201249876 六、發明說明： 【發明所屬之技術領域] 係關於水性乳液聚合物粒子’其係個別具 域及埋人該基f之高含量之多個硬離散域 【先前技術】 適用於壓敏黏合劑之微域結構化之聚合物粒子一妒 係通過溶脹聚合技術合成。為了達成具有高微域含量2聚 合物的形成，業經嘗試其他合成製程。由於微域形成階段 中難以控制形貌’依目前領域之狀態不可能增加微域含量。 包括熱力學因子及動力學因子之限制參數阻止了該等製程 簡單地應用於大量批式製備。S. Kirsch等人揭露了聚合 物粒子，其係由作為種子之與不同類型之綾酸共聚合的聚 丙烯酸正丁酯及作為小硬域之藉由溶脹聚合製程合成的6 重量（wt)%苯乙烯或6wt%曱基丙烯酸曱酯組成Q)oes morphology stick? Tailored particle morphologies by swelling polymerization process, S. Kirsch, M. Kutschera, N. Y. Choi, T. Frechen, Journal of Applied Polymer Science, Volume 101, Issue 3, Pages 1444-1455)。然而，仍需要不犧牲藉由連續基質提供之黏合性質 之較高含量的聚苯乙烯系微域，以及安定、省時且可規模 化之聚合製程。 美國專利第5, 625, 001號揭露了經微域之 (microdomained)丙稀酸系衝擊改性劑，其具有處於連續聚 3 95245 201249876 =烯中之低於約杨t%之富含曱基丙烯酸醋之硬微 域°亥等械域可含有自約20wt%至約45wt%之乙烯基芳族 Cvinyl aromatic)單體，且係使用依序之或分階段之乳液 聚合製程於第—聚合物階段中形成。，然而，該等第二階聚 σ物係、&父聯之域’該域包含自約0. 5wt%至低於約5wt% 之接枝及/或交聯単體以達到高微域含量，達成該域形貌以 及避免產生將對該域結構所賦予之獨特性質造成負面影響 的芯/殼結構。該參考文獻並未教示或建議可在沒有接枝或 交聯單體之貢獻下形成高含量之微域。 本發明解決之問題為，找到在相應黏合劑製劑中藉由 連續軟基質提供滿意之黏合性能的高聚苯乙烯系微域含量 乳液聚合物。 先前技術參考文獻201249876 VI. Description of the Invention: [Technical Fields of the Invention] A plurality of hard discrete domains of aqueous emulsion polymer particles which are individual domains and high levels of the base f. [Prior Art] Suitable for pressure sensitive bonding The microdomain-structured polymer particles of the agent are synthesized by a swelling polymerization technique. In order to achieve the formation of a polymer having a high microdomain content, other synthetic processes have been tried. It is difficult to control the morphology due to the state of the microdomain formation. It is impossible to increase the microdomain content according to the state of the current field. Limiting parameters including thermodynamic factors and kinetic factors prevent these processes from being simply applied to large batch preparations. S. Kirsch et al. disclose polymer particles which are composed of n-butyl polyacrylate as a seed copolymerized with different types of citric acid and 6 wt% by synthesis of a small hard domain by a swelling polymerization process. Styrene or 6wt% decyl methacrylate consists of Q) oes morphology stick? Tailored particle morphologies by swelling polymerization process, S. Kirsch, M. Kutschera, NY Choi, T. Frechen, Journal of Applied Polymer Science, Volume 101, Issue 3, Pages 1444-1455). However, there is still a need for higher levels of polystyrenic microdomains without sacrificing the bonding properties provided by the continuous matrix, as well as a stable, time-saving and scalable polymerization process. U.S. Patent No. 5,625,001 discloses microdomained acrylic acid impact modifiers having a sulfhydryl-rich thiol group in a continuous poly 3 95245 201249876 = olefin lower than about 8%. The hard microdomain of acryl vinegar may contain from about 20% by weight to about 45% by weight of a vinyl aromatic Cvinyl aromatic monomer, and a sequential or staged emulsion polymerization process is used for the first polymer. Formed in the stage. , however, the second-order poly-sigma system, & parental domain', the domain comprises from about 0.5 wt% to less than about 5 wt% of grafted and/or cross-linked steroids to achieve high microdomains The content, the morphology of the domain is achieved and core/shell structures that would adversely affect the unique properties imparted to the domain structure are avoided. This reference does not teach or suggest that high levels of microdomains can be formed without the contribution of grafting or crosslinking monomers. The problem addressed by the present invention is to find a high polystyrene microdomain content emulsion polymer which provides satisfactory adhesion to a continuous binder in a corresponding binder formulation. Prior technical references
Does morphology stick? Tailored particle morphologies by swelling polymerization process, S. Kirsch, M. Kutschera» N.Y. Choi, T. Frechen, Journal of Applied Polymer Science, Volume 101, Issue 3f Pages 1444 - 1455 (2006).Does morphology stick? Tailored particle morphologies by swelling polymerization process, S. Kirsch, M. Kutschera» N.Y. Choi, T. Frechen, Journal of Applied Polymer Science, Volume 101, Issue 3f Pages 1444 - 1455 (2006).
Morphology and grafting in polybutylacrylate-polystyrene core-shell emulsion polymenzation, T. I. Min, A. Klein, M. S. El*aasser, J. W. Vanderhoff, journal of Polymer Science, Volume 21, Pages 2845 — 2861 (1983).Morphology and grafting in polybutylacrylate-polystyrene core-shell emulsion polymenzation, T. I. Min, A. Klein, M. S. El*aasser, J. W. Vanderhoff, journal of Polymer Science, Volume 21, Pages 2845-2861 (1983).
EP 0040419B1 EP 0359562A2 US 6552116B1 US 5625001A 【發明内容】 本發明係關於水性乳液聚合物，係包含： 第一域，其具有-80°C至_l〇°C之Tg，且包含作為經聚 4 95245 201249876 合之單元並基於第一域之重量為80至lOOwt%之丙烯酸系 單體；以及 非交聯之第二域，其具有50°C至120°C之Tg，且包含 作為經聚合之單元並基於第二域之重量為50至lOOwt%苯 乙烯系單體； 其中，該第二域之含量範圍係自大於該第一域與第二 域之總重的6wt%至30wt%。 本發明還關於製備此水性乳液聚合物的方法，係包含 下列步驟： a) 於包含80至lOOwt%之丙烯酸系單體之第一單體乳 液之反應器中進行乳液聚合； b) 持續將包含50至lOOwt%之苯乙烯系單體之第二單 體乳液加入該反應器中，同時银料起始劑； 其中，該步驟b)實質上不含交聯單體。 【實施方式】 為了描述本發明之組成物之成份，所有包含括號之短 語係表示包括括號内之詞語以及不包括括號内之詞語的一 者或兩者。舉例而言，短語"（甲基）丙烯酸酯"係意指丙烯 酸酯、甲基丙烯酸酯及其混合物，且本文中所使用之短語" (曱基）丙烯酸系''係意指丙烯酸系、甲基丙烯酸系及其混合 物。 如本文所使用者，術語π水性"應意指水，或與50wt°/〇 或更少（基於該混合物之重量）之與水互混（mi scib 1 e)之溶 劑混合的水。 5 95245 201249876 如本文所使用者，術語”聚合物"應包括樹脂及共聚 物。 如本文所使用者，術語"苯乙烯系，I係指代含有苯乙烯 或其衍生物之分子結構的單體，或含有苯乙烯或其衍生物 之經聚合單元的聚合物，該苯乙烯或其衍生物係諸如甲基 苯乙烯、乙烯基甲苯、甲氧基苯乙烯、丁基笨乙烯或氯苯 乙烯等。 如本文所使用者，術語"丙烯酸系，，係指代含有（甲基） 丙烯酸、（曱基）丙烯酸烷基酯、（甲基）丙烯醯胺、（甲基） 丙稀腈、或其變體形式如（甲基）丙烤酸經基烧基酯之分子 結構的單體，或含有（甲基）丙烯酸、（曱基）丙烯酸烷基酯、 (甲基）丙烯醯胺、（甲基）丙烯腈、或其變體形式如（曱基） 丙烯酸羥基烷基酯之經聚合單元的聚合物。 於本發明之第一態樣，該水性乳液聚合物係包含第一 域，該第一域包含作為經聚合之單元的丙烯酸系單體。本 文中之"第一域"係意指，該聚合物粒子中形貌上連續之 相，其構築一將其他離散相或域包埋於其中之基質。適當 之丙烯酸系單體可包括，舉例而言，一種或多種（甲基）丙 烯酸Ci-Go烷基醋單體、（甲基）丙烯酸C5_C3Q環烷基酯單 體、或（曱基）丙稀酸Cs-C3。（院基）芳基g旨單體，包括，舉 例而言，甲基丙烯酸曱酯、甲基丙烯酸異癸酯及低Tg單 體。適當之低Tg單體係包括，但不限於，丙烯酸乙酯（EA)、 丙烯酸丁酯（BA)、丙烯酸第三丁酯（t-BA)、丙烯酸2-乙基 己酯（2-EHA)、丙烯酸月桂酯、甲基丙稀酸月桂酯、（甲基） 6 95245 201249876 丙烯酸十六酯、（甲基）丙烯酸二十酯、（甲基）丙烯酸十六 基二十酯（cetyleicosyl (meth)acrylate)、（曱基）丙稀酸 二十二酯、丙烯酸甲酯、曱基丙烯酸丁酯（BMA)及其混合 物。較佳之丙烯酸系單體係選自EA、BA及2-EHA。 於該第一域聚合物中，該丙烯酸系單體之量的範圍係， 基於該第一域聚合物之乾重，自80至l〇〇wt%，較佳自90 至1 OOwt% ’更佳自95至1 〇〇wt%。該第一域聚合物可視需 要包含非丙烯酸系單體如，舉例而言，（甲基）丙烯醯胺、（曱 基）丙烯腈、或其衍生物。較佳地，該第一域聚合物不包含 非丙烯酸系單體。 於本發明之乳液聚合物粒子中，該第一域係具有_8〇<t 至-10°C，較佳-80°C至-2(TC ’更佳-7〇t：至-3〇°C之低玻璃 轉化溫度（Tg)。 本文中所使用之Tg係藉由使用福克斯公式（F〇x equation)(T. G. Fox, Bull. Am. Physics Soc., volurael,EP 0 040 419 B1 EP 0 359 562 A2 US 6552116 B1 US 5 625 001 A SUMMARY OF THE INVENTION The present invention relates to an aqueous emulsion polymer comprising: a first domain having a Tg of from -80 ° C to _10 ° C and comprising as a poly 4 95245 201249876 A unit comprising 80 to 100% by weight based on the weight of the first domain; and a non-crosslinked second domain having a Tg of 50 ° C to 120 ° C and comprising as a unit of polymerization And the styrene-based monomer is 50 to 100% by weight based on the weight of the second domain; wherein the content of the second domain ranges from 6 wt% to 30 wt% greater than the total weight of the first domain and the second domain. The invention further relates to a process for the preparation of such an aqueous emulsion polymer comprising the steps of: a) performing emulsion polymerization in a reactor comprising from 80 to 100% by weight of a first monomer emulsion of an acrylic monomer; b) continuing to comprise A second monomer emulsion of from 50 to 100% by weight of the styrenic monomer is added to the reactor with a silver starter; wherein step b) is substantially free of crosslinking monomers. [Embodiment] In order to describe the components of the composition of the present invention, all short-term phrases including parentheses include one or both of the words in parentheses and the words not including the brackets. For example, the phrase "(meth)acrylate" means acrylate, methacrylate, and mixtures thereof, and the phrase "(alkyl)acrylic" Refers to acrylic, methacrylic, and mixtures thereof. As used herein, the term π aqueous " shall mean water, or water mixed with a water miscible (mi scib 1 e) solvent of 50 wt ° / 〇 or less (based on the weight of the mixture). 5 95245 201249876 As used herein, the term "polymer" shall include both resins and copolymers. As used herein, the term "styrene", I refers to a molecular structure containing styrene or a derivative thereof. a monomer, or a polymer comprising a polymerized unit of styrene or a derivative thereof, such as methyl styrene, vinyl toluene, methoxy styrene, butyl styrene or chlorobenzene Ethylene, etc. As used herein, the term "acrylic, refers to (meth)acrylic acid, alkyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile Or a variant thereof, such as a monomer having a molecular structure of (meth)propionic acid via a ketone ester, or containing (meth)acrylic acid, alkyl (meth) acrylate, (meth) acrylamide a polymer of (meth)acrylonitrile, or a variant thereof, such as a polymerized unit of a (hydroxy) hydroxyalkyl acrylate. In a first aspect of the invention, the aqueous emulsion polymer comprises a first domain , the first domain is included as a polymerized The acrylic monomer of the unit. The "first domain" herein means a morphologically continuous phase of the polymer particle that constructs a matrix in which other discrete phases or domains are embedded. The acrylic monomer may include, for example, one or more (meth)acrylic Ci-Go alkyl vine monomer, (meth)acrylic acid C5_C3Q cycloalkyl ester monomer, or (mercapto) acrylic acid. Cs-C3. (hospital based) aryl g monomer, including, for example, decyl methacrylate, isodecyl methacrylate and low Tg monomers. Suitable low Tg single systems include, but not Limited to ethyl acrylate (EA), butyl acrylate (BA), tributyl acrylate (t-BA), 2-ethylhexyl acrylate (2-EHA), lauryl acrylate, methyl acrylate Ester, (methyl) 6 95245 201249876 Cetyl acrylate, hexadecyl (meth) acrylate, cetyleicosyl (meth) acrylate, (mercapto) acrylate Dodecyl ester, methyl acrylate, butyl methacrylate (BMA) and mixtures thereof. Preferred acrylic singles The system is selected from the group consisting of EA, BA and 2-EHA. In the first domain polymer, the amount of the acrylic monomer ranges from 80 to 100% by weight based on the dry weight of the first domain polymer. Preferably, it is from 90 to 100% by weight 'more preferably from 95 to 1% by weight. The first domain polymer may optionally contain a non-acrylic monomer such as, for example, (meth) acrylamide, Acrylonitrile, or a derivative thereof. Preferably, the first domain polymer does not comprise a non-acrylic monomer. In the emulsion polymer particles of the present invention, the first domain has _8 〇 < t to -10 ° C, preferably -80 ° C to -2 (TC 'better -7 〇 t: to -3 ° ° C low glass transition temperature (Tg). The Tg used herein is by using the F〇x equation (T. G. Fox, Bull. Am. Physics Soc., volurael,
Issue No. 3, Page 123(1956))計算而得者。亦即，用於計 算單體Ml與M2之共聚物的Tg， 1 _ \ν{Μλ) MMj)Issue No. 3, Page 123 (1956)) Calculated by. That is, the Tg for calculating the copolymer of the monomers M1 and M2, 1 _ \ν{Μλ) MMj)
Tg{calc.) Tg{Mx) + Tg(M2) f 其中’TgCcalc.)為該共聚物之玻璃轉化溫度的計算值， w(Ml)為該共聚物中單體Ml之重量分率（Weight ， w(M2)為該共聚物中單體M2之重量分率，了_)為M之均 聚物的玻璃轉化溫度，而Tg⑽為M2之均聚物的玻璃轉 化溫度，所有溫度係以K計。均聚物之坡_化溫度可於 95245 7 201249876 諸如J. Brandrup及E. H. Immergut編纂之《聚合物手冊》 ("Polymer Handbook", Interscience Publishers)中查 找。 本發明之水性乳液聚合物係包含非交聯之第二域，該 第二域係包含作為經聚合單元之贫， ^ ^ 〜本乙烯系單體。本文中，' 第二域"意指該聚合物粒子中形游 规上離散之相或域，該第二 域係埋入該"第一域"之基質中。说 通虽之苯乙烯系單體可包 括，舉例而言，苯乙烯、甲基笨rJ ^ G締、乙烯基甲笨、甲盞 基曱苯、丁基苯乙烯、或氣笨乙铋“ ^ ^ ^ 〇 稀或其混合物。較佳地， 該苯乙烯系單體係苯乙烯。 本文中"非交聯之域”意指，眘 0. 5wt%(基於該第二階聚合物之總上不3或3有低於 聯單體或接枝單體之聚合結構。^《作為聚合殘基之交 可與其他早體共聚合之二乙烯系 η 其中，該等乙稀系不飽和基具有=乙烯糸不飽和單體’ 例而言，二乙稀基苯（DVB);二（相等之反應性如’舉 基）丙烯酸二醇醋如，舉例而言，f)丙稀酸二醇酉旨及三（甲 酯、1,2-乙二醇二甲基丙烯酸丁二醇二曱基丙烯酸 酯；三（曱基）丙稀酸三醇醋 ，6—己二醇二丙埽酸 文中"接枝賴"指代可與其他單=酸二烯㈣等。本 乙埽系不飽和單體，且其不飽和=口之一乙稀系或多 使得大量殘留之不飽和度在其聚、足夠低之反應性以 中，該單體係諸如，舉例而言，甲: 之後仍保留在聚合物 丙烯酸烯丙醋、馬來酸二烯_，丙烯酸烯丙醋(峨)、 曰、丙烯醯氧基丙酸烯丙酯 95245 8 201249876 等本文中#質上不含”應意指，絕對不含有、或含有作 為雜質之痕量、或低於有效量之物質。 於該第二域聚合物中，該苯乙稀系單體之量的範圍 係，基於該第二域聚合物之乾重，自50至lGGwt%，較佳 80 至 lOOwt%，更佳自 9〇至 1〇〇wt%。 於本發明之乳液聚合物粒子中，該第二域係具有5(TC 至 l2〇C，較佳 80°C 至 11〇。(：，更佳 85°C 至 105。(：之高 Tg。 就該水性乳液聚合物之所欲之硬微域含量及效能性 質之觀點來看，較佳係該第二域之重量百分率（wt%)範圍 為’基於該第—域與該第二域之總重，自大於6wt%至 3〇Wt% ’較佳自10至30wt%，更佳自20至25wt%。 ^於本發明之一個具體實施態樣中，該乳液聚合物粒子 係個別由前述第—域及第二域兩種域組成。 ^於本發明之另一具體實施態樣中，該乳液聚合物粒子 係個另]由一種或更多種域組成，例如，舉例而言，進一步 ^有具有8G°Ci 22(TC之Tg#第三域，該第三域之存在含 罝為，基於三種域之總重，自〇·〇1至40wt%。可基於兩階 ’、呈被域之聚合物粒子實施第三階聚合反應，以形成埋入該 第阳ΛΚ合物或構築該兩階聚合物粒子之殼結構的另一類 型之域預期者，額外之一階或多階聚合物也可引入微域， 其係根據潛在之應用需求（舉例而言，作為塑膠之衝擊改性 “）而„°又汁。若存在，此等額外之域可自下列者形成：丙烯 酸系單體、苯乙烯系單體或官能單體如，舉例而言，前述 交聯單體或接枝單體。 95245 9 201249876 使用布魯克海文儀器公司（Brookhaven Instruments Corporation, Holtsville，N.Y.)提供之 BR00KHAVENtm BI-90型粒子尺寸量測器測量獲知，該乳液聚合物粒子之 平均粒子直徑為自50至600奈米，較佳自150至550奈米。 本發明之第二態樣係提供製備該水性乳液聚合物之 方法，係包含下列步驟： a) 於包含80至100wt%之丙烯酸系單體之第一單體乳 液之反應器中進行乳液聚合；以及 b) 持續將包含50至100wt%之苯乙烯系單體之第二單 體乳液加入該反應器中，同時餵料起始劑； 其中，該步驟b)實質上不含交聯單體。 用以製備水性乳液聚合物之聚合技術係該技術領域中 習知者。於該乳液聚合製程中，可使用常規界面活性劑如， 舉例而言，陰離子及/或非離子乳化劑如，舉例而言，烷基、 芳基或烧基芳基之硫酸酯、續酸酯或鱗酸酯之驗金屬鹽或 銨鹽；烷基磺酸類；磺醯基琥珀酸鹽類；脂肪酸類；乙烯 系不飽和界面活性劑單體；以及乙氧基化醇類或盼類。界 面活性劑之用量往往為，基於單體之重量，〇.〇5^%至 6wt%。可使賴賴製程或氧化還原起始製程。於該反應 之整個過程中，反應溫度往往保持於低於1〇〇它之溫度。 反應溫度較佳係界於與95。(：之間，更佳界於^與 90°C之間。該單體齡物可以純淨物形式（咖）或水乳液 形式加入。第一階單體混合物可一次加入或多次加入，或 於反應期間以線性或非線性持續加入，或以兩者之址合形 95245 10 201249876 式加入而 第二階單體混合物係持續加入。 可使用常規之自由基起始劑如，舉例而言，過氧化氫、 過氧化鈉、過氧化鉀、氫過氧化第三丁基（t-buty hydroperoxide)、氫過氧化第三戊基、氫過氧化異丙苯 (cumene hydroperoxide)、過硫酸銨及/或鹼金屬過硫酸 鹽、過删酸鈉、過填酸及其鹽、高猛酸卸、以及過氧二硫 酸之銨鹽或鹼金屬鹽，其用量典型為，基於總單體之重量， O.Olwt%至3. Owt%。可使用與適當之還原劑偶合之該相同 起始劑的氧化還原系統，該還原劑係諸如，舉例而言，曱 醛次硫酸鈉（sodium sulfoxylate formaldehyde),抗壞血 酸，異抗壞血酸，含硫之酸的鹼金屬鹽及銨鹽如亞硫酸鈉、 酸式亞硫酸鹽（bisulfite)、硫代硫酸鹽、亞硫酸氫鹽 (hydrosulfite)、硫化物、硫氫化物或二亞硫續酸鹽，曱 腓亞續酸（formadinesulfinic acid)，羥基曱續酸，丙酮 酸式亞硫酸鹽（acetonebisuifite)，胺類如乙醇胺，乙醇 酸，乙醛酸水合物，乳酸，甘油酸，蘋果酸，酒石酸及前 述酸之鹽。可使用催化如鐵、銅、錳、銀、鉑、飢、鎳、 絡、把或銘之金屬鹽之氧化還原反應。可視需要使用該等 金屬之螯合劑。 可使用鏈轉移劑來降低該乳液聚合物之分子量及/或 提供不同於業經使用產生自由基之任何起始劑獲得者的分 子量分佈，該鏈轉移劑係諸如.，舉例而言，齒素化合物如 四漠甲L稀丙基化合物；或疏基化合物如魏基乙酸燒基 醋、魏基烧酸烧基酯以及C4—C22、線性或分支鍵烧基硫醇。 95245 201249876 鏈轉移劑可一次加入或多次加入，或於整個反應期間大多 數或全部時間内或於該反應期間之限制部份（如，舉例而 言’於反應釜填充過程或殘留單體降低階段）以線性或非線 性持續加入。鏈轉移劑之用量典型為，基於用以形成該水 性乳液聚合物之單體的總重’ 〇至5wt%。鏈轉移劑之較佳 含里係，基於用以形成該水性乳液聚合物之單體的總莫耳 數，自0· 01至1· Omol%，更佳自〇. 〇2至〇. 4m〇l%，最佳 0. 05 至 0. 2mole%。 可藉由以最小加熱時間澆鑄膜並隨後檢查該膜來直接 檢查該聚合物粒子，或檢查模鑄部件，從而確認該乳液聚 合物粒子之所欲形貌。可將該等樣本進行選擇性染色來強 調該苯乙烯系基或丙烯酸系基，最有效者係用於苯乙烯基 之釕染色技術（Trent 等人 ’ Macromolecules，16，588 (1983))。於TEM實驗中觀察到，本發明之乳液聚合物粒子 具有聚苯乙烯系域之集束，且此等集束係均勻分佈於該包 埋基質中。 藉由將該經微域之乳液聚合物與佐劑如，舉例而言， 增黏劑、顏料、乳化劑、聚結劑、緩衝劑、中和劑、增稠 劑或流變改性劑、保濕劑、潤濕劑、殺生物劑、塑化劑、 抗發泡劑、著色劑、蠟及抗氧化劑組合使用，該聚合物可 用作黏合劑，尤其是壓敏黏合劑、密封劑、紡織或非紡織 物黏結劑、彈性塗層或填縫組成物的一種成份ό 由於將自超過6wt%至30wt%之較廉價的苯乙烯系域合 併入本發明中揭示之乳液聚合物粒子中，該粒子及形貌表 12 95245 201249876 的優點。與彼—酸丁- 物中人成柯降低5%至i5%。於該聚合 音3 6wt/°或更低含量之苯乙烯系域並不導致令人滿 士本下降但其作為壓敏黏合劑之效能與現存聚人物 ^或略優於後者。經證實，具有超過3Gwt%之苯乙料 :體在卫薇處理巾造成安全問題，在發明人之實驗室操作 觀察到這-問題。此外，已觀察到高含量水準如約％㈣ 硬域顯著改善該黏合劑材料之抗剪切性。此外，如技術 :域中已知者’埋入該聚合物粒子中的聚苯乙烯系域越 I ’他們對粒子貢獻之疏水性越強，這顯著改善該乳液聚 s物作為黏合劑材料之抗水性。 於f說明書中’除了特別指出者之外每一較佳技術 ，、手段及更佳技術解決手段的麟特徵可彼此組合以形 八新的技術解決手段。簡而言之，申請人省略了對此等组 ς的說明。然而’藉由將此等技術特徵組合而獲得之技術 中决手段應全部視為以明確的方式清晰揭示於本說明書 [實施例] L原料縮寫 95245 13 201249876 --成乳膠化合物中使用之起始材料 化合物 化學特性 BA 丙烯酸丁酯 2-EHA 丙烯酸2-乙基己酯 ST 苯乙烯 EA 丙烯酸乙酯 MMA 曱基丙烯酸曱酯 (M)AA (曱基）丙烯酸 APS 過硫酸銨 t-AHP 氫過氧化第=戊基 SSF 曱醛次硫酸鈉 DBS 十二烷基笨磺酸鈉 SLS 十二烷基硫酸鈉 IAA 異抗壞血酸 DI水 去離子水 OPP 定向聚丙烯 11.測試方法 樣本製備：將樣本直接塗覆於經電暈處理之新鮮OPP 膜上，並於110°C乾燥5分鐘。該0ΡΡ之厚度大約為30微 米（/im)。該塗覆層之重量係控制為約21±1公克（g)/平方 公尺（in )。於測試之前，將經乾燥之樣本於經控制溫度之 室内（25±2°C，RH60±5W調節過夜。 環形初黏（Loop Tack)測試：根據第9號FINAT測試 方法（FINAT= Federation Internationale des fabricants et transformateurs df Adhesifs et Thermocollants) 於不錄鋼板上測試樣本。 剝離強度測試：使用第2號FINAT測試方法進行90。 14 95245 201249876 剝離強度測試。 抗剪切性測試：使用第8號FINAT測試方法進行抗剪 切性測試。 樣本之合成：僅用於例示性說明之目的，下述實施例 1至8揭不使用丙烯酸丁酯第一階及苯乙烯第二階製備黏 σ d乳膠的通常製程。咸信可對該等反應參數、反應物及 分離過程進行本文未揭露之改動及變更。 實施例1 將590.0g DI水及13. 7g(基於固體）之100奈米（nm) 種子乳膠加入配備搜拌器、液體加入裝置、回流裝置、冷 凝器及氮氣噴霧線之適當之反應爸中，喷氮至少10分鐘7。 另外藉由組合_.GgBA、26 2gMAA、魏6gDI水及 lUg乳化劑（22.5%，DBS)製備第—階單體乳液。亦另外 藉由、且σ 617·8δ苯乙稀、13G.4g DI水及6.2g DBS乳化 劑製備第二階單體乳液。 ^ S爸中之水於氮氣氛下加熱至88°C。於攪拌下，將 解於30. 〇g DI 7欠之〇. gg Na2C〇3以及溶解於3〇g DI水之 g APS加入5亥爸中。隨後，於6〇分鐘内將第一階單體 =液及1.5g Na2C〇3之衝DI水溶液加入該燒瓶中。將反 ’、、器/皿度料在。於第-階單體乳液餵料之開始階段 加入二· IgAPS之90gDI水溶液，且於第二_料之後結束。 ς當第一階單體乳液之餵料結束時，分別加入60g以及 g 1)1。水冲洗該單體乳液及Na2C〇3飯料線。將反應器冷卻 至85 c並在該,皿度維持1〇分鐘。維持奶傲料開始第 95245 15 201249876 二階單體乳液餵料。於66分鐘内持續加入該第二階單體乳 液，之後分別加入60g及5g DI水沖洗該單體乳液及APS 餵料線。 將該反應器之内容物冷卻至75°C之過程中，加入2. lg 硫酸亞鐵（0. 5%)及10. Og之60nm聚合物乳膠。隨後，將溫 度保持在75°C，於90分鐘内將溶解於50g DI水之4. 13g t-AHP(85%水溶液）以及溶解於50g DI水之2. 22g SSF加 入該反應器中。將該反應器之内容物冷卻至50°C，隨後以 氫氧化銨中和至pH為7. 0至8. 0。透過100目及325目紗 布過濾該乳膠以移除該乳液中之任何凝膠。不進行進一步 之配製而進行應用測試。 實施例2 於實施例2之合成中使用與實施例1相同之設備。首 先，加入590. 0g DI水及13.7g(基於固體）之100nm種子 乳膠，喷氮至少10分鐘。另外藉由組合1503. OgBA、26. 2 g MAA、404. 6g DI 水及 14. 5g 乳化劑（22. 5%，DBS)製備第 一階單體乳液。亦另外藉由組合515. 5g苯乙烯、130. 4gDI 水及6. 2g DBS乳化劑製備第二階單體乳液。 兩階聚合、殘留單體之移除、中和及過濾步驟與實施 例1相同。 實施例3 於實施例3之合成中使用與實施例1相同之設備。首 先，加入590. 0g DI水及13.7g(基於固體）之100nm種子 乳膠，喷氮至少10分鐘。另外藉由組合1605. lgBA、26. 2 16 95245 201249876 g MAA、404. 6g DI 水及 16. lg 乳化劑（22. 5%，DBS)製備第 一階單體乳液。亦另外藉由組合413. 3g苯乙烯、130. 4g DI 水及4. 81g DBS乳化劑製備第二階單體乳液。 兩階聚合、殘留單體之移除、中和及過濾步驟與實施 例1相同。 實施例4 於實施例4之合成中使用與實施例1相同之設備。首 先，加入590.0g DI水及13.7g(基於固體）之100nm種子 乳膠，喷氮至少10分鐘。另外藉由組合1708. Og BA、30. 4 g MAA、446. 8g DI 水及 17. 5g 乳化劑（22. 5°/〇，DBS)製備第 一階單體乳液。亦另外藉由組合306. 8g苯乙烯、80. 2g DI 水及3. 14g DBS乳化劑製備第二階單體乳液。 兩階聚合、殘留單體之移除、中和及過濾步驟與實施 例1相同。 實施例5 於實施例5之合成中使用與實施例1相同之設備。首 先，加入590. Og DI水及13. 7g(基於固體）之100nm種子 乳膠，喷氮至少10分鐘。另外藉由組合1809. OgBA、32. 2g MAA、473. lg DI 水及 18. 5g 乳化劑（22.5%，DBS)製備第一 階單體乳液。亦另外藉由組合204. 5g苯乙烯、53. 5g DI 水及2. 09g DBS乳化劑製備第二階單體乳液。 兩階聚合、殘留單體之移除、中和及過濾步驟與實施 例1相同。 實施例6、7及8 17 95245 201249876 基於實施例1、2及3之步驟’相應作成實施例6、7 及8。差別在於： 於第一階單體乳液之製備中’以相等重量之AA單體 替換MAA單體。 藉由加入2. lg硫酸亞鐵（〇· 5%)，隨後於15分鐘内加 入溶解於20g DI水之1. G3g t-AHP(85%水溶液）及溶解於 l〇g DI水之〇· 55g SSF，實施階段間之殘留單體的移除。 第二階聚合之起始劑變為溶解於30g DI水之2. 06g t-AHP以及溶解於30g DI水之1. llg SSF。 其他步驟過程與實施例1保持相同。 實施例9 基於實施例1作成實施例9 ’但以EHA完全替換ba。 其他步驟過程與實施例1保持相同。 實施例10 將 597. Og DI 水、6. 90g SLS(28%)、2. 74g 氨溶液（25%) 及3. 73g共乳化劑加入配備攪拌器、液體加入裝置、回流 裝置、冷凝器及氮氣喷霧線之適當之反應爸中，噴氮至少 W 分鐘。另外藉由組合 888. 〇g EHA、41. 9g AA、844. 4g ea、 5g Sty、430. 〇g DI 水、6 9〇g as (28%)、& 6以 κ诎 及2.50g共乳化劑製備第一階單體乳液。 々將該釜中之水於氮氣氛下加熱至 83°C。於攪拌下，將 冷解於26g DI水之7. 79g APS以及70. 〇g(基於固體）之1〇〇 :種子乳膠加人料中。隨後’於9G分鐘内將第一階單 乳液及2. 6gAPS< 1〇〇gDI水溶液加入該燒瓶中。將反 95245 18 201249876 應器溫度保持在83。〇。 田第一階單體乳液之餵料結束時，分別加入60g以及 5忌。1)1水冲洗該單體乳液及Aps餵料線。將反應器冷卻至 55 C，加入3·2§硫酸亞鐵（0.5%)。隨後，將該溫度保持在 L，於30分鐘内將溶解於1〇g DI水之2 9g t_BHp(7〇% 水/合液）及溶解於1〇g DI水之丨.7g SSF加入該反應器中。 將1680g第—階作成之乳膠轉移至另一反應器中並 加熱至85°c。於加熱過程中，藉由組合50. 〇gDI水、1.8 g乳化劑（22. 5%, DBS)及200g Sty製備第二階單體乳液。 § /jdl度達到85 C時’加入3_ 2g硫酸亞鐵（〇. 5%)。隨後， 將溫度保持在85t，於90分鐘内將與溶解於75gDI水之 混合有1· 4g APS之1. 3g t-AHP(85%水溶液）、溶解於75g DI 水之1.4gIAA、以及第二階單體乳液加入該反應器中。餵 料結束時，分別加入55g及5 gDI水沖洗單體乳液及氧化 還原餵料線。 將該反應器之内容物冷卻至75。(：，於30分鐘内將溶 解於25g DI水之1· 7g t-AHP(85%水溶液）及溶解於25g DI 水之1. 00g IAA加入反應器中。 冷卻至50°C之後，以氫氧化銨將該内容物中和至ρΗ 為7. 0至8. 0。透過100目及325目紗布過濾該乳膠以移 除任何凝膠。之後不進行進一步之配製而進行應用測試。 實施例11 於該等實施例之效能測試中’該實施例使用羅門哈斯 公司（Rohm and Haas Company)生產之 R〇b〇ndTM PS-90 聚 95245 19 201249876 合物乳膠作為商用壓敏黏合劑基準（benchmark)。 實施例12 將每種聚合物乳液之10%與丙烯酸丁酯（52重量份）〆 甲基丙烯酸甲酯（46. 6重量份V甲基丙烯酸（1.3重量份） 之黏結劑乳液組合，用於檢查實施例丨至1〇中製備之經微 域之聚合物粒子結構。將樣本乾燥成膜，冷凍切片，於四 氧化釕蒸汽中曝露15分鐘。隨後，藉由STEM實驗證實經 微域之开^貌。結果顯示，於實施例1至10之樣本中觀察到 聚笨乙烯系域之集束，且此等集束均勻地分佈於包埋基質 中。於實施例1至10中，該第二域之含量基於該第一域及 第一域之總重為3〇重量％、25重量％、2〇重量％、15重量％、 10^里％、3〇重量％、25重量％、2〇重量％、3〇重量％及20 重置％，這表明當該第二域之範圍為自大於6”％至3〇wt% 或自10wt%至30wt%時，達成前述之經微域之聚合物形貌。 首先藉由手指黏性（finger tack)測試上述實施例1 至1丨之乳液聚合物的乾燥膜。該樣本全部顯示令人滿意之 ^齊I產品應具有的手指黏性效能。尤其是將實施例）至 纟本塗覆於0PP膜並黏附於紙上之後，於黏附位置該 卩撕下，這表明該等樣本為令人滿意之壓敏黏合劑材 厂、據則述測試方法實施用於壓敏黏合劑性能之進一步 之測試，測試結果係列述於表i中。 20 95245 201249876 表1.壓敏黏合劑性能之評估 實施例 第二域之含 量（wt%) 環形初黏(N/ 平方英吋） 90°剝離強度 (N/英吋） 剪切強度（小 時，l"xl"xlkg) 實施例11 0 8.7 A 5.8 A 53 C 實施例1 30 13.5 A 6.4 A 75 C 實施例2 25 14.5 A 8.5 A 25 C 實施例3 20 16.2 A 10.4 A 20 C 實施例4 15 14.5 A 8.4 A 29 C 實施例5 10 18.9 A 10.8 A 17 C 注：失敗模式標記ΠΑ"用於黏合劑失敗，而”C"用於凝聚 (cohesive)失敗0 【圖式簡單說明】 無 【主要元件符號說明】 無 21 95245Tg{calc.) Tg{Mx) + Tg(M2) f where 'TgCcalc.) is the calculated value of the glass transition temperature of the copolymer, and w(Ml) is the weight fraction of the monomer M1 in the copolymer (Weight , w(M2) is the weight fraction of the monomer M2 in the copolymer, _) is the glass transition temperature of the homopolymer of M, and Tg(10) is the glass transition temperature of the homopolymer of M2, and all temperatures are K meter. The slope of the homopolymer can be found in 95245 7 201249876, such as J. Brandrup and E. H. Immergut, "Polymer Handbook" (Interscience Publishers). The aqueous emulsion polymer of the present invention comprises a non-crosslinked second domain which comprises as a polymerized unit a lean, ^^~ present vinyl monomer. Herein, the 'second domain' means a phase or a discrete phase or domain in the polymer particle, and the second domain is buried in the matrix of the "first domain". Although the styrene monomer may include, for example, styrene, methyl stupid rJ^G, vinyl stupid, indolyl benzene, butyl styrene, or acetophenone " ^ 5重量百分比( Based on the total of the second-order polymer, the styrene is a single-system styrene. Preferably, the styrene-based single-system styrene. The upper 3 or 3 has a lower polymerization structure than the monomer or the graft monomer. ^ "As a polymerization residue, the divinyl system η which can be copolymerized with other precursors, wherein the ethylenically unsaturated groups Having = ethylene fluorene unsaturated monomer' example, diethyl benzene (DVB); two (equivalent reactivity such as 'enhanced base) acryl diol vinegar, for example, f) acrylic acid diol酉 及 and three (methyl ester, 1,2-glycol dibutyl methacrylate didecyl acrylate; tris(decyl) acrylic acid triol vinegar, 6-hexanediol dipropanoic acid "grafted Lai" refers to other mono-acid diene (four), etc. The ethyl acetonitrile is an unsaturated monomer, and its unsaturated = one of the mouths of the ethylene or more than a large amount of residual unsaturation The poly-system, low enough reactivity, such as, for example, A: remains in the polymer acrylic acid propylene acrylate, maleic acid diene _, acrylic acid propylene vinegar (峨), 曰, allyl propylene oxypropionate 95245 8 201249876, etc. herein does not contain, or does not contain, or contains traces of impurities, or less than an effective amount of the substance. The amount of the styrene monomer in the domain polymer ranges from 50 to 1 GGwt%, preferably from 80 to 100% by weight, more preferably from 9 〇 to 1 基于, based on the dry weight of the second domain polymer. 〇wt%. In the emulsion polymer particles of the present invention, the second domain has 5 (TC to 12 〇C, preferably 80 ° C to 11 〇. (:, more preferably 85 ° C to 105. (: From the viewpoint of the desired hard microdomain content and performance properties of the aqueous emulsion polymer, it is preferred that the weight percentage (wt%) of the second domain is 'based on the first domain and the The total weight of the second domain, from more than 6 wt% to 3 〇 Wt% ' is preferably from 10 to 30 wt%, more preferably from 20 to 25 wt%. ^ One embodiment of the present invention The emulsion polymer particles are composed of the aforementioned first domain and the second domain. ^ In another embodiment of the present invention, the emulsion polymer particles are one or more The domain composition, for example, further has a Tg# third domain having 8G °Ci 22 (TC, the presence of the third domain is 罝, based on the total weight of the three domains, from 〇·〇1 to 40wt %. A third-order polymerization reaction may be performed based on the two-stage ', polymerized particles of the domain to form another type of domain that is embedded in the first anode compound or the shell structure of the two-stage polymer particles is expected Additional first-order or multi-stage polymers can also be introduced into the microdomains, which are based on potential application requirements (for example, as impact modification of plastics). If present, such additional domains may be formed from: acrylic acid monomers, styrenic monomers or functional monomers such as, for example, the aforementioned crosslinking monomers or grafting monomers. 95245 9 201249876 It is known from the measurement of the BR00KHAVENtm BI-90 particle size measuring instrument provided by Brookhaven Instruments Corporation (Holtsville, NY) that the average particle diameter of the emulsion polymer particles is from 50 to 600 nm. It is preferably from 150 to 550 nm. A second aspect of the present invention provides a method of preparing the aqueous emulsion polymer comprising the steps of: a) performing emulsion polymerization in a reactor comprising a first monomer emulsion of 80 to 100% by weight of an acrylic monomer; And b) continuously adding a second monomer emulsion comprising 50 to 100% by weight of a styrenic monomer to the reactor while feeding the initiator; wherein step b) is substantially free of crosslinking monomers. Polymerization techniques for preparing aqueous emulsion polymers are well known in the art. In the emulsion polymerization process, conventional surfactants such as, for example, anionic and/or nonionic emulsifiers such as, for example, alkyl, aryl or alkyl aryl sulfates, and reductates may be used. Or a metal salt or an ammonium salt of a sulphate; an alkyl sulfonate; a sulfosuccinate; a fatty acid; an ethylenically unsaturated surfactant monomer; and an ethoxylated alcohol or a desired. The amount of the surfactant is usually from 5% to 5% by weight based on the weight of the monomer. It can make the process or redox start process. The reaction temperature tends to remain below 1 Torr throughout the reaction. The reaction temperature is preferably between 95 and 95. (between, better between ^ and 90 ° C. The monomeric age may be added in the form of a pure form (coffee) or an aqueous emulsion. The first-order monomer mixture may be added one at a time or multiple times, or The addition is continued either linearly or non-linearly during the reaction, or at the same location as 95245 10 201249876 and the second-order monomer mixture is continuously added. Conventional free radical initiators such as, for example, Hydrogen peroxide, sodium peroxide, potassium peroxide, t-buty hydroperoxide, third pentyl hydroperoxide, cumene hydroperoxide, ammonium persulfate and/or Or an alkali metal persulfate, sodium sulphate, over-acid and its salt, high-acid acid unloading, and ammonium or alkali metal salt of peroxodisulfate, typically in an amount based on the weight of the total monomer, O Owt% to 3. Owt%. A redox system of the same initiator may be used in combination with a suitable reducing agent such as, for example, sodium sulfoxylate formaldehyde, ascorbic acid. , isoascorbic acid, a base of sulfuric acid Salts and ammonium salts such as sodium sulfite, bisulfite, thiosulfate, hydrosulfite, sulfide, hydrosulfide or disulfite, hydrazine Formadinesulfinic acid), hydroxy sulphuric acid, acetone sulfite (acetonebisuifite), amines such as ethanolamine, glycolic acid, glyoxylic acid hydrate, lactic acid, glyceric acid, malic acid, tartaric acid and the aforementioned acid salts. Catalyzing the redox reaction of metal salts such as iron, copper, manganese, silver, platinum, hunger, nickel, ruthenium, ruthenium or ruthenium. The chelating agent of such metals may be used as needed. Chain transfer agents may be used to reduce the emulsion polymer. Molecular weight and/or providing a molecular weight distribution different from that of any initiator that is used to generate free radicals, such as, for example, a dentate compound such as a tetramethyl L-propyl compound; Sulfhydryl compounds such as thioglycolic acid acetonate, thioglycolate, and C4—C22, linear or branched bond thiol. 95245 201249876 Chain transfer agents can be added in one or more times, or throughout Most or all of the time during the reaction or during the reaction (eg, in the reactor filling process or the residual monomer reduction phase) is continuously added linearly or non-linearly. The amount of chain transfer agent is typically That is, based on the total weight of the monomer used to form the aqueous emulsion polymer, to 5% by weight. The preferred lining of the chain transfer agent is based on the total number of moles of the monomer used to form the aqueous emulsion polymer. 2mole%, from 0. 01 to 0. 2mole%. From 0. 01 to 1·Omol%, more preferably from 〇. The desired morphology of the emulsion polymer particles can be confirmed by directly inspecting the polymer particles by casting the film with a minimum heating time and then inspecting the film, or by inspecting the molded part. The samples may be selectively dyed to emphasize the styrenic or acrylic groups, most preferably for styryl dyeing techniques (Trent et al. 'Macromolecules, 16, 588 (1983)). It was observed in the TEM experiment that the emulsion polymer particles of the present invention have a cluster of polystyrene domains, and these bundles are uniformly distributed in the embedded matrix. By using the microdomain emulsion polymer with an adjuvant such as, for example, a tackifier, a pigment, an emulsifier, a coalescent, a buffer, a neutralizing agent, a thickener or a rheology modifier, A combination of a humectant, a wetting agent, a biocide, a plasticizer, an anti-foaming agent, a colorant, a wax and an antioxidant. The polymer can be used as a binder, especially a pressure-sensitive adhesive, a sealant, and a textile. Or a component of a non-woven fabric binder, an elastomeric coating or a caulk composition ό since more than 6 wt% to 30 wt% of a relatively inexpensive styrenic domain is incorporated into the emulsion polymer particles disclosed in the present invention, Particles and Morphology Table 12 95245 201249876 Advantages. It is reduced by 5% to i5% with the human ketone in the bismuth. The styrene domain at a level of 3 6 wt/° or less does not result in a decrease in man-made ratio but its effectiveness as a pressure-sensitive adhesive is comparable to or slightly better than the latter. It has been confirmed that the benzene-containing material having more than 3 Gwt% causes safety problems in the Weiwei treatment towel, and this problem is observed in the inventor's laboratory operation. In addition, it has been observed that high levels of moisture such as about % (d) hard domains significantly improve the shear resistance of the binder material. In addition, as known in the art: "The polystyrene domain buried in the polymer particles is more I', the more hydrophobic they contribute to the particles, which significantly improves the emulsion polys as a binder material. Water resistance. The features of each of the preferred techniques, means, and better technical solutions in addition to those specifically indicated in the specification can be combined with each other to form a new technical solution. In short, the applicant has omitted the description of these groups. However, the means in the art obtained by combining these technical features should all be clearly disclosed in the present specification in a clear manner [Examples] L raw material abbreviation 95245 13 201249876 - the starting point for use in latex compounds Material Compound Chemical Properties BA Butyl Acetate 2-EHA 2-Ethylhexyl Acetate ST Styrene EA Ethyl Acrylate MMA Mercapto Acrylate (M) AA (Mercapto) Acrylic APS Ammonium Persulfate t-AHP Hydroperoxide ==pentyl SSF Sodium sulfoxylate Sodium sulfoxide DBS Sodium dodecyl sulfonate SLS Sodium lauryl sulfate IAA Isoascorbic acid DI water deionized water OPP Oriented polypropylene 11. Test method Sample preparation: Direct coating of sample The corona treated fresh OPP film was dried at 110 ° C for 5 minutes. The thickness of this layer is approximately 30 micrometers (/im). The weight of the coating layer is controlled to be about 21 ± 1 gram (g) / square meter (in). Prior to testing, the dried samples were conditioned overnight at a controlled temperature (25 ± 2 ° C, RH 60 ± 5 W. Loop Tack test: according to FINAT test method No. 9 (FINAT = Federation Internationale des Fabricants et transformateurs df Adhesifs et Thermocollants) Test specimens on unrecorded steel plates Peel strength test: 90 using the FINAT test method No. 2. 14 95245 201249876 Peel strength test. Shear resistance test: use No. 8 FINAT test method The shear resistance test was carried out. Synthesis of the sample: For the purpose of illustration only, the following Examples 1 to 8 disclose the usual process for preparing the viscous σ d emulsion of the first order of butyl acrylate and the second stage of styrene. The reaction parameters, reactants, and separation process may be modified and modified as disclosed herein. Example 1 590.0 g DI water and 13.7 g (solids based) of 100 nanometer (nm) seed latex were added. Equipped with a suitable mixer, liquid addition device, reflux device, condenser and nitrogen spray line, the nitrogen is sprayed for at least 10 minutes. 7. Also by combination _.GgBA, 26 2gMAA, Wei 6gDI water and lUg emulsifier (22.5%, DBS) to prepare the first-order monomer emulsion. Also by σ 617·8δ styrene, 13G.4g DI water and 6.2g The DBS emulsifier is used to prepare the second-order monomer emulsion. ^ The water in the water is heated to 88 ° C under nitrogen atmosphere. Under stirring, it will be dissolved in 30. 〇g DI 7 owed to 〇. gg Na2C〇3 and dissolved Add 3 Ag of DI water to A 5 Dad. Then, add the first-order monomer = liquid and 1.5 g of Na2C〇3 aqueous solution of DI to the flask in 6 minutes. Adding a 90gDI aqueous solution of di-IgAPS at the beginning of the first-stage monomer emulsion feeding, and ending after the second material. ς When the feeding of the first-order monomer emulsion is finished, 60 g and g 1) 1 were added, respectively. The monomer emulsion and the Na2C〇3 rice feed line were rinsed with water. The reactor was cooled to 85 c and maintained at this level for 1 minute. Maintain milk to start the first 95245 15 201249876 second-order monomer emulsion feed. The second-order monomer emulsion was continuously added over 66 minutes, after which the monomer emulsion and the APS feed line were rinsed by adding 60 g and 5 g of DI water, respectively. The 5% ferrous sulfate (0.5%) and 10. Og of a 60 nm polymer latex were added to the process. Subsequently, the temperature was maintained at 75 ° C, and 4.23 g of t-AHP (85% aqueous solution) dissolved in 50 g of DI water and 2.22 g of SSF dissolved in 50 g of DI water were added to the reactor over 90 minutes. 0至8. 0。 0. 0. 0. 0. 0. 0. The latex was filtered through a 100 mesh and 325 mesh gauze to remove any gel from the emulsion. Application testing was performed without further formulation. Example 2 The same equipment as in Example 1 was used in the synthesis of Example 2. First, add 900.0 g of DI water and 13.7 g (solids based) of 100 nm seed latex and spray nitrogen for at least 10 minutes. Further, a first-order monomer emulsion was prepared by combining 1503. OgBA, 26.2 g MAA, 404.6 g DI water, and 14.5 g emulsifier (22.5%, DBS). A second-order monomer emulsion was also prepared by combining 515. 5 g of styrene, 10.4 g of DI water, and 6.2 g of DBS emulsifier. The second-order polymerization, removal of residual monomers, neutralization, and filtration steps were the same as in Example 1. Example 3 The same apparatus as in Example 1 was used in the synthesis of Example 3. First, add 900.0 g of DI water and 13.7 g (solids based) of 100 nm seed latex and spray nitrogen for at least 10 minutes. Further, a first-order monomer emulsion was prepared by combining 1605. lgBA, 26.2 16 95245 201249876 g MAA, 404.6 g DI water, and 16. lg emulsifier (22.5%, DBS). A second-order monomer emulsion was also prepared by combining 411.3 g of styrene, 10.4 g of DI water, and 4.81 g of DBS emulsifier. The second-order polymerization, removal of residual monomers, neutralization, and filtration steps were the same as in Example 1. Example 4 The same apparatus as in Example 1 was used in the synthesis of Example 4. First, 590.0 g DI water and 13.7 g (solids based) of 100 nm seed latex were added and nitrogen was sprayed for at least 10 minutes. Further, a first-order monomer emulsion was prepared by combining 1708. Og BA, 30.4 g MAA, 446.8 g DI water, and 17.5 g emulsifier (22.5 °/〇, DBS). A second-order monomer emulsion was also prepared by combining 306.8 g of styrene, 80.2 g of DI water, and 3.14 g of DBS emulsifier. The second-order polymerization, removal of residual monomers, neutralization, and filtration steps were the same as in Example 1. Example 5 The same equipment as in Example 1 was used in the synthesis of Example 5. First, 590. Og DI water and 13.7 g (solids based) of 100 nm seed latex were added and nitrogen was sprayed for at least 10 minutes. Further, a first-order monomer emulsion was prepared by combining 1809. OgBA, 32.2 g MAA, 473. lg DI water, and 18.5 g emulsifier (22.5%, DBS). A second-order monomer emulsion was also prepared by combining 20.45 g of styrene, 53.5 g of DI water, and 2.09 g of DBS emulsifier. The second-order polymerization, removal of residual monomers, neutralization, and filtration steps were the same as in Example 1. Examples 6, 7, and 8 17 95245 201249876 Based on the steps of Examples 1, 2, and 3, Examples 6, 7, and 8 were prepared accordingly. The difference is that the MAA monomer is replaced by an equal weight of AA monomer in the preparation of the first order monomer emulsion. By adding 2. lg ferrous sulfate (〇·5%), then adding 1. G3g t-AHP (85% aqueous solution) dissolved in 20g DI water and dissolved in l〇g DI water in 15 minutes. 55 g SSF, removal of residual monomers between stages of implementation. The llg SSF is dissolved in 30 g of DI water and dissolved in 30 g of DI water. The other steps are the same as in Embodiment 1. Example 9 Example 9 was made based on Example 1 but the BA was completely replaced with EHA. The other steps are the same as in Embodiment 1. Example 10 597. Og DI water, 6. 90 g SLS (28%), 2.74 g ammonia solution (25%) and 3.73 g co-emulsifier were added to a mixer, a liquid addition device, a reflux device, a condenser, and The proper reaction of the nitrogen spray line is to spray nitrogen for at least W minutes. In addition, by combining 888. Eg EHA, 41.9 g AA, 844. 4g ea, 5g Sty, 430. 〇g DI water, 69 〇g as (28%), & 6 with κ诎 and 2.50g The emulsifier prepares a first order monomer emulsion. The water in the kettle was heated to 83 ° C under a nitrogen atmosphere. Under stirring, the solution was cooled to 7.79 g of APS and 70. 〇g (based on solids) of 1 g of the DI: seed latex plus human. The first stage single emulsion and 2. 6 g of APS < 1 〇〇gDI aqueous solution were then added to the flask in 9 G minutes. Keep the temperature of the counter 95245 18 201249876 at 83. Hey. At the end of the feeding of the first-order monomer emulsion of the field, 60 g and 5 bogey were added respectively. 1) 1 water rinse the monomer emulsion and Aps feed line. The reactor was cooled to 55 C and 3·2 § ferrous sulfate (0.5%) was added. Subsequently, the temperature was maintained at L, and 9 g of t_BHp (7〇% water/liquid mixture) dissolved in 1〇g DI water and 丨7g SSF dissolved in 1〇g DI water were added to the reaction in 30 minutes. In the device. 1680 g of the first-stage latex was transferred to another reactor and heated to 85 °C. A second-order monomer emulsion was prepared by heating 50. 〇gDI water, 1.8 g emulsifier (22.5%, DBS), and 200 g Sty during heating. § When the /jdl degree reaches 85 C, add 3_2g of ferrous sulfate (〇. 5%). Subsequently, the temperature was maintained at 85 t, and mixed with 75 g of DI water in a period of 90 minutes, 1. 3 g of APS, 1.3 g of t-AHP (85% aqueous solution), 1.4 g of DIA dissolved in 75 g of DI water, and a second A monomer emulsion is added to the reactor. At the end of the feed, the monomer emulsion and the redox feed line were rinsed with 55 g and 5 g of DI water, respectively. The contents of the reactor were cooled to 75. (:, 1. 7g of t-AHP (85% aqueous solution) dissolved in 25g of DI water and 1. 00g of IAA dissolved in 25g of DI water were added to the reactor within 30 minutes. After cooling to 50 ° C, hydrogen was dissolved. The ammonium oxide was neutralized to a pH of 7. 0 to 0.8. The latex was filtered through a 100 mesh and 325 mesh gauze to remove any gel. The application test was then carried out without further formulation. In the performance tests of these examples, 'this example uses R〇b〇ndTM PS-90 poly 95245 19 201249876 latex produced by Rohm and Haas Company as a benchmark for commercial pressure sensitive adhesives (benchmark) Example 12 10% of each polymer emulsion was combined with a butyl acrylate (52 parts by weight) 〆 methyl methacrylate (46. 6 parts by weight of V methacrylic acid (1.3 parts by weight) of a binder emulsion, The microstructures of the microdomains prepared in Examples to 1 were examined. The samples were dried to form a film, frozen sections, and exposed to osmium tetroxide vapor for 15 minutes. Subsequently, the microdomains were confirmed by STEM experiments. The appearance is shown in the examples 1 to 10 A bundle of polystyrene-based domains is observed, and the bundles are uniformly distributed in the embedded matrix. In Embodiments 1 to 10, the content of the second domain is based on the total of the first domain and the first domain. The weight is 3〇% by weight, 25% by weight, 2% by weight, 15% by weight, 10% by weight, 3% by weight, 25% by weight, 2% by weight, 3% by weight, and 20% by weight. It is shown that when the range of the second domain is from more than 6"% to 3% by weight or from 10% by weight to 30% by weight, the above-mentioned microdomain polymer morphology is achieved. First, by finger tack The dried films of the emulsion polymers of the above Examples 1 to 1 were tested. The samples all showed satisfactory finger sticking properties which the product should have. In particular, the examples) were applied to the 0PP film. After adhering to the paper, the enamel is torn off at the adhesion position, which indicates that the samples are satisfactory pressure sensitive adhesive materials factories, and further tests for testing the performance of the pressure sensitive adhesives are carried out according to the test method. The results are described in Table i. 20 95245 201249876 Table 1. Evaluation of the properties of pressure sensitive adhesives Content of the second domain of the example (wt%) Ring initial tack (N/square inch) 90° peel strength (N/inch) Shear strength (hours, l"xl"xlkg) Example 11 0 8.7 A 5.8 A 53 C Example 1 30 13.5 A 6.4 A 75 C Example 2 25 14.5 A 8.5 A 25 C Example 3 20 16.2 A 10.4 A 20 C Example 4 15 14.5 A 8.4 A 29 C Example 5 10 18.9 A 10.8 A 17 C Note: Failure mode flag ΠΑ" for adhesive failure, and "C" for cohesive failure 0 [Simple diagram description] No [Main component symbol description] None 21 95245