣化乙烧基含有率 比2重量％高之比率 % 1.5 0 0 26 38 30 45 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格<210 χ 297公釐）Graft ratio (%) = 100 × (N-MxL / 100) / (M x L / 100) Reduced viscosity: Using a Ubbel iron viscometer at a measurement temperature of 30 ° C and a sample concentration of 0 · Measurement of 4g / dj? Methyl ethyl ketone solution. 0 Average vinyl cyanide content: Press the sample into a film of 40 m with a heating press, and obtain it with an infrared spectrophotometer. Composition distribution of cyanide vinyl group printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs: Dissolve 2 g of sample in methyl ethyl ketone of 8 Omi? * Then add cyclohexane, and then dry the precipitated cyanide under vacuum The vinyl-based copolymer was measured for weight, and the cyanide-containing vinyl cyanide-based copolymer was obtained from the absorbance ratio of infrared ^ spectroscopic analysis. After that, the cumulative weight% and the halogenated vinyl content were plotted, and the ratio of the average vinyl cyanide content higher than 2 weight% was calculated. Izod impact strength: Injection-resistant thermoplastic resin composition was injection-molded. Later, measured in accordance with ASTM D256 with 1/2 of the paper size. Applicable to Chinese national standards (CNS > A4 specification (210 X 297)) -13 467 938 A7 B7 5. Description of the invention (11) Izod with X cut Impact strength》 Tone stability during melting: When injection-resistant thermoplastic resin composition is injection-molded, it is allowed to stay in a molding machine at 230 ° C for 30 minutes, and is used by Nippon Denshoku Industries in accordance with JIS K7103. The yellowness (YI) of the molded product obtained by measuring the color difference and color difference measured by the company. The consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs Du printed printing resistance: The injection resistance thermoplastic resin composition is injection molded, and then Acrylic-based coating solution was sprayed on the obtained molded product (coating made by Fujikura Kasei Co., Ltd. Acrylic line # 6 6 E '/ ene-acrylic line I-type thinner = 50/50 weight ratio), and thereafter After drying at 70 ° C for 30 minutes, the appearance Estimate the surface properties of the coating surface. In addition, urethane-based coatings are made of Japanese white cloth (inner layer: Pu Blush White Base * middle layer: pu Blush White Coctail # 1, outer layer: Pu Pearl dear * hardened) Agent: Po 1 yar em i gh ty 1 ac Hardenner 'Thin material: Polyuremightylac), and then dried at 70 ° C for 30 minutes, then evaluate the adhesion of the coating film on the coating surface. Flowability: I SO 1 1 33 As a benchmark, measure the melt flow rate at a load of 10 kg at 220 ° C .: See Example 1 (manufacturing rubber-containing graft copolymers (I)) This paper size is in accordance with China National Standard (CNS) A4 (210 x 297) (Mm). -14-467938 A7 B7 V. Description of the invention (12) I ^ ^ 1 ϋ ^ ^ nn H 1 · I i Please read the special note on the back of the item, and then Wk this page) 120 units of pure water 0.5 units of glucose, 0.5 units of sodium pyrophosphate, 0.5 units of first ferric sulfate, polybutadiene latex (rubber particle size 0.3 m, gel content 85%) 50 units (solid (In terms of composition), put it in a nitrogen-substituted reactor, and raise the temperature in the reactor to 65 ° C while stirring. When the internal temperature reaches 65 ° C, the polymerization is started by continuously dripping the monomer (40 units of styrene and 10 units of acrylonitrile) and t-dodecanethiol 0 · 3 units continuously for 5 hours. . At the same time, an aqueous solution of cumene hydroperoxide at 0 -25 units, potassium oleate 2.5 units, and 25 units of pure water was continuously added dropwise over 7 hours to complete the reaction. Thereafter, the obtained graft copolymer latex was coagulated with sulfuric acid, and then neutralized with caustic soda, washed, filtered, and dried to obtain a rubber-containing graft copolymer (I) »This rubber-containing graft copolymer (.1) The rubbery polymer content is 50%, the graft ratio is 45%, and the reduced viscosity of the resin component is 0-68d5 / g. Reference Example 2 (Manufacture of cyanide-based vinyl copolymer content (II)) Printed and used by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. It is formed by a 2-tank with the style shown in Table 1, a preheater, and a demonomer. The continuous block polymerization device continuously supplies a monomer mixture formed of 25 units of acrylonitrile, 75 units of styrene, and 0 units of η-octyl mercaptan at a speed of 135 kg / hour to the first unit. Polymerization tank for continuous block polymerization. In addition, the polymerization rate of the first polymerization tank was controlled to 5 8 to 6 1%, and the polymerization rate of the polymer out of the second polymerization tank was controlled to 90 to 9 1%. Then, the uniaxial extrusion was performed. Monomer machine recovers unreacted monomer from the outlet under reduced pressure, and then obtains the records in Table 3 from the front of the de-singer. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 Public Love > ~- 15-Α7 Β7 467938 V. Description of the invention (13) The cyanated vinyl-based copolymer (II) A. In addition, the average ethylene cyanide-containing ethylene cyanide copolymer (II) A contains The ratio (%) of the ratio and the average content of ethylene cyanide groups higher than 2% by weight is described in Table 3 0 Reference Example 3 (Manufacture of cyanide vinyl copolymer (II) B) Use the pattern with Table 2 It is a continuous block polymerization device formed by a single tank, a preheater, and a demonomerizer. At a speed of 1 3 5 kg / hour, the unit will be 25 units of benzene, 75 units of styrene, and η-octyl. The monomer mixture formed by thiol 0.1 IQ units is continuously supplied to the polymerization tank to continuously polymerize in blocks. In addition, the polymerization rate of the polymer out of the polymerization tank is controlled to 7 4 ~ 7 6% 'After that, the polymerization reaction mixture was preheated with a single-shaft extrusion type preheater, and then a 2-axis extrusion type demonomerizer was used to decompress and recover the unreacted monomer from the outlet under reduced pressure. Then, a cyanide vinyl polymer (II) B having the composition described in Table 3 is obtained from the front end of the demonomerizer. The average cyanide vinyl content of the obtained cyanide vinyl copolymer (II) B contains Ratio and average cyanide vinyl, and the ratio (%) higher than 2% by weight is described in Table 3. Reference Example 4 (Production of cyanide vinyl-based copolymer (II) C) The pattern having Table 2 was used It is a continuous block polymerization device formed by a single tank, a preheater, and a demonomerizer. At a speed of 1 3 5 kg / hour, 28 units of acrylonitrile and 72 units of styrene are used. Η-octyl mercaptan. The monomer mixture formed by the 18 units should be continuously fed to the polymerization tank, so that the continuous paper size of this paper applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm >) ----------- -'-. I 装 ------- Order_, τ--ι--! Line 7 ^ · (Please read the precautions on the back before ¥ this page) ί. Consumer Cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs Printing—16 _ A7 467938 ______B7__ 5. Description of the invention (14) Polymerization. In addition, the polymerization rate of the polymer out of the polymerization tank is controlled to 7 4 ~ 76%, and then, a uniaxial extrusion type preheater is used. After preheating the polymerization reaction mixture, the unreacted monomer was recovered from the outlet under reduced pressure by using a two-axis extrusion type demonomerizer to recover the unreacted monomer, and then the cyanidation having the composition described in Table 3 was obtained from the front of the demonomerizer Vinyl-based copolymer (II) C. Table 3 shows the average vinyl cyanide content of the obtained vinyl cyanide-based copolymer (i I) C and the ratio (%) in which the average vinyl cyanide content is higher than 2% by weight. Examination Example 5 (Manufacture of a cyanide-based vinyl copolymer (III) a) In a stainless steel autoclave with a baffle and a Fauda-type stirring blade with a capacity of 20 J2, methyl methacrylate / The acrylamide copolymer (described in Japanese Patent Publication No. 45-24151) was dissolved in 0.05 units of ion exchange unit, and the solution was stirred at 400 r pm and the system was replaced with nitrogen. Next, a mixed solution of 31 units of acrylonitrile, 69 units of styrene, 0 · 3 units of t-dodecanethiol, and 0.5 · 52 units of 2,2-azobisisobutyronitrile was added to the stirring reaction system. Then, the temperature was raised to 60 ° C to start polymerization. The temperature was raised to 65 ° C within the time from the start of polymerization to 100 minutes *, and then the temperature was raised to 100 ° C in 50 minutes to complete the polymerization. Thereafter, the reaction system was cooled, the polymer was separated, washed, and dried by a general method to obtain a cyanide-based vinyl copolymer (I I I) a. The ratio of the average halogenated vinyl content and average vinyl cyanide content of the obtained vinyl cyanide-based copolymer (I I) a to 2% by weight or more is described in Test 3. This paper size applies Chinese national standard (CNS > A4 specification (210 X 297 mm) !!!! ^! — Order ·! Line (Please read the precautions on the back before rking this page) Employees ’Bureau of Intellectual Property, Ministry of Economy Printed by the cooperative 17-46793 8 A7 ------- B7 V. Description of the invention (15) Reference-Examination example 6 (Manufacture of cyanide vinyl copolymer (III) b) Except for the change of propionitrile 3 7 units, styrene changed to 6 3 units, the others are the same as in Reference Example 5 'to get the cyanide vinyl copolymer (III) described in Table 3 b »Reference-Test Example 7 (manufacturing cyanide vinyl copolymer Polymer (III) c) Except changing acrylic acryl to 20 units and styrene to 80 units, the same procedure as in Reference Example 5 was performed to obtain the cyanidated vinyl copolymer (III) c shown in Table 3. »I Case 8 (manufactured vinyl cyanide-based copolymer (III) d) Same as in Reference Example 5 except that the acrylic lens was changed to 37 units and the styrene was changed to 63 units. Cyanide vinyl-based copolymer (III) d. Examples 1 to 3. 3 The female-containing rubber obtained in Reference Example 1 was mixed with a female shell mixer at the mixing ratio shown in Table 4. Graft copolymers (I), cyanided vinyl-based copolymers (II) A to C obtained in Reference Examples 2 to 4, and cyanidated vinyl-based copolymers (III) obtained in Reference Examples 5 to 6 After a ~ b and pentaerythritol tetrastearate, melt-knead with a single extruder of 4 mm to obtain a coating-resistant thermoplastic resin composition. Then measure the content of the rubbery polymer of the obtained resin composition The average cyanide vinyl content of the copolymer (B) contains the paper standard applicable to the Chinese National Standard (CNS) A4 specification (210 X 297) >> -------------. Packing- -(Please read the precautions on the back before ^^ this page) Order:-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -18-467938 A7 B7 V. Description of the invention (16) Rate, co-polymer ( B) The ratio (%) of the average vinyl cyanide content is higher than 2% by weight, the Izod impact strength with a 1/2 inch notch, the yellowness (YI), the paintability, and the melt flow rate. Results It is described in Table 4. 眢 Example 4 The same as Reference Example 3 was used to obtain a cyanated vinyl copolymer (II) B as described in Table 3 by continuous block polymerization. A rubber-containing graft copolymer (I) prepared in Reference Example 1 with a speed of 20 kg / hour with a heating device and a 2-axis extruder-type feeder with a barrel of 1/3 length at the front of the demonomerizer. The powder and the ethylene oxide copolymer (III) b prepared in Reference Example 6 at a speed of 7 kg / hour and pentaerythritol tetrastearate at a speed of 1 kg / hour were sent to a demonomerizer. After being melt-kneaded with a cyanide vinyl copolymer (II) B at a speed of 7 3 kg / ', unreacted monomers were recovered by evaporation under reduced pressure from the outlet, and obtained from the discharged single-stranded residue. Coating-resistant thermoplastic resin composition particles. Next, the rubber polymer content of the obtained resin composition and the average cyanide content of the copolymer (B) were measured. The vinyl content and the average cyanide content of the copolymer (B) were higher than 2% by weight. The ratio (%) of Izod impact strength, yellowness (YI), coating resistance, and melt flow rate with a 1/2 inch notch are shown in Table 4 »Comparative Examples 1 to 8: Using females The shell mixer mixes the rubber-containing graft copolymer (I) obtained in Reference Example 1 at the compounding ratio in Table 4, and the cyanide paper sizes obtained in Reference Examples 2 to 4 are in accordance with Chinese national standard < CNS) A4 specification (210 X 297 mm-) ------------- Please read the precautions on the back before loading this 11 t), -Ί; line. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs- 19-467938 A7 B7 V. Description of the invention (17) Vinyl vinyl copolymer (II) A ~ C, cyanidated vinyl copolymer (III) a ~ d and pentaerythritol tetra obtained in reference examples 5 to 8 After hardening the acid ester, it is melt-kneaded with an extruder of 4 mm to obtain a coating-resistant thermoplastic resin composition. Then, the content of the rubbery polymer of the obtained resin composition, the average cyanide vinyl content of the copolymer (B), and the average halogenated vinyl content of the copolymer (B) were measured. The ratio (%), Izod impact strength with a 1/2 inch notch, yellowing degree (YI), paintability and melt flow rate are shown in Table 4 〇 Known from Examples 1 to 4 * Consistent The specified coating-resistant thermoplastic resin composition of the present invention has excellent balance of impact resistance, coating resistance, hue stability during melting and molding processability. In Comparative Examples 1 to 8, the ratio of the average content of the cyanide vinyl in the copolymer (B) and the average content of the cyanide vinyl in the copolymer (B) was 2% by weight ( %) Does not meet the requirements of the present invention, so the paintability of Comparative Examples 1 and 7 is poor, the color tone properties and paintability of Comparative Example 4 are poor, the impact strength of Comparative Example 6 is low, and Comparative Examples 2, 3, 5, 8 The yellowing degree is large, and therefore, the hue stability is poor. As can be seen from the examples and comparative examples, the coating-resistant thermoplastic resin composition of the present invention has excellent balance of impact resistance, coating resistance, hue stability during melting and molding processability. In addition, it is an invention first achieved by combining a vinyl cyanide copolymer having a specific cyanide vinyl content and composition distribution, a rubber-containing graft copolymer, and pentaerythritol tetrastearate supported when necessary. . _ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --------------: installed --- (Please read the λί. (f page), " SJ ·: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -20-46 7 93 8 A7 B7 V. Description of the invention (18) The coating-resistant thermoplastic resin composition system of the present invention It is characterized in that it is a combination of a cyanide vinyl copolymer, a rubber-containing graft copolymer, and pentaerythritol tetrastearate with a specific cyanide vinyl content and composition distribution. Balance of impact resistance, coating resistance, hue stability during melting and molding processability. Since the coating-resistant thermoplastic resin composition of the present invention has the above-mentioned characteristics, it can be supplied to various molding applications. Among them, it is particularly suitable for resins for automotive and motorcycle exterior parts for acrylic-based coatings and urethane-based coatings. material. (Please read the back of this article; i), and then ^^ this page) This paper is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the paper size is applicable to China National Standard (CNS) A4 (210 X 297 public love ·) 6 4 8 3 9 A7B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (19) Table 1 Model of polymerization device. Wing plug flow type temperature (° c) 115 upper 1 3 0 middle 1 5 5 lower 1 9 5 pressure (kg / cm2G) 0 · 9 1 · 2 cooling device with jacket and condenser for evaporation and reflux of monomer vapor- ------ II ---- * II (Please read the precautions on the back before clicking this page) -'sj. .Line · This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) %) -22-A7 467938 _____B7 V. Description of the invention (20) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 2 Agitation type of the polymerization device. Fully mixed temperature with spiral wings. Rc) 13 5 Pressure (kg / cm2G) 0 · 9 cooling unit with jacket and unit Condenser for evaporation and return of gas -------------- Installation—— (Please read the precautions on the back before Jrk page) Order: -line. This paper size applies to Chinese national standards ( CNS) A4 specification (210 X 297 males-) -23-4 6 7 9 3 8 A7 _ _ B7 V. Description of the invention (21) Table 3 Gasified ethylene copolymers UU and ft-based vinyls Copolymer (III) Gasified ethylene copolymer (II) Gasified vinyl copolymer CI II) Reference Example NO 2 3 '4 5 6 7 8 NO A, BC abcd Acrylonitrile% 25 25 28 31 37 20 37 Styrene% 75 75 72 69 63 80 63 Average content of gasified ethyl sulphur base is higher than 2% by weight% 1.5 0 0 26 38 30 45 Paper printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Standards apply to Chinese National Standard (CNS) A4 specifications < 210 χ 297 mm)
-24 - 4 6 7 9 3 8 a? B7 五 經濟部智慧財產局員工消費合作社印製 、發明説明（j 表 4耐塗性熱可塑性樹脂組成物 寅施例NO 雌例NO 1 2 3 4 1 2 3 4 5 6 7 8 含橡膠接枝共聚合物⑴單位 30 36 20 20 30 30 36 36 36 5 14 36 氛化乙稀基系共聚合物(II) A單位 50 70 54 70 ft化乙稀基系共聚合物(II) B單位 54 73 44 29 氣化乙烯基系共聚合物(11) C單位 60 66 氛化乙烯基系共聚合物(II) a單位 20 70 25 氛化乙嫌基系共聚合物(II) b單位 10 20 7 64 35 氰化乙嫌基系共聚合物(Π) C單位 10 匕乙烯基系共聚合物(II) d單位 20 季戊四醇四硬脂酸酯單位 2 1 2 橡膠質聚合體之含有率 % 15 18 10 10 15 15 18 18 18 2.5 7 IS 共聚合物(B)之平均氣化 乙烯基含有率 % 25.5 25,4 29,1 25,4 24.1 29.1 33.2 23.3 26.8 26-4 27.4 29.0 共聚合物(B)之平均§1化乙 烯基含有率比高;% 17.0 12.0 15.6 8.0 2.5 41.2 54.6 30.2 22.0 Π.9 0.4 29.9 1/2" Izod衝擊強度_/cm 25 35 31 20 25 25 32 31 30 5 12 31 黃變度(ΪΙ) 22 26 25 21 21 40 45 38 37 25 22 50 溶體·率g/l〇分 14 12 12 16 14 10 8 18 10 18 17 11 塗性 丙嫌基塗料*1 _ 〇 〇 〇 〇 X 〇 〇 X 〇 〇 X 〇 尿院塗料*2 - 〇 〇 〇 〇 X 〇 〇 △ 〇 〇 X 〇 * 1 〇.未吸入X *吸入 * 2 :〇：未剝離△:部分剝離X :幾乎剝離 本紙張尺度適用中國國家標準（〇JS ) A4規格（210X297公釐） 25-24-4 6 7 9 3 8 a? B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed description of invention (j Table 4 Coating resistance thermoplastic resin composition Example No. Female No. 1 2 3 4 1 2 3 4 5 6 7 8 Rubber-containing graft copolymers Units 30 36 20 20 30 30 36 36 36 5 14 36 Aromatic vinyl copolymers (II) A units 50 70 54 70 ft Base copolymer (II) B unit 54 73 44 29 Gasified vinyl copolymer (11) C unit 60 66 Aromatic vinyl copolymer (II) a unit 20 70 25 Atomized ethylene Copolymer (II) b unit 10 20 7 64 35 Ethylene cyanide copolymer (Π) C unit 10 D vinyl group copolymer (II) d unit 20 Pentaerythritol tetrastearate unit 2 1 2 Content of rubbery polymer% 15 18 10 10 15 15 18 18 18 2.5 2.5 Average content of gasified vinyl of IS copolymer (B)% 25.5 25,4 29,1 25,4 24.1 29.1 33.2 23.3 26.8 26-4 27.4 29.0 The average §1 vinyl group content ratio of the copolymer (B) is high;% 17.0 12.0 15.6 8.0 2.5 41.2 54.6 30.2 22.0 Π.9 0.4 29.9 1/2 " Izod impact strength_ / cm 25 35 31 20 25 25 32 31 30 5 12 31 Yellowness (变 Ι) 22 26 25 21 21 40 45 38 37 25 22 50 Solution · g / l0 points 14 12 12 16 14 10 8 18 10 18 17 11 Coatable acrylic paint * 1 _ 〇〇〇〇〇〇 × 〇〇X 〇〇X 〇 Urinary paint * 2-〇〇 〇〇X 〇〇 △ 〇〇X 〇 * 1 〇. Not inhaled X * Inhaled * 2: 〇: Not peeled △: Partially peeled X: Almost peeled The paper size applies Chinese national standard (〇JS) A4 specification (210X297) Centimeters) 25