^14489 A6 B6 經濟部中央標準局8工消費合作社印製 五、發明説明（） 益昍：> 铕城 本發明係有拥具有抗靜霣之多層聚合物，其製法，及 含有該聚合物之抗靜電樹脂組成物。 生前抟術 一般而言，熱塑樹脂具有离霣胆，及容易因摩擦或撕 離而帶靜電。因而使其吸引灰塵及塵垢而破壞外觀，或當 樹脂模製成或用於薄片，薄膜或繼雒時產生多個領域的問 題。欲對此等容易帶靜電的熱塑樹脂賦予抗靜電性，曾將 多種抗靜電劑捏練成熱塑樹脂或施於樹脂表面上，或樹脂 接受表面處理，如電翬處理，或經由與抗靜電單體進行共 聚合反應而作化學改質。 抗靜電性須儘可能永久，抗靜電劑不可造成樹脂性質 的劣化。有關對聚合物提供抗靜電性曾有多棰提議。 舉例言之，美國第4，302，558號專利案及美國第 4 , 384, 078號專利案（英國第2036762號專利案）揭示一 種接枝共聚物，包括一種由共轭二烯及/或丙烯酸酯與含 聚烷撐氧基之單體所生成的橡膠主幹聚合物作內層，主幹 聚合物Μ—種乙烯單體或偏乙烯單體進行接枝共聚合。該 等美國專利案也揭示包括所述接枝共聚物與熱塑樹脂之一 種抗靜電樹脂組成物。 至於前述抗靜電樹脂組成物之改良，美國第4,315,081 號專利案（英國第2070046號專利案）提示將多種界面活性 劑加入組成物内。 美國第4 , 332 , 919號專利案（DE第3122805號專利案） ，請先S讀背面之注意事項再填寫本頁) •丨裝. 訂‘ ά 本紙張尺度適用中國國家標準（CNS)甲4規格（210 X 297公货） 3 314489 經濟部中央標準局貝工消費合作社印製 A6 B6_ 五、發明説明（） 中，一棰烯屬不飽和單醱聚合而生成主幹聚合物顆粒，然 後共轭二烯及/或丙烯酸酯舆一種聚烷播氧單體接枝於其 上，接著為烯屬不飽和單居之接枝聚合反應而生成一種多 層抗靜電樹脂。所述美國專利案也揭示一棰包括所述多層 抗靜電樹脂及熱塑樹脂之抗靜電樹脂。 日本特許公開案第195143/ 1985號揭示一棰聚合物複 合物，其製法係經由於有或無橡膠聚合物存在下聚合乙烯 單體，然後於所生成之乙烯聚合物存在下，進行主要包括 一棰含聚烷撐氧_的乙烯單賭之單體混合物的乳液聚合反 應。該公開案也揭示一種包括所述聚合物複合物及乙烯聚 合物之抗靜電樹脂組成物。 藉著抗靜電方法，其中抗靜電劑藉混練或施於樹脂表 面而摻混入樹脂內，於表面附近或表面上存在的抗靜電劑 可被水洗去或磨耗，因而最終喪失其靜霣效果。抗靜電劑 也可瀋至表面，因而使得表面發粘或吸引灰塵及塵垢。 至於美國第 4,302,558 ; 4,384,078; 4,315,081 及 4,332,919號專利案所揭示之多層抗靜電樹脂，用作一棰 單體成分的含聚烷撐氧基之單體可有效提供抗靜電性，但 對樹脂固有的耐熱性及機械性質產生不良影逛。 發明夕婢给 本發明提供一種樹脂，其可提髙每單位用量之含聚烷 撐氧基單體之抗靜電性，同時抑制樹脂之耐熱性及機械性 質的下降。 依據本發明，提供一種多層聚合物包括： ，請先Η讀背面之注意事項再填寫本頁) 丨年 訂· ά 本紙張尺度適用中國國家標準（CNS)甲4規格（210 X 297公釐） 4 經濟部中央標準局R工消費合作社印製 A6 B6_ 五、發明説明（） (a〉約10至约50«t%之最内層，其係由具有50*C或以上之 Tg (玻璃轉變溫度）之交聯聚合物生成者，交聯聚合物 係經由將約80至约99.5wt%之烯屬不飽和官能單體， 與約0.5至約20wt%之至少含2烯屬不飽和基之多官能 單體，所組成之單體混合物聚合而製備者； • > · (b) 約5至約25wt%之第二層，其係在最内層上生成，且 係由具有Tg爲l〇*C或以下之软質聚合物生成者，軟質 聚合物係經由將選自共軛二烯及丙烯酸酯中之至少一 者聚合而製備者； (c) 約10至約40wt%之第三層，其係於第二層上生成，且 係由具有爲l〇t或以下之聚合物生成者，聚合物係 經由將包括至少25wt%之一種含聚烷撐氧鏈的不飽和 官能單體之不飽和單體聚合而裂備；及 (d>約10至約50wt%之最外層，其係於第三層上生成，且 係由具有Tg為50¾或Μ上之聚合物生成者，聚合物係 經由將烯羼不飽和官能單體聚合而製備。 本發明也提供一棰多層聚合物包括： (a>约10至約50wt%之最內層，其係由具有501C或Μ上之 Tg之交聯聚合物生成者，交聯聚合物係經由将約80至 約99.5wt%之烯屬不飽和官能單體與约〇.5至約20wt %之至少含二烯屬不飽和基之多官能單體所組成之單 體混合物聚合而製備者； (b>約5至約25wt%之第二層，其係在最内層上生成，且 係由具有Tg為101C或Μ下之軟質聚合物生成者，軟質 ，請先閲讀背面之注意事項再場寫I頁) —裝· 訂· ά 本紙張尺度通用中國國家標準（CNS)甲4規格（210 X 297公釐〉 5 經濟部中央標準局OK工消費合作杜印製 314489 A6 B6 五、發明説明（） 聚合物係經由將選自共軛二烯及丙烯酸酯中之至少一 者聚合而製備者； (c)約10至約40wt%之第三層，其係於第二層上生成，且 係由具有Tg為101C或Μ下之聚合物生成者，軟質聚合 物係經ώ將包括下列各者之單體混合物聚合而製備者 :(i)約25至約45wt%之含聚烷撐氧鐽之不飽和官能單 體，（i i >約70至約50wt%之選自共轭二烯及丙烯酸酯 中之至少一者，及（iii)約5至約10wt%之含有至少一 烯属不飽和基及至少一親水基之有機化合物；及 (d〉約10至约50wt%之最外層，其係於第三層上生成，且 係由具有Tg爲50X：或Μ上之聚合物生成者，聚合物係 經由將烯屬不飽和官能單醱聚合而製備。 本發明也提供一種製備多層聚合物之方法，所述多層 聚合物包括一最内層，在最內層上生成一第二層，在第二 層上生成一第三層，及於第三層上生成之最外層，所述方 法包括下列各步驟： (Α)生成聚合物顆粒作最內層，係經由於含水介質内將下 述單體混合物聚合而生成者：約80至約99.5wt%之烯 羼不飽和官能單體，及約0.5至約20wt%之含至少二 烯屬不飽和基之多官能單體； (B)生成二層聚合物顆粒，係經由於含該最内層聚合物顆 粒之含水介質內，聚合選自共轭二烯及丙烯酸酯中之 至少一者，而在最内層聚合物顆粒上生成第二層聚合 物顆粒而製備者； ----^------------^ -----嚷---^---#------M V請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)甲4規格（210 X 297公釐〉 6 A6 B6_ 五、發明説明（） (C)生成三層聚合物顆粒，係經由於含該二層聚合物顆粒 之含水介質內，聚合包括至少25wt%之一種含聚烷撐 氧鐽之不飽和官能單體的不飽和單體，而在二層聚合 物顆粒上生成第三層而製備者；及 (D>在三層聚合物顆粒上生成最外層，係經由於含該三層 聚合物顆粒之含水介質内，聚合至少一種烯屬不飽和 官能單體而製備者； 其中各步驟所用之單體數量之重量比，Μ所用單體總重爲 準， (Α)步驟（Α)中生成之最内層之單體用量為約1〇至約50wt % » (B) 步驟（B)中生成第二層之單體用量為約5至約25 wt % > (C) 步驟（C)中生成第三層之單體用量為约1〇至約40 wt% ，及 (D) 步驟（D)中生成最外層之單體用量為約1〇至約50 wt %。 本發明又提供一種製備多層聚合物之方法，所述多層 聚合物包括一最内層，在最内層上生成一第二層，在第二 層上生成一第三層，及於第三層上生成之最外層，所述方 法包括下列各步驟： (A)生成聚合物顆粒作最内層，係經由於含水介質内將下 述箪體混合物聚合而生成者：約80至約99.5wt%之烯 羼不飽和官能單體，及約0.5至約20wt%之含至少二 一請先閲讀背面之注意Ϋ項再填寫本頁> -裝- 訂. •丨铨 經濟部中央標準局貝工消費合作社印製 本紙張尺度通用中國國家標準（CNS)甲4規格（210 X 297公釐） 7 經濟部中央標準居貝工消費合作社印製 A6 B6 五、發明説明（） 烯屬不飽和基之多官能單體： (B) 生成二層聚合物顆粒，係經由於含該最內層聚合物顆 粒之含水介質内，聚合選自共轭二烯及丙烯酸酯中之 至少一者，而在最内層聚合物顆粒上生成第二層聚合 物顆粒而製備者； (C) 生成三層聚合物顆粒，係經由於含該二層聚合物顆粒 之含水介質内，聚合如下單體混合物而製備者：（i)約 25至約45 wt%之含聚烷撐氣鏈之不飽和官能單體， (i i >約70至約50wt%之逛自共軛二烯及丙烯酸酯中之 至少一者，及（iiU約5至約10wt%之分子内含至少一 烯靥不飽和基及至少一親水基之有機化合物，而在二 層聚合物顆粒上生成第三層；及 (D) 在三層聚合物顆粒上生成最外層，係經由於含該三層 聚合物顆粒之含水介質内，聚合至少一種烯屬不飽和 官能單體而製備者； 其中各步驟所用之單體數量之重量比，Μ所用單體總重為 準， (Α>步驟（Α>中生成之最内層之單體用量為約10至約50wt %， (B) 步驟（B)中生成第二層之單體用量爲约5至約25 wt %， (C) 步® (C)中生成第三層之單體用量為約10至約40 wt% ，及 (D) 步驟（D)中生成最外層之單體用量為約1〇至約50 wt -装---，---.玎------^ V請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)甲4規格（210 X 297公釐） 8^ 14489 A6 B6 Printed by the Ministry of Economic Affairs, Central Bureau of Standards, 8 Industrial and Consumer Cooperatives V. Description of the invention () Yi Zhan: > Eucheng This invention is a multilayer polymer with anti-static properties, its preparation method, and the polymer containing it The antistatic resin composition. Lifetime surgery Generally speaking, thermoplastic resins have gall bladders and are easily charged with static electricity due to friction or tearing. Therefore, it attracts dust and dirt and damages the appearance, or when resin is molded or used in a sheet, film, or glaze, problems in various fields arise. To impart antistatic properties to these thermoplastic resins that are easily charged with static electricity, a variety of antistatic agents have been kneaded into thermoplastic resins or applied to the surface of the resin, or the resins have been subjected to surface treatments such as electrospray treatment, or The electrostatic monomer undergoes copolymerization and undergoes chemical modification. The antistatic property must be as permanent as possible, and the antistatic agent must not cause deterioration of the resin properties. There have been many proposals for providing antistatic properties to polymers. For example, U.S. Patent No. 4,302,558 and U.S. Patent No. 4,384,078 (UK Patent No. 2036762) disclose a graft copolymer including a conjugated diene and / or The rubber backbone polymer produced by the acrylic ester and the polyalkylene oxide-containing monomer is used as the inner layer, and the backbone polymer M-type vinyl monomer or vinylidene monomer is graft copolymerized. These US patents also disclose an antistatic resin composition including the graft copolymer and thermoplastic resin. As for the improvement of the aforementioned antistatic resin composition, US Patent No. 4,315,081 (UK Patent No. 2070046) suggests adding a variety of surfactants to the composition. U.S. Patent No. 4, 332, 919 (DE Patent No. 3122805), please read the precautions on the back and then fill out this page) • Install. Order 'ά' This paper size applies to the Chinese National Standard (CNS) A 4 Specifications (210 X 297 public goods) 3 314489 A6 B6_ printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. In the description of invention (), monoethylenically unsaturated mono-pyropolymerized to form main polymer particles, and then totaled The conjugated diene and / or acrylate and a polyalkylene oxide monomer are grafted on it, and then a multi-layer antistatic resin is formed by the graft polymerization of ethylenically unsaturated monomer. The U.S. patent case also discloses an antistatic resin including the multilayer antistatic resin and thermoplastic resin. Japanese Patent Laid-open No. 195143/1985 discloses a polymer composite, the production method of which is by polymerizing ethylene monomer in the presence or absence of a rubber polymer, and then in the presence of the resulting ethylene polymer, mainly including a Emulsion polymerization of monomer mixtures containing polyalkylene oxide ethylene. The publication also discloses an antistatic resin composition including the polymer composite and the ethylene polymer. By the antistatic method, in which the antistatic agent is blended into the resin by kneading or applying to the surface of the resin, the antistatic agent present near or on the surface can be washed away or worn away by water, thus eventually losing its static effect. Antistatic agents can also sink to the surface, thus making the surface sticky or attract dust and dirt. As for the multi-layer antistatic resins disclosed in the US Patent Nos. 4,302,558; 4,384,078; 4,315,081 and 4,332,919, the polyalkyleneoxy group-containing monomer used as a monomer component can effectively provide antistatic properties, but it is inherent to the resin Heat resistance and mechanical properties produce undesirable shadows. The invention provides a resin to the present invention, which can improve the antistatic property of the polyalkylene oxide group-containing monomer per unit amount, while suppressing the decrease in heat resistance and mechanical properties of the resin. According to the present invention, providing a multi-layer polymer includes:, please read the precautions on the back and then fill out this page) 丨 Annual order · ά This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm) 4 A6 B6_ printed by the R-Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention () (a> The innermost layer of about 10 to about 50 «t%, which consists of a Tg (glass transition temperature of 50 * C or more ) Of the cross-linked polymer, the cross-linked polymer is obtained by combining about 80 to about 99.5 wt% of ethylenically unsaturated functional monomer and about 0.5 to about 20 wt% of at least 2 ethylenically unsaturated groups Functional monomer, prepared by polymerizing the composed monomer mixture; • > · (b) about 5 to about 25% by weight of the second layer, which is formed on the innermost layer and has a Tg of 10 * C or less soft polymer producer, the soft polymer is prepared by polymerizing at least one selected from conjugated diene and acrylate; (c) about 10 to about 40 wt% of the third layer, It is produced on the second layer and is produced from a polymer with a value of 10 t or less. Unsaturated monomers including at least 25wt% of a polyalkylene oxide chain-containing unsaturated functional monomer are polymerized and cracked; and (d > about 10 to about 50wt% of the outermost layer, which is formed on the third layer , And is produced by a polymer having a Tg of 50¾ or M, the polymer is prepared by polymerizing ethylenically unsaturated functional monomers. The present invention also provides a multi-layer polymer including: (a> about 10 to The innermost layer of about 50 wt%, which is produced by a crosslinked polymer having a Tg of 501C or M, is obtained by combining about 80 to about 99.5 wt% of ethylenically unsaturated functional monomer with about 〇.5 to about 20wt% of at least a diethylenically unsaturated group-containing multifunctional monomer is prepared by polymerization of a monomer mixture; (b> about 5 to about 25wt% of the second layer, which is in the most It is produced on the inner layer and is produced by a soft polymer with a Tg of 101C or Μ. For soft, please read the precautions on the back and then write page I)-Binding · Order · ά This paper standard is universal Chinese national standard ( CNS) A 4 specifications (210 X 297 mm) 5 Central Government Bureau of Economy, Ministry of Economic Affairs, OK Industrial and Consumer Cooperation Du Printing 314489 A6 B6 Description of the invention () The polymer is prepared by polymerizing at least one selected from conjugated diene and acrylate; (c) about 10 to about 40 wt% of the third layer, which is on the second layer It is produced by a polymer with a Tg of 101C or M. The soft polymer is prepared by polymerizing a monomer mixture including the following: (i) about 25 to about 45 wt% of polymer-containing The unsaturated functional monomer of alkylene oxide, (ii> about 70 to about 50 wt% of at least one selected from conjugated diene and acrylate, and (iii) about 5 to about 10 wt% containing at least An organic compound of an ethylenically unsaturated group and at least one hydrophilic group; and (d> about 10 to about 50 wt% of the outermost layer, which is formed on the third layer and is formed by having a Tg of 50X: or M For the polymer producer, the polymer is prepared by polymerizing an ethylenically unsaturated functional monohydric monomer. The present invention also provides a method for preparing a multilayer polymer, the multilayer polymer including an innermost layer, a second layer formed on the innermost layer, a third layer formed on the second layer, and a third layer For the outermost layer, the method includes the following steps: (A) The polymer particles are formed as the innermost layer, which is produced by polymerizing the following monomer mixture in an aqueous medium: about 80 to about 99.5 wt% Ethylenically unsaturated functional monomers, and about 0.5 to about 20% by weight of polyfunctional monomers containing at least diethylenically unsaturated groups; (B) the formation of two-layer polymer particles by passing through the innermost polymer particles In the aqueous medium, polymerize at least one selected from conjugated diene and acrylate, and produce a second layer of polymer particles on the innermost polymer particles; ---- ^ ----- ------- ^ ----- Xuan --- ^ --- # ------ MV, please read the precautions on the back before filling in this page) This paper scale is applicable to the Chinese National Standard (CNS ) A 4 specifications (210 X 297 mm> 6 A6 B6_ V. Description of the invention () (C) The formation of three layers of polymer particles, through the polymerization containing the two layers In the aqueous medium of the particles, the polymerization includes at least 25% by weight of an unsaturated monomer containing a polyalkylene oxide-containing unsaturated functional monomer, and a third layer is formed on the two-layer polymer particles; and (D >; The outermost layer is formed on the three-layer polymer particles, prepared by polymerizing at least one ethylenically unsaturated functional monomer in an aqueous medium containing the three-layer polymer particles; wherein the number of monomers used in each step The weight ratio is based on the total weight of the monomers used in Μ. The amount of monomer in the innermost layer generated in (Α) step (Α) is about 10 to about 50 wt% »(B) the second layer in step (B) The amount of monomer is about 5 to about 25 wt% (C) the amount of monomer used to form the third layer in step (C) is about 10 to about 40 wt%, and (D) the most generated in step (D) The amount of monomer in the outer layer is about 10 to about 50 wt%. The present invention also provides a method for preparing a multilayer polymer, the multilayer polymer includes an innermost layer, a second layer is formed on the innermost layer, and the second layer A third layer is generated on the layer, and the outermost layer generated on the third layer. The method includes the following steps: (A) The polymer particles are formed as the innermost layer, which is formed by polymerizing the following mixture of the following bodies in an aqueous medium: about 80 to about 99.5 wt% of ethylenically unsaturated functional monomer, and about 0.5 to about 20 wt % Contains at least 21, please read the note Ϋ on the back before filling in this page > -installation- ordering. • 丨 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, Beigong Consumer Cooperative, paper size General Chinese National Standard (CNS) A 4 Specifications (210 X 297 mm) 7 A6 B6 printed by Jubei Consumer Cooperative, a central standard of the Ministry of Economic Affairs 5. Description of invention () Polyfunctional monomer with ethylenic unsaturated group: (B) Generate two layers of polymer particles, It is prepared by polymerizing at least one selected from conjugated diene and acrylate in an aqueous medium containing the innermost polymer particles, and producing a second layer of polymer particles on the innermost polymer particles (C) The three-layer polymer particles are produced by polymerizing the following monomer mixture in an aqueous medium containing the two-layer polymer particles: (i) about 25 to about 45 wt% of polyalkylene-containing Unsaturated functional monomer of the gas chain, (ii> about 70 to about 50wt% of organic compounds from at least one of conjugated diene and acrylate, and (iiU about 5 to about 10wt% of the molecule contains at least one ethylenic unsaturated group and at least one hydrophilic group, and in the two A third layer is formed on the layer of polymer particles; and (D) an outermost layer is formed on the three-layer polymer particles by polymerizing at least one ethylenically unsaturated functional monomer in an aqueous medium containing the three-layer polymer particles And the preparer; wherein the weight ratio of the number of monomers used in each step, the total weight of the monomers used in M shall prevail, (the amount of monomer used in the innermost layer generated in step (Α > is about 10 to about 50 wt%, ( B) The amount of monomer used to form the second layer in step (B) is about 5 to about 25 wt%, (C) The amount of monomer used to form the third layer in step ® (C) is about 10 to about 40 wt%, And (D) The amount of monomer used to form the outermost layer in step (D) is about 10 to about 50 wt -installed ---, ---. 玎 ------ ^ VPlease read the notes on the back first (Fill in this page again) This paper scale is applicable to China National Standard (CNS) Grade 4 (210 X 297 mm) 8
A6 BO ^14489 五、發明説明（） X請先閲讀背面之注意事項再填寫參頁> %。 本發明又提供一種包括約100重量份之熱塑樹脂及約 40至約100重量份之所述多層聚合物之抗靜電樹脂组成 物。 發明 > 註細銳昍 (a)軎由靥 用以於本發明之多餍聚合物生成最內層的烯羼不飽和 官能單體為一種可生成所謂的刚質聚合物及每分子含有一 餾烯羼不飽和基（官能基）之單體。此種單體之例有（甲代〉 丙烯酸之烷基（如Ci-C4)酯，如甲基甲代丙烯酸酯，乙烯 化合物如（甲代）丙烯醯胺，氯乙烯，乙烯基乙酸酯及丙烯 睛；芳香乙烯化合物，如苯乙烯；及烷基（如Ci-C*)乙烯 基醚，烷基（如G-C*)乙烯基甲嗣，2-羥烷基（甲代）丙烯 睃酯，特別（甲代〉丙烯酸之匕气* 2-羥烷基酯，及偏氯乙 烯。此等單體可單獨使用或其中至少二者可合併使用。其 中，單體混合物含有70wt%以上之甲基甲代丙烯酸酯及30 wt%以下之選自丙烯酸之烷基（如Ci-C*)酯及苯乙烯中之 任一種單體。 經濟部中央標準局貝工消費合作社印製 具有至少二烯屬不飽和基之多官能單體之範例為經由 使用丙烯睃或甲代丙烯酸將乙二醇或其寡聚物（例如H0-(CHaCHa〇)n-H，其中η為2至10之整數）之兩個端末羥基 酯化生成的二酯，例如乙二酵二（甲代 > 丙烯酸酯，二乙二 醇二（甲代）丙烯酸酯，三乙二醇二（甲代）丙烯酸酯，四乙 二醇二（甲代〉丙烯酸酯，五乙二醇二（甲代）丙烯酸酯及十 9 本紙張尺度適用中國國家標準（CNS〉甲4規格（210 X 297公釐） A6 B6 經濟部中央標準局貝工消#合作社印製 五、發明説明（） 四乙二醇二（甲代）丙烯酸酯；經由使用丙烯酸或甲代丙播 酸將二羥基醇，特別具有2至10磺原子之二羥基醇之二個 羥基酯化生成之酯，例如新戊二醇二（甲代）丙烯酸酯，己 二醇二（甲代 >丙烯酸酯及丁二醇二（甲代〉丙烯酸酯；經由 使用丙烯酸或甲代丙烯酸將雙酚A或雙酚A之環氧烷加合 物，特別雙酚A之環氧烷加合物（Η0-(Α0)„-Η，其中A爲 C3-C3烷撐及m為1-10之整數），其可各自取代Μ至少一値 鹵原子者之兩個端未羥基予Μ酯化所生成之二酯；經由使 用丙烯酸或甲代丙烯酸將具有至少3羥基之醇，特別具有 5至20碩原子及3至6羥基之多羥基醇，例如三羥甲基丙 垸，季戊四醇及二季戊四醇酯化所生成之酯；經由將縮水 甘油基丙烯酸酯或縮水甘油基甲代丙烯酸酯之環氧基與前 述二羥基或多羥基醇之端末羥基進行開環加成反應所生成 之化合物；經由缩水甘油基丙烯酸酯或縮水甘油基甲代丙 烯酸酯之環氧基與二元酸（可取代有至少一鹵原子，例如 丁二酸，己二酸，對肽酸或酞酸），或其瓖氧烷加合物 〔待別此等任意鹵基取代之二元酸之環氧烷加合物（Η0-(Α0)η-Η，其中Α為Ca-C3烷撐而m為1至10之整數）進行 開環加成反應所生成之化合物〕；烯丙基甲代丙烯酸酯； 二乙烯苯等。此等單體為已知且易得。可單獨使用或其中 至少二者可合併使用。 前述多官能單體作為交聯劑，其用量係足夠有效生成 最内層用之交聯構造者。一般用量Μ生成最内層之單體用 量總重為準，爲約0. 5至約20 wt%，較好約〇. 5至約10 r請先Η讀背面之注意事項再場寫本頁) 丨裝· 訂. 丨埃 本紙張尺度通用中國國家標準（CNS)甲4规格（210 X 297公釐） 經濟部中央標準局貝工消費合作杜印製 A6 B6 五、發明説明（） »t96 ° 具有Tg (玻璃轉變溫度）為5〇υ或Μ上之最内層聚合物 為所諝硬質或剛氧聚合物。較好最內層具有約50至約120 υ 之 Tg。 最内層聚合物之Tg值以及第二，第三及最外層之Tg值 ，可經由将各別組成單體獨立聚合，及测量所生成之聚合 物之Tg而測知。如此，可經由測定候選單體之比例關係 ，及由候選單體製備之聚合物之Tg值而選擇適當單體及其 比例。 說明害及申請專利範圍中，Tg係使用視差掃描卡計 (型號DS-10，精工電子工業公司製造〉依據ASTM-D-3418测 定0 多層聚合物的最內層之功能係防止多層聚合物在加工 過程中破裂或被軋碎，及防止含該多層聚合物之樹脂組成 物的耐熱性及機械強度下降。欲達此目的，Μ本發明之多 層聚合物爲準，最內層之存在量為約10至約50wt%，較好 約20至約50wt%，更好約30至約40wt%。最內層之比例過 高，易使加工性降低。 (h)笛二靥 第二層係由具有Tg為lOt：或以下，較好約-70至10t： 之軟質聚合物生成者。軟質聚合物係由丙烯酸之烷基（如 Ci-Ci»)酯（例如甲基丙烯酸酯，乙基丙烯酸酯，丙基丙烯 酸酯，丁基丙烯酸酯，辛基丙烯酸酯或壬基丙烯酸酯）或 共軛二烯（例如1，3-丁二烯，異戊間二烯，1，3-戊二烯 本紙張尺度適用中國國家標準（CNS)甲4規格（210 X 297公釐） -装---：---.玎------政 v請先Μ讀背面之注意事項再填寫本頁) 經濟部中央標準局B工消費合作社印製 A6 B6 五、發明説明（） ，氯丁二烯等〉製備者。可與前述丙烯酸之烷基酯或共軛 二烯進行共聚合的任意其它單體用量係可有效獲得具有Tg 為10¾或Μ下，較好約-70至10¾之共聚物。所述其他可 共聚合單體例如包含苯乙烯，丙烯睛，乙烯，丙烯及甲代 丙烯酸之院基（如h-Co〉酯。 第二層之功能係顯著加大第三層的體積，因此即使使 用小比例的第三層也可賦予期望的抗靜電性程度〇換言之 ，當多層聚合物加入熱塑樹脂而賦予抗靜電性時，第二層 的功能係允許組成物見有充分抗靜電性，即使當使用小量 多層聚合物時亦如此。欲達成此一功能，第二層係佔多層 聚合物之約5至約25wt%，較好約5至約15wt%，更好約 5至約10wt%。第二層的比例過高，容易使得多層聚合物 本身或有多層聚合物顆粒分散其中的熱塑樹脂之耐熱性及 機械強度降低。A6 BO ^ 14489 V. Invention description () X Please read the notes on the back before filling in the reference page>%. The present invention also provides an antistatic resin composition including about 100 parts by weight of a thermoplastic resin and about 40 to about 100 parts by weight of the multilayer polymer. Invention > Note fine sharp 昍 (a) is used to produce the innermost layer of ethylenically unsaturated functional monomers in the polycrystalline polymer of the present invention is a kind of so-called rigid polymer and contains one per molecule Diethylen unsaturated monomer (functional group) monomer. Examples of such monomers are (meth) acrylic acid alkyl (eg Ci-C4) esters, such as methyl methacrylate, vinyl compounds such as (meth) acrylamide, vinyl chloride, vinyl acetate And acrylonitrile; aromatic vinyl compounds, such as styrene; and alkyl (such as Ci-C *) vinyl ether, alkyl (such as GC *) vinyl methyl, 2-hydroxyalkyl (methyl) propylene dimethacrylate , Especially (a generation> acrylic acid * 2-hydroxyalkyl ester, and vinylidene chloride. These monomers can be used alone or at least two of them can be used in combination. Among them, the monomer mixture contains more than 70wt% of a Methacrylate and less than 30% by weight of any monomer selected from the group consisting of acrylic acid alkyl (such as Ci-C *) esters and styrene. Printed by the Ministry of Economic Affairs, Central Bureau of Standards, Beigong Consumer Cooperatives with at least diene An example of a polyfunctional monomer which is an unsaturated group is the use of propylene oxide or methacrylic acid to convert ethylene glycol or its oligomer (for example, H0- (CHaCHa〇) nH, where η is an integer from 2 to 10). The diesters formed by esterification of the terminal hydroxyl groups, such as glyphosate (meth) acrylate, diethylene glycol di ( Generation) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate and ten 9 This paper size is applicable to Chinese national standards (CNS> A4 specifications (210 X 297 mm) A6 B6 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Beigongxiao #Cooperative V. Description of the invention () Tetraethylene glycol di (A generation) acrylate; Propionic acid esters esters of dihydroxy alcohols, especially dihydroxy alcohols with 2 to 10 sulfonic atoms, such as neopentyl glycol di (meth) acrylate, hexanediol di (meth) > Acrylates and butanediol di (meth) acrylates; alkylene oxide adducts of bisphenol A or bisphenol A, especially alkylene oxide adducts of bisphenol A, by using acrylic acid or methacrylic acid (Η0- (Α0) "-Η, where A is C3-C3 alkylene and m is an integer of 1-10), which can each replace the two hydroxyl groups of the at least one halogen atom at the two ends of the ester is not esterified by M The resulting diester; by using acrylic acid or methacrylic acid will have an alcohol with at least 3 hydroxyl groups, especially with 5 to 2 0 Polyatomic alcohols with 3 atoms and 3 to 6 hydroxyl groups, such as trimethylolpropane, esters of pentaerythritol and dipentaerythritol; esters produced by the epoxy of glycidyl acrylate or glycidyl methacrylate A compound formed by the ring-opening addition reaction between the hydroxyl group and the terminal hydroxyl group of the aforementioned dihydroxy or polyhydric alcohol; via the epoxy group and dibasic acid of glycidyl acrylate or glycidyl methacrylate (which can be substituted with at least A halogen atom, such as succinic acid, adipic acid, p-peptidic acid or phthalic acid), or its oxalane adducts (to be added to these alkylene oxide adducts of any halogen-substituted dibasic acid ( Η0- (Α0) η-Η, where Α is Ca-C3 alkylene and m is an integer from 1 to 10) Compound produced by ring-opening addition reaction]; allyl methacrylate; divinylbenzene, etc. . These monomers are known and readily available. It can be used alone or at least two of them can be used in combination. The aforementioned multifunctional monomer is used as a cross-linking agent in an amount sufficient to effectively generate the cross-linking structure for the innermost layer. The general amount of Μ to produce the inner layer of the total amount of monomers prevails, is from about 0.5 to about 20 wt%, preferably from about 0.5 to about 10 r Please read the notes on the back before writing this page)丨 Installation and ordering. 丨 Abn paper standard General Chinese National Standard (CNS) A4 specification (210 X 297 mm) A6 B6 printed by Beigong Consumer Cooperation, Central Bureau of Standards, Ministry of Economy V. Invention description () »t96 ° The innermost polymer having a Tg (glass transition temperature) of 50 ° or Μ is a hard or rigid oxygen polymer. Preferably, the innermost layer has a Tg of about 50 to about 120 υ. The Tg value of the innermost polymer and the Tg values of the second, third, and outermost layers can be measured by independently polymerizing the individual constituent monomers, and measuring the Tg of the resulting polymer. In this way, the appropriate monomer and its ratio can be selected by measuring the ratio relationship of candidate monomers and the Tg value of the polymer prepared from the candidate monomer. In the description and the scope of patent application, Tg uses a parallax scanning card meter (model DS-10, manufactured by Seiko Instruments Inc.). It is measured according to ASTM-D-3418. The function of the innermost layer of the multilayer polymer is to prevent the multilayer polymer from Cracked or crushed during processing, and to prevent the heat resistance and mechanical strength of the resin composition containing the multilayer polymer from decreasing. For this purpose, the multilayer polymer of the present invention shall prevail and the amount of the innermost layer shall be About 10 to about 50% by weight, preferably about 20 to about 50% by weight, more preferably about 30 to about 40% by weight. The ratio of the innermost layer is too high, which easily reduces the workability. (H) The second layer of flute Producers of soft polymers with a Tg of lOt: or less, preferably from about -70 to 10 t. The soft polymer is composed of alkyl (eg Ci-Ci ») esters of acrylic acid (eg methacrylate, ethyl acrylic acid) Ester, propyl acrylate, butyl acrylate, octyl acrylate or nonyl acrylate) or conjugated diene (eg 1,3-butadiene, isoprene, 1,3-pentadiene This paper scale is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) -installed ---: ---. -------- Politics v Please read the precautions on the back first and then fill out this page) A6 B6 printed by B Industry and Consumer Cooperative of Central Bureau of Standards of the Ministry of Economy V. Description of invention (), chloroprene, etc. The amount of any other monomer that can be copolymerized with the aforementioned alkyl ester of acrylic acid or conjugated diene is effective to obtain a copolymer having a Tg of 10¾ or M, preferably about -70 to 10¾. Co-monomers include, for example, styrene, acrylonitrile, ethylene, propylene and methacrylic acid (such as h-Co> ester). The function of the second layer is to significantly increase the volume of the third layer, so even if a small proportion is used The third layer can also impart the desired degree of antistatic properties. In other words, when multilayer polymers are added with thermoplastic resins to impart antistatic properties, the function of the second layer allows the composition to have sufficient antistatic properties, even when used The same is true for small amounts of multilayer polymers. To achieve this function, the second layer accounts for about 5 to about 25 wt% of the multilayer polymer, preferably about 5 to about 15 wt%, more preferably about 5 to about 10 wt%. If the ratio of the two layers is too high, it is easy to make the multilayer polymer itself The heat resistance and mechanical strength of the thermoplastic resin in which the polymer particles are dispersed are reduced.
(c.)m IB 第二層係由具有Tg為10它或以下，較好約-70至1〇υ 之聚合物生成者，聚合物主要係由含聚烷撐氧鏈之不飽 和官能單體單位組成者。 第三層可單獨由含聚烷撐氧鍵之不飽和官能單體之聚 合物生成。由於此種官能單體之聚合反應性相當低，故 可由一棰共聚物生成第三層，所述共聚物係經由將所述一 官能單體與其它具有高聚合反應性之不飽和單體共聚合而 製備者。當如此共聚合時，有待與此一官能單體共聚合之 其它不飽和單體須能生成Tg為10¾或W下之共聚物。有用 本紙張尺度適用中國囷家標準（CNS)甲4规格（210 X 297公釐） ^----^-------------- -----^---；---訂------^ V請先閲讀背面之注意事項再項寫本萸> ^14489 Α6 Β6 經濟部中央標準局員工消費合作社印製 五、發明説明（） 的可共聚合單體，例如有就生成第二層之單體所舉例者。 第三層之共聚物中，含聚烷撐氧鏈之不飽和官能單醴單位 之比例至少為25 wt%，較好至少40 wt%，更好至少50wt %。 本發明之較佳具體例中，第三層係由具有Tg為1〇它或 Μ下，較好約-70至IOC之软質聚合物生成者，其中之軟察合 質聚合物係經由將下列各者所組成之單體混合製備者 :(i)含聚烷撐氧鏈之不飽和官能單體，（ii)選自共轭二 烯及丙烯酸酯中之至少一者，及（iii)含至少一烯靥不飽 和基及至少一親水基之有機化合物。 前述第三層之較佳具體例中，Μ單體總量為準，含聚 烷撐氧鍵之不飽和官能單體之用量比例為约25至約45wt% ，較好約25至約40wt% ;所述選自共軛二烯及丙烯酸酯中 之至少一棰單體之用量比例約70至約50wt%，較好約70至 約55wt% ;及含至少一烯屬不飽和基及至少一親水基的有 機化合物之用量比例由約5至約10wt%。 含聚烷撐氧鏈之不飽和官能單體之例，例如包含具有 一値聚烷撐氧鍵及在該聚烷撐氧鏈一端具有一個不飽和雙 鍵者。此種具有一個不飽和雙鍵之單體包含如下式所代表 之單體： D-0-(R0)„-X (1) 式中D為具有不飽和雙鍵之基，如乙烯基，烯丙基，（甲 代）丙烯醯基等，R為具有1至4碳原子之烷撐基，n為 5至50，較好9至25之整數，X並無待殊限制，可為氫原 ，請先閲讀背面之注意事項再填寫本頁) is. •Tr. •綾 本紙張尺度適用中國國家標準（CNS)甲4規格（210 X 297公釐） 經濟部中央標準局員工消費合作社印5农 A6 _ B6_ 五、發明説明（） 子，具有9或9 Μ下硪原子之垤基，磺酸基，羧睃基， 磷酸基及此等酸基之鹽，如納馥，鉀鹽，銨S等中之任一 者。 含聚烷撐氧鏈之不飽和官能單體為已知且易得。此等 單體之較隹例有聚乙二醇（甲代）丙烯酸酯，甲氧基聚乙二 醇（甲代）丙烯酸酯及聚乙二醇（甲代〉丙烯酸酯磺酸酯，其 中之聚乙二醇部分具有約6至約25環氧烷重複單位。 至於選自共轭二烯及丙烯酸酯中之至少一者，就生成 第二層之單體而舉例的單體偏好用於較佳具體例中。 含至少一烯屬不飽和基及至少一親水基之有機化合物 ，較好爲含一親水基如磺酸鹽基，羧酸鹽基或磷酸鹽基者 。鑑於高度抗靜電功效，Μ具有磺酸鹽基之有機化合物為 佳。鹽之例有Na鹽，Κ鹽或其它鹾金靥盏及銨鹽。 有機化合物之較佳例有不飽和二羧酸之（甲代〉丙烯基 酯磺酸鹽，特別C4-Ce烷基（甲代）烯丙基硫基丁二酸鹽， 如納月桂基（甲代）烯丙基硫基丁二酸鹽，鈉十六基（甲代> 烯丙基硫基丁二酸鹽等；及（C4-Cle烷基）苯基（甲代）烯丙 基硫基丁二酸鹽，如鉀辛基苯基（甲代〉烯丙基硫基丁二酸 鹽。 也可用作有機化合物者有芳香乙烯基磺酸鹽，如鈉苯 乙烯磺酸鹽，銨3-乙烯基甲苯磺酸鹽等。 又可用作有機化合物者有脂肪族乙烯基磺酸鹽如鈉乙 烯基磺酸鹽，丙烯酸磺酸鹽，如鈉（甲代）丙烯酿胺烷（如 C«-CaD)磺睃鹽等。其它有用的有機化合物包含不飽和羧 本紙張尺度通用中國國家標準（CNS)甲4规格（210 X 297公釐） ----r-------------- -----裝---，---訂------Μ I V請先閲讀背面之注意事項再塡寫本頁) 514489 M B6 經濟部中央標孕局貝工消費合作社印製 五、發明説明（） 酸酯磺酸鹽，例如鈉2-硫基乙基丙烯酸鹽，鈉2-硫基乙基 ct -乙基-丙烯酸鹽等。 此等含有至少一烯屬不飽和基及至少一親水基之有機 化合物爲已知及易得。其可單獨使用，或其中至少二者可 混合使用。 /·- 第三層可對多層聚合物賦予抗靜電性。本發明之多層 聚合物中之第三層比例爲約10至約40wt%，較好約15至約 3〇wt%。 ffll篇外履 最外層係由具有Tg約50*C或Μ上，較好约50至约120 〇之硬質或剛質聚合物生成，係經由烯靥不飽和官能單體 聚合而製備者。有用之單體範例包含用Μ生成最內層之烯 屬不飽和官能單體。 最外層用來使矚多層聚合物，與其中將加入多層聚合 物的熱塑樹脂相容。因此選用之單體類別將依據樹脂組成 物之期望用途而定。 Μ多層聚合物為準，最外層占約10至約50wt%，較好 約20至約50wt%。 在約0.05/im至約1 wm範圍之多層聚合物顆粒大小 ，適用於將聚合物分散於熱塑樹脂内。 本發明之多層聚合物例如係經由於含水介質内依序加 入單體，並進行聚合反應而將各層沈澱於前一層上，生成 最内層，第二層，第三層及最外層而製備者。 例如習知乳化劑及習知水溶性聚合引發劑可用於依次 〃請先閱讀背面之注意事項再填寫本頁) 丨装. 訂_ -線 本紙張尺度適用中國國家標準（CNS)甲4規格（210 X 297公釐〉 ^14489 Α6 Β6 五、發明説明（） 乳液聚合反應。或者也可經由使用乳化剤及油溶性聚合引 發劑，進行撤懸浮液聚合反應而單獨生成最内層，接著使 用水溶性聚合引發劑依次進行乳液聚合反應。 有用的乳化劑之例包含陰離子，陽雔子及非離子乳化 劑。一般K陰離子乳化劑為佳。乳化劑中，特佳者爲烷基 磺酸鹽，烷基苯磺酸鹽，烷基萘磺酸鹽，烷基磷酸鹽，聚 氧乙撐烷基K硫酸鹽（其中各烷基部分具有8至16碩原子） ，以及二烷基硫基丁二酸鹽（其中烷基部分具有4至16碳 原子）。此等鹽可爲鈉鹽，鉀鹽或銨鹽。 乳液聚合反應使用之引發劑包含水溶性過氧化物及水 溶性過硫酸留，例如過氧化氫及過硫酸納；及氧化還原引 發劑，包括氧化劑*如過氧化劑*如過氧化氫或過硫酸鈉 ，及水溶性還原劑如亞硫酸鹽，亞硫酸氳鹽，甲醛-次硫 酸鈉或亞鐵鹽。撤懸浮液聚合反應中使用之引發劑包含油 溶性過氧化物，如過氧化苯甲醯，過氧化月桂醢，異丙苯 過氧氫，或過氧基月桂酸三级丁酯；及包括此種油溶性過 氧化物及水溶性還原劑（如前述者）之氧化還原引發劑。 經濟部中央標準局貝工消费合作社印5衣 V請先閲讀背面之注意事項再填寫本頁) 第三層之聚合反應中，含有至少一烯屬不飽和基及至 少一親水基之有機化合物也可用作乳化劑，因此可免除加 入乳化劑，或添加小量即足Μ進行聚合反應。 聚合溫度可依所用引發劑選擇，通常於由約30至約90 C之範圍。聚合反應可進行至期望的聚合反應完成為止， 總反應時間在約30分鐘至約30小時之範圍，但依據所用單 體及其它條件，可有廣泛變化。 本紙張尺度適用中國國家標準（CNS)甲4規格（210 X 297公货） 經濟部中央標準局貝工消費合作社印製 A6 B6 五、發明説明（) 第二，第三及最外層之聚合反應進行中，單體，引發 劑，水及若有所需，乳化剤，可一次或連續或間歇加入反 應糸统内。 任何情況下，可藉習知方法（依據所用單體類別及重 量比而選擇 > 聚合單體，因而生成期望的最内，第二，第 三及最外層。 由於所用各單體之聚合產率接近100%，故最内，第 二》第三及最外層之重量比大體與單體之進料重量比相等 。此外，當進行共聚合反應時，饋入反應条統之成分共聚 單體之重量比實質對應於所生成之共聚物内存在的共聚單 體單位之重量比。 如此，各步驟所用單體之重量比，Μ單體用量總重爲 準， (Α)步驟（Α)中生成之最内層之單體用量為約10至約50wt %，較好約20至約50wt%， (B) 步驟（B)中生成第二層之單體用量為約5至約25 wt% ，較好約5至約15wt%， (C) 步驟（C)中生成第三層之單體用量為約1〇至約40 wt% ，較好约15至約30wt%，及 (D) 步驟（D)中生成最外層之單體用量為約10至約50 wt% ，較好約20至約50wt%。 聚合反應完成時，可藉習知方法分離所生成之本發明 之多層聚合物。舉例言之，將金屬鹽如CaCla，MgSo,或 Ala(S04)3加入所得聚合物膠乳内，進行所得多層聚合物 本紙張尺度適用中國國家標準（CNS)甲4规格（210 X 297公釐） --------------------· -----裝-------訂------^ v請先閲讀背面之注意事項再塡寫表頁) A6 B6_ 五、發明説明（） 顆粒之鹽析，然後Μ習知方式分離及乾燥。另外，所得聚 合物膠乳可噴乾而得期望的多層聚合物顆粒。 藉前述方法所得多層聚合物之適當顆粒大小，如前述 ，係在0.05wm至約1 Aim之範圍。 藉前述方法所得之多層聚合物可就此模製，或可與熱 塑樹脂混合模製而對樹脂賦予抗靜電性。 如此，本發明提供一種包括熱塑樹脂及本發明之多層 聚合物抗靜電樹脂组成物。 熱塑樹脂之種類並無特殊限制。較佳者為苯乙烯樹脂 ，聚乙烯，聚丙烯，偏氯乙烯樹脂，丙烯酸樹脂如甲基甲 代丙烯酸酯之均聚物或共聚物，聚醯胺樹脂，聚碩酸酯樹 脂，丙烯腈樹脂等。其中，更佳者為與構成多層聚合物之 最外餍的聚合物具有良好相容性者。 多層聚合物用量相對於每100重量份之熱塑樹脂為約 40至100重量份，較好約50至80重量份。在此範圍之真實 混合比可經測定，因而在期望的抗靜電性及期望的機械強 度與耐熱性間達成良好的平衡。 經濟部中央揉準局貝工消費合作社印製 (請先Η讀背面之注意事项再場寫表頁) 任一種習知混合方法皆可用以由多層聚合物及熱塑 樹脂生產抗靜電樹脂組成物。例如可藉V型摻混機， Henschel混合機，轉滾機等完成混合。接著使用混合滾 軸，班伯力混合機，單軸或雙軸擠壓機等以熔融狀態混練 。另外*多層聚合物可分散於熱塑樹脂製備用之單體糖漿 狀物内，然後分散液進行單體之懸浮聚合或本體聚合。 本紙張尺度適用中國國家標準（CNS)甲4規格（210 X 297公釐） 一18 - 經濟部中央標準局貝工消費合作社印製 A6 B6_ 五、發明説明（） 混合遇程中，若有所需可添加安定剤，潤滑劑，增塑 劑，顔料或染料，填充劑等。 所得樹脂组成物可藉各棰模製熱塑樹脂之習知方法模 製。 依據本發明，本發明之多層聚合物摻混或分散於熱塑 樹脂内，藉此對熱塑樹脂提供抗靜電性，而其固有樹脂性 質並無顯著改變。此外，如此所賦予的抗靜電性並未因與 水或其它物質接觸或因摩擦而減低。 奮掄俐 Μ下將參照下列實施例進一步詳細說明本發明。例中 之份數及百分率皆為Κ重量計。例中可藉下列方法評估物 理性質： U)荷電電壓半生期 50mm X 50mm X 3mm樣品於23X3於50%相對濕度靜置24 小時，然後於相同氛圍下，使用靜電儀（商品名“Static Honest Meter” ，Shishido Shokai 製造）使用施加電荷 10 KV，施加時間1分鐘及檯面轉速1300rpin之條件，測量荷 電電壓半生期。 (Π)比表面及體積電阻係數 50mm X 50mm X 3mm樣品於23C於50%相對濕度靜置24 小時，然後於相同氛圍下使用絕緣儀（SM-10E，Toa Dempa 工業公司製造）測量比表面及體積電阻係數。 (iii>熱變形溫度（HDT):使用於901退火3小時之試 驗件依據ASTM D638測量。 本紙張尺度通用中國國家標準（CNS)甲4规格（210 X 297公釐） ---^-------------------裝---；---.玎------埃 κ請先閲讀背面之注意事项再塡寫本頁) 經濟部中央標準居A工消费合作社印製 A6 B6___ 五、發明説明（） (iv)彎折模量：依據ASTM D-790測量。 審掄期I 1 (A) 配備有回滾冷凝器之聚合容器內饋入225份水。以 氮清洗後及攪拌中，加入20份甲基甲代丙烯酸酯，0.2份 二乙烯苯，0.2份鈉十二基苯磺酸鹽，26份水及0.05份過 硫酸鈉之混合物，所得混合物於70Ό聚合反應1小時而生 成最內層，其Tg爲103t!。 (B) 其次，於如上（A)所得之聚合物膠乳内加入4份丁 基丙烯酸酯，0.1份納十二基苯磺酸鹽，10份水及0.05份 過硫酸鈉，及於70t聚合3小時而在最內層聚合物顆粒上 生成第二層（Τ3-54·〇〉，因而獲得二層聚合物顆粒。 (C〉其次，於如上（Β)所得之聚合物膠乳内加入8份丁 基丙烯酸酯，8份甲氧基聚乙二醇一甲代丙烯酸酯（環氧 乙烷單位數目==16)，0.1份鈉十二基苯磺酸鹽，10份水及 0.07份過硫酸納，及於70t聚合3小時而在二層聚合顆粒 上生成第三層（Tg-621C〉，因而獲得三層聚合物顆粒。 (D〉其次，於如上（C)所得之聚合物膠乳内加入20份甲 基甲代丙烯酸酯，0.2份月桂基硫醇，0.2份納十二基苯磺 睃鹽，25份水及0.02份過硫酸納，且於70T：聚合1小時而 在三層聚合物顆粒上生成最外層（Tg 102t：)〇 所得聚合物膠乳使用硫酸鎂水溶液鹽折，脫水，洗滌 及乾燥而得四層聚合物。 40份所得多層聚合物與60份甲代丙烯酸樹脂珠〔藉懸 浮液聚合反應 <商品名“Sumipex Β ΜΗ0” ，住友化學公司 本紙張尺度適用中國國家標準（CNS)甲4规格（210 X 297公货） -----------------------裝------.玎------, - - (請先閲讀背面之注意事項再填寫本頁) 314489 A6 B6 五、發明説明（） (請先閲讀背面之注意事項再填寫本頁) 製迨）而得〕使用Henschel混合機混合，然後混合物於200 -250Ό之汽缸溫度通過直徑20mm之通氣單螺桿擠壓機（東 洋精密儀器公司製造）擠壓而生成九粒。九粒射出成型成 試驗樣品（使用Meiki製作所製迨的M-140射出成型機>。評 估結果示於下表1。 hh m m 1 重複例1之程序，但並非如例1生成第二及第三層， 反而藉箸於步驟（A)所得之聚合物膠乳内加入12份丁基丙 烯酸酯，8份甲氧基聚乙二醇一甲代丙烯酸酯（環氧乙烷 單位數目= 16)，0.2份鈉十二基苯磺酸鹽* 20份水及0. 1 份過硫酸鈉，及進行聚合反應歴5小時生成第二層（Tg = -601D )，藉此獲得三層聚合物。所得聚合物Μ例1之相同 方式處理及評估。評估結果示於表1。 審掄例2 重複例1之程序，但使用5份甲氧基聚乙二醇一甲代 丙烯酸酯取代8份而生成第三層。所得第三層具有Tg為 -60Ό。所得四層聚合物以例1之柑同方式處理及評估。 評估結果不於表1。 hh龄例2 經濟部中央標準局R工消費合作社印製 重複比較例1之程序，但使用5份甲氧基聚乙二醇一甲 代丙烯酸酯取代8份而生成第二層。所得第二層具有Tg-59t：。所得三層聚合物Μ例1之相同方式處理及評估。評 估結果示於表1。 本紙張尺度適用中國酉家標準（CNS)甲4規格（210 X 297公釐） 經濟部中央標準局R工消費合作社印製 A6 B6 五、發明説明（） 表 1 比表面電 比餿積電 荷電電壓 HDT 竃折模量 顆粒 阻係數 胆係數 半生期 大小 (χ1014)Ω (χ10")Ω (sec) (¾) (kg/cma) U) 實施例1 1.7 0.46 2 86.0 17000 0.25 實施例2 8.0 2.0 4 91.0 18140 0.25 比較例1 9.0 2.5 5 86.7 16700 0.25 比較例2 30.0 9.0 9 89.1 18100 0.24 空白組 1000.0 1000.0 〇〇 104 32000 — 表1顯示下列结果。與比較例1所得之對應試驗樣品 比較，例1所得之試驗樣品之抗靜電性質，亦即比表面電 阻係數，比體積電阻係數及荷電電壓半生期優異，而HDT 與彎折模量可相比擬。 與比較例2所得之對應試驗樣品比較，實施例2所得 之試驗樣品之比表面電咀係數，比體積電阻係數及荷電電 壓半生期優異，而HDT及彎折模量可相比擬。 與空白組（亦即例1所用甲代丙烯酸樹脂但不含多層聚 合物）比較，含多層聚合物之試驗樣品具有較低的HDT及彎 折模量。但本發明之多層聚合物可引起HDT及彎折模量之 小量降低，及對樹脂組成物賦予顯著改良的抗靜電性質。 本紙張尺度適用中國國家標準（CNS)甲4规格（210 x 297公釐） ------------------------裝------訂------ - - - - (請先閲赛面之注意事項再場寫本頁)(c.) m IB The second layer is produced from a polymer having a Tg of 10 or less, preferably from about -70 to 1〇υ, the polymer is mainly composed of unsaturated functional monomers containing polyalkylene oxide chains Composition of body units. The third layer may be formed solely from a polymer of unsaturated functional monomers containing polyalkylene oxide bonds. Since the polymerization reactivity of this functional monomer is quite low, a third layer can be formed from a copolymer, which is obtained by copolymerizing the monofunctional monomer with other unsaturated monomers having high polymerization reactivity Produced by polymerization. When copolymerizing in this way, other unsaturated monomers to be copolymerized with this functional monomer must be able to produce copolymers with a Tg of 10¾ or less. The standard of this paper is applicable to the specifications of China National Standard (CNS) A 4 (210 X 297 mm) ^ ---- ^ -------------- ----- ^- -; --- Subscribe ------ ^ V Please read the precautions on the back first and then write the booklet> ^ 14489 Α6 Β6 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Invention Instructions () Polymerizing monomers are exemplified by monomers that form a second layer. In the copolymer of the third layer, the proportion of the unsaturated functional monohydric unit containing polyalkylene oxide chain is at least 25 wt%, preferably at least 40 wt%, more preferably at least 50 wt%. In a preferred embodiment of the present invention, the third layer is produced from a soft polymer having a Tg of 10 or less, preferably about -70 to 10C, where the soft-synthetic polymer is formed by The following monomers are prepared by mixing: (i) unsaturated functional monomer containing polyalkylene oxide chain, (ii) at least one selected from conjugated diene and acrylate, and (iii) Organic compounds containing at least one ethylenic unsaturated group and at least one hydrophilic group. In the preferred specific examples of the aforementioned third layer, the total amount of M monomers shall prevail, and the proportion of unsaturated functional monomers containing polyalkylene oxide bonds is about 25 to about 45% by weight, preferably about 25 to about 40% by weight The proportion of at least one monomer selected from conjugated diene and acrylate is about 70 to about 50 wt%, preferably about 70 to about 55 wt%; and contains at least one ethylenically unsaturated group and at least one The proportion of the hydrophilic group organic compound is from about 5 to about 10 wt%. Examples of the unsaturated functional monomer containing a polyalkylene oxide chain include, for example, those having a large polyalkylene oxide bond and an unsaturated double bond at one end of the polyalkylene oxide chain. Such a monomer having an unsaturated double bond includes a monomer represented by the following formula: D-0- (R0) „-X (1) where D is a group having an unsaturated double bond, such as vinyl, vinyl Propyl, (meth) acryloyl, etc., R is an alkylene group having 1 to 4 carbon atoms, n is 5 to 50, preferably an integer of 9 to 25, X is not subject to special restrictions, but can be hydrogen , Please read the precautions on the back and then fill out this page) is. Nong A6 _ B6_ V. Description of the invention (), with 9 or 9 Μ 塪 atomic base, sulfonic acid group, carboxyl group, phosphoric acid group and salts of these acid groups, such as nafion, potassium salt, ammonium Any of S, etc. Unsaturated functional monomers containing polyalkylene oxide chains are known and readily available. Examples of such monomers include polyethylene glycol (meth) acrylate, methoxy Polyethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate sulfonate, of which the polyethylene glycol portion has about 6 to about 25 alkylene oxide repeating units. From at least one of conjugated dienes and acrylates, the monomers exemplified for the formation of the second layer of monomers are preferably used in the preferred embodiments. Containing at least one ethylenically unsaturated group and at least one hydrophilic group Organic compounds are preferably those containing a hydrophilic group such as a sulfonate group, a carboxylate group or a phosphate group. In view of the high antistatic effect, organic compounds having a sulfonate group are preferred. Examples of salts include Na salt , Κ salt or other thallium and ammonium salt. Preferred examples of organic compounds are (meth) propenyl ester sulfonate of unsaturated dicarboxylic acid, especially C4-Ce alkyl (meth) allyl Thiosuccinates, such as sodium lauryl (meth) allyl thiosuccinate, sodium cetyl (meth> allyl thiosuccinate, etc.); and (C4-Cle Alkyl) phenyl (meth) allyl thiosuccinate, such as potassium octylphenyl (meth> allyl thiosuccinate). They can also be used as organic compounds with aromatic vinyl Sulfonates, such as sodium styrene sulfonate, ammonium 3-vinyl tosylate, etc. Also used as organic compounds are aliphatic vinyl sulfonates Sodium vinyl sulfonate, acrylic acid sulfonate, such as sodium (meth) acrylamine (such as C «-CaD) sulfonium salt, etc. Other useful organic compounds include unsaturated carboxylated papers. General Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) ---- r -------------- ----- installed ---, --- order ---- --Μ IV, please read the precautions on the back before writing this page) 514489 M B6 Printed by the Beigong Consumer Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs V. Description of invention () Acid sulfonate, such as sodium 2-sulfo Ethyl acrylate, sodium 2-thioethyl ct-ethyl-acrylate, etc. Such organic compounds containing at least one ethylenically unsaturated group and at least one hydrophilic group are known and readily available. It can be used alone, or at least two of them can be used in combination. / ·-The third layer can impart antistatic properties to the multilayer polymer. The proportion of the third layer in the multilayer polymer of the present invention is about 10 to about 40 wt%, preferably about 15 to about 30 wt%. ffll Outer outer layer The outermost layer is produced from a hard or rigid polymer having a Tg of about 50 * C or M, preferably about 50 to about 120 °, and is prepared by polymerizing an ethylenic unsaturated functional monomer. Examples of useful monomers include the use of M to form the innermost ethylenically unsaturated functional monomer. The outermost layer is used to make the multilayer polymer compatible with the thermoplastic resin to which the multilayer polymer will be added. Therefore, the type of monomer used will depend on the intended use of the resin composition. The M multilayer polymer is prevailing, and the outermost layer accounts for about 10 to about 50 wt%, preferably about 20 to about 50 wt%. Multilayer polymer particle sizes in the range of about 0.05 / im to about 1 wm are suitable for dispersing polymers in thermoplastic resins. The multilayer polymer of the present invention is prepared, for example, by sequentially adding monomers in an aqueous medium and performing a polymerization reaction to precipitate each layer on the previous layer to form an innermost layer, a second layer, a third layer, and an outermost layer. For example, conventional emulsifiers and conventional water-soluble polymerization initiators can be used in turn 〃 please read the precautions on the back and then fill out this page) 丨 installation. Order_ -The size of the paper is applicable to China National Standard (CNS) A4 specifications ( 210 X 297 mm> ^ 14489 Α6 Β6 V. Description of the invention () Emulsion polymerization. Alternatively, the innermost layer can be separately produced by using suspension polymerization reaction through the use of emulsifier and oil-soluble polymerization initiator, followed by water-soluble polymerization The initiator is sequentially subjected to emulsion polymerization. Examples of useful emulsifiers include anions, catharsis and nonionic emulsifiers. Generally, K anionic emulsifier is preferred. Among emulsifiers, alkyl sulfonates and alkyl groups are particularly preferred. Benzene sulfonate, alkyl naphthalene sulfonate, alkyl phosphate, polyoxyethylene alkyl K sulfate (wherein each alkyl part has 8 to 16 atoms), and dialkylthio succinate (The alkyl part has 4 to 16 carbon atoms.) These salts can be sodium, potassium or ammonium. The initiator used in emulsion polymerization reaction includes water-soluble peroxide and water-soluble persulfate, such as peroxide Hydrogen and sodium persulfate; and redox initiators, including oxidizing agents * such as peroxidizing agents * such as hydrogen peroxide or sodium persulfate, and water-soluble reducing agents such as sulfite, sulfite, formaldehyde-sodium hyposulfite or sulfite Iron salts. The initiator used in the suspension polymerization reaction contains oil-soluble peroxides, such as benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, or tertiary butyl peroxylaurate; And redox initiators including such oil-soluble peroxides and water-soluble reducing agents (as mentioned above). Printed on the 5th V of the Beigong Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs, please read the precautions on the back before filling this page) In the polymerization reaction of the third layer, an organic compound containing at least one ethylenically unsaturated group and at least one hydrophilic group can also be used as an emulsifier, so it is possible to avoid adding an emulsifier or add a small amount of sufficient M to carry out the polymerization reaction. The polymerization temperature can be selected according to the initiator used, and usually ranges from about 30 to about 90 ° C. The polymerization reaction can be carried out until the desired polymerization reaction is completed, and the total reaction time is in the range of about 30 minutes to about 30 hours, but can vary widely depending on the monomers used and other conditions. This paper scale is applicable to the Chinese National Standard (CNS) Grade A 4 (210 X 297 public goods). The A6 B6 is printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention () Second, third and outermost polymerization reactions During the process, monomers, initiators, water and, if necessary, emulsifiers can be added to the reaction system at once or continuously or intermittently. In any case, the conventional method (selected according to the type and weight ratio of the monomers used> polymerized monomers, thus forming the desired innermost, second, third and outermost layers. Due to the polymerization of each monomer used The rate is close to 100%, so the weight ratio of the innermost, second, third, and outermost layers is roughly equal to the feed weight ratio of the monomer. In addition, when the copolymerization reaction is carried out, the components of the reaction system are fed into the comonomer The weight ratio substantially corresponds to the weight ratio of the comonomer units present in the resulting copolymer. In this way, the weight ratio of the monomers used in each step, the total weight of the monomers used in M shall prevail, (Α) in step (Α) The amount of the monomer used in the innermost layer is about 10 to about 50% by weight, preferably about 20 to about 50% by weight, (B) the amount of the monomer used for the second layer in step (B) is about 5 to about 25% by weight, Preferably about 5 to about 15 wt%, (C) the amount of monomer used to form the third layer in step (C) is about 10 to about 40 wt%, preferably about 15 to about 30 wt%, and (D) step ( D) The amount of the monomer used to form the outermost layer is about 10 to about 50 wt%, preferably about 20 to about 50 wt%. When the polymerization reaction is completed, you can refer to Separate the multi-layer polymer of the present invention produced. For example, metal salts such as CaCla, MgSo, or Ala (S04) 3 are added to the resulting polymer latex, and the resulting multi-layer polymer is prepared according to the Chinese National Standard (CNS ) A 4 specifications (210 X 297 mm) -------------------- · ----- installed ------- ordered ---- -^ vPlease read the precautions on the back before writing the table page) A6 B6_ V. Description of the invention () The salting out of the particles, then separate and dry them in the conventional way. In addition, the resulting polymer latex can be spray dried to obtain the desired multilayer polymer particles. The appropriate particle size of the multilayer polymer obtained by the foregoing method, as described above, is in the range of 0.05 wm to about 1 Aim. The multilayer polymer obtained by the aforementioned method may be molded as such, or may be mixed and molded with a thermoplastic resin to impart antistatic properties to the resin. In this way, the present invention provides a multilayered polymer antistatic resin composition including a thermoplastic resin and the present invention. There are no special restrictions on the type of thermoplastic resin. Preferred are styrene resin, polyethylene, polypropylene, vinylidene chloride resin, acrylic resin such as homopolymer or copolymer of methyl methacrylate, polyamide resin, polyester resin, acrylonitrile resin Wait. Among them, the better ones are those having good compatibility with the outermost polymers constituting the multilayer polymer. The amount of the multilayer polymer is about 40 to 100 parts by weight, preferably about 50 to 80 parts by weight, per 100 parts by weight of the thermoplastic resin. The true mixing ratio in this range can be determined, thus achieving a good balance between the desired antistatic properties and the desired mechanical strength and heat resistance. Printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs (please read the precautions on the back and then write the table page). Any conventional mixing method can be used to produce antistatic resin compositions from multilayer polymers and thermoplastic resins. . For example, V-type blender, Henschel mixer, tumbler, etc. can be used to complete the mixing. Then use a mixing roller, Banbury mixer, single-shaft or twin-shaft extruder, etc. to knead in the molten state. In addition, the multi-layer polymer can be dispersed in the monomer syrup used for the preparation of the thermoplastic resin, and then the dispersion liquid can be subjected to suspension polymerization or bulk polymerization of the monomer. This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 1.18-A6 B6_ printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention () In the mixed encounter, if any Stabilizers, lubricants, plasticizers, pigments or dyes, fillers, etc. can be added if necessary. The resulting resin composition can be molded by conventional methods for molding thermoplastic resins. According to the present invention, the multilayer polymer of the present invention is blended or dispersed in a thermoplastic resin, thereby providing antistatic properties to the thermoplastic resin without significantly changing the inherent resin properties. In addition, the antistatic properties imparted in this way are not reduced by contact with water or other substances or by friction. The following will further illustrate the present invention with reference to the following examples. In the example, the parts and percentages are based on K weight. In the example, the physical properties can be evaluated by the following methods: U) The 50mm X 50mm X 3mm sample of the charged voltage half life is allowed to stand at 23X3 at 50% relative humidity for 24 hours, and then use an electrostatic meter (trade name "Static Honest Meter" under the same atmosphere ", Manufactured by Shishido Shokai) Using the conditions of applying an electric charge of 10 KV, an application time of 1 minute and a table top speed of 1300rpin, the half-life of the charged voltage is measured. (Π) Specific surface and volume resistivity 50mm X 50mm X 3mm samples were allowed to stand at 23C at 50% relative humidity for 24 hours, and then measured the specific surface and the insulation surface (SM-10E, manufactured by Toa Dempa Industrial Co., Ltd.) under the same atmosphere. Volume resistivity. (iii> Heat distortion temperature (HDT): The test piece used for 901 annealing for 3 hours is measured according to ASTM D638. The paper size is in accordance with the Chinese National Standard (CNS) A 4 specification (210 X 297 mm) --- ^- ----------------- Installed ---; ---. 玎 ------ Egyptian κ Please read the precautions on the back before writing this page) Ministry of Economic Affairs A6 B6___ printed by the Central Standard Ju A Consumer Cooperative. V. Description of the invention () (iv) Bending modulus: measured according to ASTM D-790. Trial period I 1 (A) A polymerization vessel equipped with a roll-back condenser is fed with 225 parts of water. After purging with nitrogen and stirring, add a mixture of 20 parts of methyl methacrylate, 0.2 parts of divinylbenzene, 0.2 parts of sodium dodecylbenzenesulfonate, 26 parts of water and 0.05 parts of sodium persulfate. 70 Ό polymerization reaction for 1 hour to form the innermost layer, the Tg is 103t !. (B) Next, add 4 parts of butyl acrylate, 0.1 part of sodium dodecylbenzenesulfonate, 10 parts of water and 0.05 part of sodium persulfate to the polymer latex obtained in (A) above, and polymerize at 70 t After a short time, a second layer (Τ3-54 · 〇> is formed on the innermost polymer particles, thus obtaining two-layer polymer particles. (C> Secondly, add 8 parts of butyl nitrate to the polymer latex obtained as above (B) Acrylate, 8 parts methoxypolyethylene glycol monomethacrylate (number of ethylene oxide units == 16), 0.1 part sodium dodecylbenzenesulfonate, 10 parts water and 0.07 parts sodium persulfate , And polymerized at 70t for 3 hours to form a third layer (Tg-621C>) on the two-layer polymer particles, thus obtaining three-layer polymer particles. (D> Second, add 20 to the polymer latex obtained as above (C) Parts methyl methacrylate, 0.2 parts lauryl mercaptan, 0.2 parts nadodecyl benzenesulfonate, 25 parts water and 0.02 parts sodium persulfate, and at 70T: polymerized for 1 hour in three layers of polymer particles The outermost layer (Tg 102t :) is formed on the upper layer. The obtained polymer latex is obtained by salting with magnesium sulfate aqueous solution, dehydrating, washing and drying. Polymer. 40 parts of the obtained multilayer polymer and 60 parts of methacrylic resin beads [by suspension polymerization < trade name "Sumipex Β ΜΗ0", Sumitomo Chemical Co., Ltd. This paper scale is applicable to China National Standard (CNS) A4 specifications ( 210 X 297 public goods) ----------------------- installed ------. 玎 ------,--(please first Read the precautions on the back and then fill out this page) 314489 A6 B6 V. Description of the invention () (Please read the precautions on the back and then fill out this page) The system is obtained) Use Henschel mixer to mix, then the mixture is 200-250Ό The temperature of the cylinder was extruded by a ventilating single screw extruder (manufactured by Toyo Precision Instruments Co., Ltd.) with a diameter of 20 mm to produce nine pellets. The nine pellets were injection-molded into test samples (using the M-140 injection molding machine manufactured by Meiki Manufacturing). The evaluation results are shown in the following table 1. hh mm 1 The procedure of Example 1 was repeated, but instead of generating the second and third layers as in Example 1, instead, 12 parts of butyl acrylic acid was added to the polymer latex obtained in step (A) Ester, 8 parts methoxypolyethylene glycol monomethacrylate (number of ethylene oxide units = 16), 0.2 parts sodium ten Diyl benzene sulfonate * 20 parts of water and 0.1 part of sodium persulfate, and the polymerization reaction was conducted for 5 hours to form a second layer (Tg = -601D), thereby obtaining a three-layer polymer. Examples of the obtained polymer M Process and evaluate in the same manner as in 1. The evaluation results are shown in Table 1. Examination Example 2 The procedure of Example 1 was repeated, but 5 parts of methoxypolyethylene glycol monomethacrylate were used instead of 8 parts to generate a third layer. The resulting third layer had a Tg of -60Ό. The resulting four-layer polymer was treated and evaluated in the same manner as the citrus of Example 1. The evaluation results are not shown in Table 1. hh age Example 2 Printed by R Industry and Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs The procedure of Comparative Example 1 was repeated, but 5 parts of methoxypolyethylene glycol monomethacrylate were substituted for 8 parts to generate the second layer. The resulting second layer has Tg-59t :. The obtained three-layer polymer M was processed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1. This paper scale is applicable to China Unitary Standards (CNS) A4 specifications (210 X 297 mm) A6 B6 printed by R Industry and Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of invention () Voltage HDT Plasma modulus of resistance Particle resistance coefficient Bile factor Half-life size (χ1014) Ω (χ10 ") Ω (sec) (¾) (kg / cma) U) Example 1 1.7 0.46 2 86.0 17000 0.25 Example 2 8.0 2.0 4 91.0 18140 0.25 Comparative Example 1 9.0 2.5 5 86.7 16700 0.25 Comparative Example 2 30.0 9.0 9 89.1 18100 0.24 Blank group 1000.0 1000.0 〇〇104 32000 — Table 1 shows the following results. Compared with the corresponding test sample obtained in Comparative Example 1, the antistatic properties of the test sample obtained in Example 1, that is, the specific surface resistivity, specific volume resistivity and charging voltage half life are excellent, and HDT is comparable to the bending modulus . Compared with the corresponding test sample obtained in Comparative Example 2, the test sample obtained in Example 2 is superior in specific surface electric nozzle coefficient, specific volume resistivity and charged voltage half-life, while HDT and bending modulus are comparable. Compared with the blank group (that is, the methacrylic resin used in Example 1 but not containing the multilayer polymer), the test sample containing the multilayer polymer has a lower HDT and bending modulus. However, the multilayer polymer of the present invention can cause a small decrease in HDT and bending modulus, and impart significantly improved antistatic properties to the resin composition. This paper scale is applicable to China National Standard (CNS) A4 specifications (210 x 297 mm) ------------------------ installed ----- -Subscribe ----------(Please read the notes on the game surface before writing this page)
A6 B6 314489 五、發明説明（） 窗掄例 (A)配備有回流冷凝器之聚合容器内饋入225份水。Μ 氮清洗後及攪拌中，加入19份甲基甲代丙烯酸酯，1份乙 基丙烯酸酯，0.2份二乙烯苯，0.2份鈉十二基苯磺酸鹽， 26份水及0· 05份過硫酸鈉之混合物，所得混合物於70C聚 合反應1小時而生成最內層，其Tg為l〇〇t。 (B>其次，於如上（A)所得之聚合物膠乳內加入4份丁 基丙烯酸酯，0.1份納十二基苯磺酸鹽，10份水及0.05份 過硫酸鈉，及於70它聚合3小時而在最内層聚合物顆粒上 生成第二層（Tg-54t：)，因而獲得二層聚合物顆粒。 (C) 其次，於如上〇)所‘得之聚合物膠乳內加入8份丁 基丙烯酸酯，5份甲氧基聚乙二醇一甲代丙烯酸酯（環氧 乙烷單位數目= 16)，1份鈉烷基（13碳原子）烯丙^"二 酸鹽，10份水及0.07份過硫酸鈉，及於701：聚合3小時而 在二層聚合顆粒上生成第三層（Tg-65t )，因而獲得三層 聚合物顆粒。 (D) 其次，於如上（C)所得之聚合物膠乳内加入20份甲 基甲代丙烯酸酯，0.2份月桂基硫醇* 0.2份納十二基苯磺 蒙兹鹽，25份水及0.02份過硫酸鈉，且於70^聚合1小時而 在三層聚合物顆粒上生成最外層（Tg 1〇1它）。 所得聚合物膠乳使用硫酸鎂水溶液鹽析，脫水，洗滌 及乾燥而得四層聚合物。 40份所得多層聚合物與60份申代丙烯酸樹脂珠〔藉懸 浮液聚合反應（商品名“Sumipex Β ΜΗ0” ，住友化學公司 (請先閲讀背面之注意事项再場寫本頁) -裝· 訂. 經濟部中央標準渴Η工消費合作社印黎 本紙張尺度適用中國國家標準（CNS)甲4規格（210 X 297公釐） -23 - A6 B6 五、發明説明（） 裂造）而得〕使用Henschel混合機混合，然後混合物於 200-2501：之汽缸溫度通過直徑20mm之通氣單螺桿擠壓機 (東洋精密儀器公司製造〉擠壓而生成九粒。九粒射出成型 成試驗樣品（使用Me iki製作所製造的M-140射出成型機）。 評估結果示於下表2。 審掄俐4 重複例3之程序，但使用3份甲氧基聚乙二醇一甲代 丙烯酸酯取代5份而生成第三層。所得第三層具有Tg為 -581C。所得四層聚合物Μ例3之相同方式處理及評估。 評估結果示於表2。 表 2 (*先閲讀背面之注意事項再填寫本頁) .裝. 經濟部中央搮準局8工消費合作社印髮 比表面電 比體積電 荷電電壓 HDT 鸯折模量 顆粒 阻係數 阻係數 半生期 大小 (χ10“）Ω (χ10“）Ω (sec) (V) (kg/cma) (U) 實施例3 1.0 0.8 5 89.4 16900 0.26 實施例4 20.0 6.0 15 93.6 18100 0.25 訂 •f- 本紙張尺度適用中酉國家標準（CNS)甲4規格（210 X 297公發〉A6 B6 314489 V. Description of the invention () Window case (A) A polymerization vessel equipped with a reflux condenser is fed with 225 parts of water. Μ After nitrogen cleaning and stirring, add 19 parts of methyl methacrylate, 1 part of ethyl acrylate, 0.2 parts of divinylbenzene, 0.2 parts of sodium dodecylbenzenesulfonate, 26 parts of water and 0.05 parts A mixture of sodium persulfate. The resulting mixture was polymerized at 70C for 1 hour to form the innermost layer, with a Tg of 100t. (B> Next, add 4 parts of butyl acrylate, 0.1 part of nadodecyl benzene sulfonate, 10 parts of water and 0.05 part of sodium persulfate to the polymer latex obtained in (A) above, and polymerize it at 70 After 3 hours, a second layer (Tg-54t :) was formed on the innermost polymer particles, thereby obtaining two layers of polymer particles. (C) Secondly, add 8 parts of butyl nitrate to the polymer latex obtained as above) Acrylate, 5 parts methoxypolyethylene glycol monomethacrylate (number of ethylene oxide units = 16), 1 part sodium alkyl (13 carbon atoms) allyl ^ " diacid, 10 parts Water and 0.07 parts of sodium persulfate, and at 701: polymerization for 3 hours to form a third layer (Tg-65t) on the two-layer polymer particles, thereby obtaining three-layer polymer particles. (D) Secondly, add 20 parts of methyl methacrylate, 0.2 parts of lauryl mercaptan * 0.2 parts of nadodecylbenzenesulfonate, 25 parts of water and 0.02 to the polymer latex obtained in (C) above Sodium persulfate was polymerized at 70 ° C for 1 hour to form the outermost layer (Tg 100) on the three-layer polymer particles. The resulting polymer latex was salted out using an aqueous magnesium sulfate solution, dehydrated, washed and dried to obtain a four-layer polymer. 40 parts of the obtained multilayer polymer and 60 parts of acrylic resin beads [by suspension polymerization (trade name "Sumipex Β ΜΗ0", Sumitomo Chemical Co., Ltd. (please read the precautions on the back before writing this page))-Pack · Order . The Central Standard of the Ministry of Economic Affairs thirteen H Industrial Consumer Cooperatives. The paper size of the paper is applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) -23-A6 B6 V. Description of invention () Cracked)) Henschel mixer was used to mix, and the mixture was extruded at a cylinder temperature of 200-2501: 20 mm in diameter through a vented single screw extruder (manufactured by Toyo Precision Instruments Co., Ltd.) to produce nine pellets. The nine pellets were injection molded into test samples (using Me iki M-140 injection molding machine manufactured by the company). The evaluation results are shown in the following table 2. Review 4 The procedure of Example 3 was repeated, but 3 parts of methoxypolyethylene glycol monomethacrylate were used instead of 5 parts. The third layer. The resulting third layer has a Tg of -581C. The resulting four-layer polymer M was processed and evaluated in the same manner as in Example 3. The evaluation results are shown in Table 2. Table 2 (* Please read the precautions on the back before filling this page ). Installed. Ministry of Internal Affairs and Communications Bureau of Industry and Commerce 8 Cooperatives Co., Ltd. publishes specific surface charge ratio volume charge charge voltage HDT mandarin folding modulus particle resistance coefficient resistance coefficient half-life size (χ10 “) Ω (χ10“) Ω (sec) (V) (kg / cma) (U) Example 3 1.0 0.8 5 89.4 16900 0.26 Example 4 20.0 6.0 15 93.6 18100 0.25 order