TW406100B

TW406100B - Aqueous silylated polymer curable compositions

Info

Publication number: TW406100B
Application number: TW85112712A
Authority: TW
Inventors: Ming J Chen; Frederick D Osterholtz
Original assignee: Ck Witco Corp
Priority date: 1995-05-26
Filing date: 1996-10-17
Publication date: 2000-09-21

Abstract

Curable composition comprising a stable, water dispersible, curable polymer containing a sterically hindered alkoxylated silane group at 0.1 to 75 weight percent of the total composition; a water dispersible or water soluble, hydrolytically stable organometallic catalyst, at 0.1 to 10 weight percent of the total composition; and water at 99.8 to 24.9 weight percent of the total composition are taught herein. These compositions are useful as adhesives, sealants and paints. The compositions have improved properties including solvent resistance, adhesion, hardness, abrasion resistance and mar resistance. Particular catalysts for use herein include dihydroxy bis [2-hydroxypropanato (2-)-O1, O2] titanate, mixed titanium ortho ester complexes, acetylacetonate chelate, bis(ethyl-3-oxobutanolato-O1, O3) bis(2-propanolato) titanium, alkanolamine complex of titanium and mercaptoalcohol, mercaptide or sulfide forms of diorganotins having either a Sn-S or Sn=S bond.

Description

經濟部中央標準局員工消费合作社印製 _ 4061G0 ；；五、發明説明（1 ) ' 發明背景由於其它固化技術之環保，健康和安全顧慮提高，以具可水解珍虎部份之熱塑性聚合物爲基本之水可固化組合物逐漸變得令人感興趣。此類組合物具優良之耐氣候性，耐化學性及耐水性，因爲該矽烷基係以碳.矽鍵連接於聚合物鍵，而非不安定性碳-氧-矽鍵結；因而相較於具有以物理添加矽酸鹽或矽烷之系統，顯著地改良了耐水性，耐鹼性和耐酸性。然而，水可固化矽烷化聚合物組合物缺點之一在於其易於交聯，尤指倘若分散碑水中，在正常之製備 ’操作及保存·ί衣境下。結果’此類•組合物較不良彳闇置壽命頃易於限制其廣泛之商業接受力，且頃將矽燒化聚合物之用途保持於具非常低矽燒濃度者，典型上在水合聚合物產品中低於1.0重量％。調整水可固化組合物以減輕早期交聯問題係敘述於美國專利第4,526,930號中，其敘述具可水解矽烷部分之較水安定’可熔化加工之熱塑性聚合物，這些矽烷化聚合物僅由與具至少一即可水解基之有機鈦酸鹽反應活化或製成即水可固化，該酯與矽烷之酯基交換。雖然該鈦酸鹽係作爲一碎烷醇縮合觸媒，但其係分散於烯-丙烯酸鹽固體基質中，而非水中。未檢定之曰本專利申請案第6025502號敘述一種包括聚合物乳液之組合物，該乳液係藉著在乳液聚合作用後將一種不溶於水之锡觸媒（一種二有機錫羧酸鹽）添加於矽烷化乙烯聚合物得到。然而，對於此類薄膜而言，添加非水溶 -4- l·----；-----裝-----1訂^------線 * (請先閎讀背面之注意事項再填寫本頁} 本紙張尺度適用中囷國家標準（CNS )A4規格（210X297公釐）五、發明説明（ A7 捕1〇〇陘錫觸媒並不適當，因爲均相之觸媒與乳液聚合物混合物產生缺·點’如在表面上形成陷坑及顆辛立，以及在薄膜結構中$成不均句之交聯。此外，其中所述之β垸具有含至少 8個碳且通常爲直鏈結構之烷氧基。此日本專利申請案亦敘述通常用於矽烷/酯水解作用和縮合反應之無區別性固化觸媒。矽烷酯觸媒和含矽烷醇組合物之類似實例能夠於該文獻中發現，其揭示觸媒溶於以有機落劑爲基底之系統以確定適當固化。例如，長期以來頃知道二有機錫碳酸氫鹽係有機矽酮化口物來ο反應之觸媒。然而，不管其已證實用途，二有機錫碳酸氫鹽遭遇幾個缺點。一個是化合物之不安定性，如同當搁置時，尤指在濕潤環境下活性損失所示。當觸媒爲水性乳液形成時，該現象甚至更顯著。許多錫化合物亦可以在延長保存期間水解，並轉變爲催化祕形式。 1而，清楚地需要一種組份，在保存於水中期間具良好安疋性之水基底分散石夕燒化聚合物系、统，當應用及乾燥時產生良好品質之薄膜。發明摘要本發明提供水可分散或可乳化可固化聚合物之組合物，製備方法及使用方法，該聚合物具至少—燒氧料可水解基且其清楚地面臨以上問題之挑戰。本發明係關於碎坑化聚合物組合物之組成及製造方法，其可以有機金屬觸媒固化，且在保存於水中期間具良好安定性。這些組合物亦包括觸媒，水及視需要之其它成份。該組合物可以用於塗層 -5- ‘紙張尺度ϋ中國國家標準（c"nS ) I . .^-----------^ f - (請先閲讀背面之注意事項再填寫本頁) 經濟部_央標準局員工消費合作·社印製經濟部中央標準局員工消費合作杜印製 -406100____ _B7____ 五、發明説明（3 ) ’黏合劑及密封劑》—實例用途係玻璃纖維膠劑。該組合物之擱置壽命爲至少12個月。這些組合物之擱置壽命爲至少24個月更佳。附圖簡述圖1表示不銹鋼上乙婦丙烯酸系乳膠塗層，其由水解安定水可混溶且水可分散觸媒固化。圖2表示不銹鋼上乙烯丙烯酸系乳膠塗層，其由水解安定非水溶性觸媒固化。發明詳述，本發明之可固化水性組合物包括·：（I) 一含立體阻礙矽氧化矽烷基之安定性水可分散可固化聚合物，佔總組合物之〇. 1至75重量％ ; (II)水可分散或水溶性有機金屬觸媒，佔總組合物之0.1至10重量％ ; (III)水，佔99.8至24.9重量％ ; 及視需要之（IV)其它成份。 (I)聚合物用於此之聚合物係水可分散或可乳化可固化聚合物，其上聚懸掛和/或末端矽烷酯基（即烷氧基矽烷），其中至少一些懸掛和/或末端碎炫§旨基係立體阻礙之妙燒。碎娱:醋之立體阻礙避免矽烷酯水解並容許更長擱置壽命。該聚合物之矽烷單體部份應該以用以形成聚合物之單體之0.1至 50莫耳％存在。變化聚合物中矽烷量影響組合物之效能性質。該聚合物可以以乳液或分散液般添加於水。倘若該聚合物爲乳液，將需要一些乳化劑。 -6- 本紙張尺度適用中國國家標準（CNTS ) A4規格（210X297公釐） ---------批衣------------^ - - * - (請先閲讀背面之注意事項再填寫本頁) A7 B7 406100 五、發明说明（4 ) 用於此之聚合物包括但不限於乙烯聚合物，丙烯酸聚合物，乙烯丙烯酸聚合物，聚胺酯，聚醯胺，環氧化物，聚苯乙晞’聚酯，乙缔醋，聚烯，聚乙烯，聚丙缔及醇酸物。亦可以使用至少二種不同單體之共聚物。矽烷酯基（即 RMil^/OR1)34)最常經由伸烷基連接於聚合物。該聚合物之分子量應該介於1，000及三百萬之間。當使用自由基添加聚合作用時，用以摻入聚合物之單體有機官能矽烷説明實例包括丙烯酸根烷基烷氧矽烷，甲丙烯酸根烷基烷氧矽烷或乙缔基烷氧矽烷單體，如3_甲基丙烯酸氧丙基三異丙氧矽烷，3-甲基两烯酸氧丙基三異丁氧矽烷，3-甲基丙烯酸氧丙基三辛氧矽烷，乙烯基三異丁氧矽烷，乙缔基三正癸氧矽烷及乙晞基三特丁氧矽烷。其它可聚合矽烷，如順丁缔二酸酯官能之矽烷，亦可以使用。矽烷基末端之聚合物係由反應鏈轉移劑形成，如3_巯丙基三異丁氧矽烷。當以縮合聚合作用形成聚合物時，用以摻合聚合物之單體有機官能矽烷說明實例包括3-胺丙基三異丙氧矽烷，N_ (2-胺乙基）-3-胺丙基二異丁氧矽烷，4_巯丁基二甲基辛基氧矽烷，3-異氰酸根丙基三_二級·丁氧矽烷，及3縮水甘油氧丙基曱基二戍氧矽烷。以縮合聚合作用形成之聚合物包括聚胺酯，環氧化物，聚酯，乙烯酯，聚尿素，聚醯胺和類似型態之聚合物。泫矽烷可以接枝或封端於現存聚合物上，或者可以是生產聚合物中之共單體。 I---------1衣-----ί ------Φ • - - - * . (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs _ 4061G0; 5. Description of the invention (1)' Background of the invention Due to the environmental protection of other curing technologies, health and safety concerns have increased. Basic water-curable compositions are becoming increasingly interesting. Such compositions have excellent weather resistance, chemical resistance, and water resistance, because the silane group is connected to the polymer bond with a carbon. Silicon bond, rather than a unstable carbon-oxygen-silicon bond; With a system for physically adding silicate or silane, it has significantly improved water resistance, alkali resistance and acid resistance. However, one of the disadvantages of water-curable silylated polymer compositions is that they are easily cross-linked, especially if the water in the stele is dispersed, under normal preparation and handling and storage conditions. Result 'This type of composition is relatively poor. The dark life is likely to limit its wide commercial acceptance, and it will keep the use of the siliconized polymer at a very low siliconized concentration, typically in hydrated polymer products. Medium is less than 1.0% by weight. Adjusting water-curable compositions to mitigate early crosslinking problems is described in U.S. Patent No. 4,526,930, which describes more water-stable, 'melt-processable thermoplastic polymers with hydrolyzable silane moieties. These silane-based polymers are composed only of The organic titanate with at least one hydrolyzable group is activated by reaction or made water-curable, and the ester group is exchanged with silane. Although the titanate acts as a crushing alkanol condensation catalyst, it is dispersed in a solid olefin-acrylate matrix, not in water. Untested Japanese Patent Application No. 6025502 describes a composition including a polymer emulsion by adding a water-insoluble tin catalyst (a diorganotin carboxylate) after emulsion polymerization. Obtained from silylated ethylene polymers. However, for this type of film, add non-water soluble -4- l · ----; ----- install ----- 1 order ^ ------ line * (please read the back first Please note this page before filling in this page} This paper size applies the China National Standard (CNS) A4 specification (210X297 mm) V. Description of the invention (A7 Catalyzed by 100% tin catalyst is not suitable because of homogeneous catalyst With the emulsion polymer mixture, there are defects such as the formation of pits and particles on the surface, and the crosslinking in the film structure. In addition, the β 垸 has at least 8 carbons and Usually an alkoxy group with a linear structure. This Japanese patent application also describes an indiscriminate curing catalyst commonly used for silane / ester hydrolysis and condensation reactions. Similar examples of silane ester catalysts and silanol-containing compositions can It is found in this document that it reveals that the catalyst is dissolved in an organic solvent-based system to determine proper curing. For example, diorganotin bicarbonate-based organosilicon compounds have been known for a long time for catalysts to react. However, despite its proven use, diorganotin bicarbonate suffers from several disadvantages. This is the instability of the compound, as shown by the loss of activity when placed on hold, especially in a wet environment. This phenomenon is even more pronounced when the catalyst is formed from an aqueous emulsion. Many tin compounds can also be hydrolyzed during extended storage, and Transformed into a catalytic form. 1 And, there is a clear need for a component, a water-based dispersing stone-based calcined polymer system and system with good stability during storage in water, which produces a good quality film when applied and dried Abstract of the Invention The present invention provides a water-dispersible or emulsifiable curable polymer composition, a preparation method and a use method thereof. The polymer has at least an oxygen-burning material hydrolyzable group and it clearly faces the challenges of the above problems. The present invention It relates to the composition and manufacturing method of pitted polymer compositions, which can be cured by organometallic catalysts and have good stability during storage in water. These compositions also include catalysts, water and other ingredients as required. The composition can be used for coating -5- 'paper size ϋ Chinese National Standard (c " nS) I.. ^ ----------- ^ f-(Please read the back (Please fill in this page again for the matters needing attention)) Ministry of Economic Affairs _ Central Standards Bureau employee consumer cooperation · Social printing Department of the Ministry of Economic Affairs Central Standards Bureau employee consumer cooperation Du printed -406100 ____ _B7____ V. Description of the invention (3) 'Adhesives and Sealants》 —Example The application is glass fiber glue. The shelf life of the composition is at least 12 months. The shelf life of these compositions is at least 24 months. Brief description of the drawings Figure 1 shows a stainless steel acrylic latex coating on stainless steel. It is cured by hydrolytically stable water-miscible and water-dispersible catalyst. Figure 2 shows an ethylene acrylic latex coating on stainless steel, which is cured by hydrolytically stable water-insoluble catalyst. DETAILED DESCRIPTION OF THE INVENTION The curable aqueous composition of the present invention The materials include: (I) a stable water-dispersible curable polymer containing sterically hindered siloxysilane groups, accounting for 0.1 to 75% by weight of the total composition; (II) water-dispersible or water-soluble organic metal Catalyst, 0.1 to 10% by weight of the total composition; (III) Water, 99.8 to 24.9% by weight; and (IV) other ingredients as needed. (I) Polymer The polymer-based water-dispersible or emulsifiable curable polymer used herein has a pendant and / or terminal silyl group (ie, an alkoxysilane), at least some of which are pendant and / or terminal Suan Hyun§ is based on the mysterious burning of three-dimensional obstruction. Broken entertainment: The steric hindrance of vinegar avoids the hydrolysis of silane esters and allows longer shelf life. The silane monomer portion of the polymer should be present at 0.1 to 50 mole% of the monomers used to form the polymer. Varying the amount of silane in the polymer affects the performance properties of the composition. The polymer can be added to water as an emulsion or dispersion. If the polymer is an emulsion, some emulsifier will be required. -6- This paper size applies to the Chinese National Standard (CNTS) A4 specification (210X297 mm) --------- Approval of clothes ------------ ^--*-(Please Read the notes on the back before filling this page) A7 B7 406100 V. Description of the invention (4) The polymers used for this include, but are not limited to, ethylene polymers, acrylic polymers, ethylene acrylic polymers, polyurethanes, polyamides, Epoxides, Poly (phenylene terephthalate) polyester, Ethylene, Polyethylene, Polyethylene, Polypropylene and Alkyd. Copolymers of at least two different monomers can also be used. Silyl ester groups (ie RMil ^ / OR1) 34) are most often attached to the polymer via an alkylene group. The molecular weight of the polymer should be between 1,000 and three million. Illustrative examples of monomeric organic functional silanes used to incorporate polymers when using free radical addition polymerization include acrylate alkyl alkoxy silane, methacrylate alkoxy silane or ethylene alkoxy silane monomers, Such as 3-propyl methacrylate triisopropoxysilane, 3-methyldienoyl oxypropyl triisobutoxysilane, 3-methacrylic oxypropyl trioctyloxysilane, vinyl triisobutoxy Silane, Ethyltri-n-decoxysilane and Ethyltritert-butoxysilane. Other polymerizable silanes, such as maleate-functional silanes, can also be used. Silyl-terminated polymers are formed from reactive chain transfer agents, such as 3-mercaptopropyltriisobutoxysilane. Examples of organic functional silanes used to blend polymers when forming polymers by condensation polymerization include 3-aminopropyltriisopropoxysilane, N_ (2-aminoethyl) -3-aminopropyl Diisobutoxysilane, 4-mercaptobutyldimethyloctyloxysilane, 3-isocyanatopropyltri-secondary · butoxysilane, and 3-glycidyloxypropylfluorenyldioxane. Polymers formed by condensation polymerization include polyurethanes, epoxides, polyesters, vinyl esters, polyureas, polyamides and similar types of polymers. Perylene silane can be grafted or capped on an existing polymer, or it can be a comonomer in the production polymer. I --------- 1 衣 ----- ί ------ Φ •---*. (Please read the notes on the back before filling out this page) Staff of the Central Standards Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives

406100 A7 __________B7_ 五、發明説明（5 ) (請先閱讀背面之注意事項再填寫本頁) 此外，聚合物之懸掛和/或末端矽烷基可以以結構 ^•^(WOh-aSiR3表示，其中R1爲主體阻礙之直鏈或支鏈組態C3_C1〇燒基；R2爲i至} 〇個碳原子之一價烴基；r3爲伸燒基，伸芳基，伸芳烷基或聚合物主體本身，條件爲該 SiR3係經由Si-C鍵結合於聚合物；a爲〇，1或2。使用作爲上述化學式中R1之適當立體阻礙直鏈烴基實例包括η-丁基’ η-戍基，n_己基，η·庚基，n_辛基，n•壬基， η-癸基等，及如環戊基，環己基，環庚基，環辛基，二環庚基等之環系反應基β作爲R 1之適當,支鍵烴基實例爲淀基 ’如異辛基，3-甲基戊基，丨，5_二甲基己基，4_甲基_2•丙基等。最佳R1爲低於5個碳原子之立體阻礙基，低於4個碳原子更佳’如異丙基’二級丁基，異丁基及二級壬基。經濟部中央標隼局員工消費合作社印製 R-爲1至1 0個碳_原子之一價烴，例如淀基（例如甲基，乙基，丙基，辛基或癸基）或芳基（例如苯基，芊基或甲苯基）。R3係將矽烷懸掛或末端基鍵結於聚合物本體之基，可以爲直鏈或支鏈烷基，芳烷基或芳基，通常具1至18個碳原子’其上可以具取代基或可以爲該聚合物本身。矽原子係經由R3上之矽碳鍵結合於聚合物，其提供該矽烷化聚合物水解及熱力安定性。R3基之取代基可以包括以如氧，氣或硫取代碳原子之取代基，條件爲鄰近矽之碳原子未被取代。其它取代基包括以画素原子，氮，硫，氧取代連接於碳之氫之取代基，及有機官能基，如氰，尿素，酯，臨胺，羰氧等。聚合物可以以該技藝中已知之任何聚合技術製備，如懸 • 8 - 本纸張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） A7 406100 --------- 五、發明説明（6 ) 汗液來：’界面聚合，溶液聚合或乳液聚合作用。乙烯系不飽和早體在某些界面活性劑存在下之乳液聚合作用對於乙烯基和丙烯酸聚合物而言係較佳之聚合技術，因爲如此 (成之礼膠聚合物水性分散液能夠直接使用，或在製備本發明〈水性組合物具最少處理。這些聚合作用可以如同於該技藝中已知般進行。、適以分散於水中之聚合物經常摻入溶解基，如非離子，陰離子及陽離子基。非離子基包括胺基，經基，幾基，聚氧化晞等。陰離子基包括硫酸鹽，_酸鹽，㈣鹽等。陽離子基包括質子化胺，四級銨鹽等,。以上非離子溶解基與陽離子或陰離子基任一之結合物亦可以使用。聚合物分散液可以以該技藝中已知之技術製備。含具JL體阻礙烷氧基之矽烷基之聚合物乳液能夠以使用該技藝中已知之乳化劑及技術製備。用於此之乳化劑包括非離子，陰離子及陽離子界面活性劑或非離子與陰離子或陽離子界面活性劑之混合物。非離子界面活性劑之實例包括聚氧乙烯烷基醚，聚氧乙烯烷基苯基醚，聚氧乙烯脂肪酸酯，花楸丹脂肪酸酯，及聚氧乙晞花楸丹脂肪酸酯◊陰離子界面活性劑之實例包括脂肪酸鹽，燒基硫酸酯鹽，坡基苯磺酸鹽’烷基磷酸鹽’烷基晞丙基硫酸酯鹽及聚氧乙缔燒基續酸醋。陽離子界面活性劑之實例包括四級按鹽，如長鍵燒基二甲基按鹽’長鍵院基爷基二甲棊按鹽，及二 (長鏈烷基）二甲基銨鹽β本發明中有用之界面活性劑進一步列表可以是1994年麥克考道（MeCutcheon)所著之第1册： -9 - 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ..---裝-----^丨訂^------旅 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作杜印製經濟部中央標準局員工消費合作社印製 406100 A7 __^_B7 五、發明説明（7 ) 乳化劑及清潔劑（Vol. 1: Emulsifiers and Detergents)，1994 年北美版（製造糖果出版公司（The Manufacturing Confectioner Publishing Co.，）葛蘭洛克（Glen Rock》，併入本文供參考。乳化劑應該以聚合物重量之0,05至30重量％間存在，聚合物組合物之〇·2至20重量％更佳。406100 A7 __________B7_ V. Description of the invention (5) (Please read the precautions on the back before filling out this page) In addition, the polymer suspension and / or terminal silane group can be structured ^ • ^ (WOh-aSiR3, where R1 is Straight chain or branched chain configuration of host hindering C3_C10 alkyl group; R2 is a monovalent hydrocarbon group of i to} 0 carbon atoms; r3 is alkylene group, alkylene group, alkylene group or polymer host itself, conditions Is that the SiR3 is bonded to the polymer via a Si-C bond; a is 0, 1 or 2. Examples of suitable stereo-blocking straight-chain hydrocarbon groups that are used as R1 in the above chemical formula include n-butyl 'n-fluorenyl, n-hexyl , Η · heptyl, n_octyl, n • nonyl, η-decyl, etc., and ring system reactive groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, dicycloheptyl, etc. β As appropriate for R1, examples of branched hydrocarbon groups are y'yl, such as isooctyl, 3-methylpentyl, 5-dimethylhexyl, 4-methyl_2 • propyl, etc. The best R1 is Stereo hindering groups with less than 5 carbon atoms, and better with less than 4 carbon atoms, such as isopropyl, secondary butyl, isobutyl, and secondary nonyl. Employees of the Central Bureau of Standards, Ministry of Economic Affairs Cooperatives print monovalent hydrocarbons with R- of 1 to 10 carbon atoms, such as hydroxy (such as methyl, ethyl, propyl, octyl, or decyl) or aryl (such as phenyl, fluorenyl) Or tolyl). R3 is a silane pendant or terminal group bonded to the polymer body. It can be a straight or branched chain alkyl, aralkyl or aryl group, usually with 1 to 18 carbon atoms. It may have a substituent or it may be the polymer itself. The silicon atom is bonded to the polymer via a silicon-carbon bond on R3, which provides the silylated polymer with hydrolysis and thermal stability. The substituent of the R3 group may include, for example, oxygen , Carbon or carbon atoms are replaced by carbon or carbon atoms, provided that the carbon atoms adjacent to silicon are unsubstituted. Other substituents include substituting hydrogen atoms attached to carbon with pixel atoms, nitrogen, sulfur, and oxygen, and organic functional groups, Such as cyanide, urea, ester, amine, carbonyl oxide, etc. The polymer can be prepared by any polymerization technology known in the art, such as suspended • 8-This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) ) A7 406100 --------- V. Description of Invention (6) Khan Here: 'Interfacial polymerization, solution polymerization or emulsion polymerization. Emulsion polymerization of ethylenically unsaturated precursors in the presence of certain surfactants is a better polymerization technology for vinyl and acrylic polymers because of this (into Zhejia polymer aqueous dispersion can be used directly, or in the preparation of the "aqueous composition of the present invention with minimal processing. These polymerizations can be carried out as known in the art. Polymers suitable for dispersion in water are often mixed Dissolving groups, such as non-ionic, anionic and cationic groups. Non-ionic groups include amine groups, warp groups, several groups, polyfluorene oxide, etc. Anionic groups include sulfates, salts, phosphonium salts, and the like. Cationic groups include protonated amines, quaternary ammonium salts, and the like. Combinations of the above non-ionic dissolving groups and either cationic or anionic groups can also be used. Polymer dispersions can be prepared by techniques known in the art. Polymer emulsions containing silane groups with JL-blocking alkoxy groups can be prepared using emulsifiers and techniques known in the art. Emulsifiers used herein include nonionic, anionic and cationic surfactants or mixtures of nonionic and anionic or cationic surfactants. Examples of non-ionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, lantana fatty acid esters, and polyoxyethylene lantana fatty acid esters. Examples of the anionic surfactant include a fatty acid salt, a thiosulfate salt, a polybenzenesulfonate 'alkyl phosphate', alkyl propyl sulfate, and a polyoxyethylene sulfonate. Examples of cationic surfactants include quaternary press salts, such as long bond alkyl dimethyl salt, long bond alkyl dimethyl dimethyl sulfonium salt, and bis (long chain alkyl) dimethyl ammonium salt. A further list of useful surfactants in the invention can be published in the first volume of MeCutcheon in 1994: -9-The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ..-- -Pack ----- ^ 丨 Order ^ ------ Brigade (Please read the notes on the back before filling out this page) Staff Consumer Co-operation of the Central Standards Bureau of the Ministry of Economic Affairs Printed 406100 A7 __ ^ _ B7 V. Description of the Invention (7) Emulsifiers and Detergents (Vol. 1: Emulsifiers and Detergents), 1994 North American Edition (The Manufacturing Confectioner Publishing Co.) Glen Rock (Glen Rock ", incorporated herein by reference. Emulsifiers should be present at from 0.05 to 30% by weight of the polymer, more preferably from 0.2 to 20% by weight of the polymer composition.

界面活性劑之適當HLB(親水·親油平衡）經選擇相當於將乳化之特定矽規化聚合物之HLB。一物質之最佳HLB選擇方法對於諳熟該技藝者係已知，並執述於ICI美國公司（icIThe appropriate HLB (hydrophilic-lipophilic balance) of the surfactant is selected to correspond to the HLB of the specific silicon-regulated polymer to be emulsified. The best HLB selection method for a substance is known to those skilled in the art and is described by ICI American Corporation (icI

Americas Inc.)之"HLB 系統（The HLB'System)··中。含立體阻礙烷氧化矽烷基之安定水可分散或可乳化可固化聚合物應該以總組合物之0.1至75重量％存在。 (Π)觸媒本發明以使用水溶性或可乳化固化觸媒固化此聚合物，而非先前與矽烷化聚合物之水性組合物一起使用，而解決先前技藝之問題。適用於此之觸媒係水解安定，水可乳化或水溶性有機金屬觸媒’如水解安定之有機鈦酸鹽，有機錫，螯化鈥，鋁及結化合物及其結合物。水解安定表示該有機金屬觸媒在水存在下，於介於55和 8.5間之pH充分安定，使得低於50%之有機金屬觸媒在12個月期間内失去活性。由於共價鍵結和/或配位鍵結之配位子解離進入水中，導致觸媒自溶液沉澱或形成鈍性金屬物，如金屬氧化物，因而有機金屬觸媒失去活性。水溶性表示在室溫之水溶解度大於2重量。/。。重要的是 -10- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公fp------ I---------裝-----.——訂-------娘 - - - - , (請先閲讀背面之注意事項再填寫本頁) 406100Americas Inc.) &Quot; The HLB'System ". The stable water-dispersible or emulsifiable curable polymer containing a sterically hindered alkoxysilane group should be present at 0.1 to 75% by weight of the total composition. (Π) Catalyst The present invention solves the problems of the prior art by using a water-soluble or emulsifiable curing catalyst to cure the polymer instead of using it with an aqueous composition of a silylated polymer. Suitable catalysts are hydrolytically stable, water-emulsifiable or water-soluble organometallic catalysts, such as hydrolytically stable organic titanates, organotin, chelation, aluminum, and compounds and combinations thereof. Hydrolytic stability means that the organometallic catalyst is sufficiently stable at a pH between 55 and 8.5 in the presence of water, so that less than 50% of the organometallic catalyst loses its activity within 12 months. As the covalently bonded and / or coordinated ligands dissociate into the water, the catalyst precipitates from solution or forms passive metal objects, such as metal oxides, and the organometallic catalyst loses its activity. Water solubility means that the water solubility at room temperature is greater than 2 weight. /. . The important thing is that -10- this paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 male fp -------- I --------- installation -----.---- order- ------ Mother----, (Please read the notes on the back before filling this page) 406100

五、發明説明（8 經濟部中央標準局員工消費合作社印製 =可扎化觸媒將需要添加乳化劑。乳化劑及乳 '孔化聚4物中所述者相同，條件爲用以製造觸媒乳 ?化劑與用以製造聚合物乳液之乳化 :: 較切乳化觸媒佳，因爲該可乳化觸媒可能可間几降’並影響組合物之固化及性質。用於此之有機金屬觸媒之_般結構係以R、MLc表示，其中Μ爲過渡金屬離子’如鈦，錫，鋁或锆，至1〇個碳原子之-價㈣；L可以各爲共價或配位鍵結於金展離予之相同或不同配位子；1)爲〇至4 ;:c爲1至6，條件爲b+c 係介於2及6之間。實例之R4爲烷基（例如甲基，乙基，辛基或癸基），芳基 (例如苯基或茬基），取代之芳基（例如氣苯基，甲苯基或氰笨基）或芳烷基（例如芊基或苯乙基）。實例之L爲硫，硫醇鹽’水，羥基’氨，醯胺或較佳爲1至2〇個碳原子之雜原子未取代伸烷基，伸芳基或伸芳烷基，其上具取代基，且可以具如氧，氮或硫之雜原子。該取代基包括由素，氤 ’硫’氧’氰’尿素，酯’醯胺及類似基。L可以含大於 1個能夠與金屬離子共價鍵結之雜原子。用於此之鈦酸鹽螯合劑一般結構係以 r4o X - ——Υ 〇 Ή η Γ 1 1 -t\ L 1 Y 1 ' X 11 - 良紙張尺度適用中國國家標準（CNS ) A4規格（210X297公瘦） I ：--：---裝-----Γ訂 ----^---Λ (請先閲讀背面之注意事項再填寫本頁) 406100 五、發明説明（9 ) 其中X表示含氧或氮之官能基，γ表示1至1〇個碳原子之烷基鏈，R4表示氩或1至10個碳原予之烷基，芳基或芳烷基。溶解性螯合鈦酸鹽及水性螯合鈦酸鹽之實例爲二羥基雙 [2-羥丙酸根（2-)-〇1，〇2]鈦酸鹽，混合鈦原酸酯錯合物，乙醯丙酮酸鹽螯合物，雙（乙基-3-氧代丁醇基_〇ι，〇3)雙（2_丙酵基）鈦，及鈦之醇胺錯合物。其它水解安定鈦觸媒係列於費付（Feld) et al.，”鈥化學（The Chemistry of Titaniuq)" (1 965)中。較佳之觸媒爲TYZ9R@131，tYZ〇RLA及 TYZOR 101，商業上可取自杜邦德奈麥司公司（DuP〇nt de Nemours & Co.) 〇可乳化，_水解安定之有機錫觸媒對於本發明亦是有用的。其實例爲具Sn-S或Sn=S鍵之巯醇，硫醇或硫化物形式二有機錫。此外，説明之實例爲R2Sn(SCOO)形式化合物，如 (n-C4H9)2Sn(SCH2COO) ; R2Sn(SS)形式化合物，如 (n-C8H17)2Sn(SCH2CO〇CH2CH2OCOCH2S) ； R2Sn(SCH2COOR)2 形式化合物，如（n-C4H9)2Sn(SCH2COOC8H17-iso)2 ; RSn(SCH2COOR)3形式化合物，如（n-C4H9) Sn(SCH2COOC8H17-iso)3 ;R2Sn=S化合物，如（n-C8H17)2Sn=S等；及 I----------^-------.^1------^ - * * ' (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製V. Description of the invention (8 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs = Emulsifiers will need to be added with emulsifiers. The emulsifiers and emulsions are the same as those described in the "Polymerization Polymers", provided that they are used to make contacts. Emulsifiers and emulsifiers used to make polymer emulsions :: better than cutting emulsification catalysts, because the emulsifiable catalysts may decrease in time and affect the curing and properties of the composition. Organometals used for this The general structure of the catalyst is represented by R and MLc, where M is a transition metal ion such as titanium, tin, aluminum or zirconium, to -10 valences of 10 carbon atoms; L may each be a covalent or coordination bond The same or different ligands at Jinzhanliu; 1) are 0 to 4;: c is 1 to 6, provided that b + c is between 2 and 6. Examples of R4 are alkyl (e.g. methyl, ethyl, octyl or decyl), aryl (e.g. phenyl or stubyl), substituted aryl (e.g. phenyl, tolyl or cyano) or Aralkyl (such as fluorenyl or phenethyl). Examples of L are sulfur, thiolate 'water, hydroxyl' ammonia, ammonium or heteroatom unsubstituted alkylene, arylene or aralkyl, preferably having 1 to 20 carbon atoms. Substituents, and may have heteroatoms such as oxygen, nitrogen or sulfur. The substituent includes sulfonium, thio, thio, oxy, cyano, urea, ester, fluoramine, and the like. L may contain more than one heteroatom capable of covalently bonding to a metal ion. The general structure of the titanate chelating agent used is r4o X-—— 〇〇 η Γ 1 1 -t \ L 1 Y 1 'X 11-Good paper size applies to China National Standard (CNS) A4 specification (210X297 (Male thin) I:-: --- -------------- order ---- ^ --- Λ (Please read the precautions on the back before filling out this page) 406100 V. Description of the invention (9) X represents a functional group containing oxygen or nitrogen, γ represents an alkyl chain of 1 to 10 carbon atoms, and R4 represents argon or an alkyl group of 1 to 10 carbon atoms, an aryl group or an aralkyl group. Examples of soluble chelated titanates and aqueous chelated titanates are dihydroxybis [2-hydroxypropionate (2-)-0.1, 02] titanates, mixed titanate complexes, Acetylpyruvate chelate, bis (ethyl-3-oxobutanol group, 03) bis (2-propionyl) titanium, and titanium alcohol amine complex. Other series of hydrolyzed stable titanium catalysts are in Feld et al., "The Chemistry of Titaniuq" (1 965). The preferred catalysts are TYZ9R @ 131, tYZ〇RLA and TYZOR 101, Commercially available from DuPont de Nemours & Co. Emulsifiable, hydrolytically stable organotin catalysts are also useful for the present invention. Examples are Sn-S or Sn = S bond in the form of mercaptan, thiol or sulfide diorganotin. In addition, the illustrated examples are compounds in the form of R2Sn (SCOO), such as (n-C4H9) 2Sn (SCH2COO); compounds in the form of R2Sn (SS), such as (n-C8H17) 2Sn (SCH2CO〇CH2CH2OCOCH2S); R2Sn (SCH2COOR) 2 form compounds, such as (n-C4H9) 2Sn (SCH2COOC8H17-iso) 2; RSn (SCH2COOR) 3 form compounds, such as (n-C4H9) Sn ( SCH2COOC8H17-iso) 3; R2Sn = S compounds, such as (n-C8H17) 2Sn = S, etc .; and I ---------- ^ -------. ^ 1 ----- -^-* * '(Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

RszSn Z 1/ W 其中R5s=l-8個竣原子之烷基或芳基；W=-S-或-0- ·’且 -12- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公变) 經濟部中央標準局貝工消費合作社印製 406100__B7__ 五、發明説明（1〇) Z=-CH2CH(CH2OH)-或·<：Η2(：Η(ΟΗ)(：Η2-。較佳之實例爲取自威特可（Witco)之 FOMREZ UL-1，UL-22及 UL-32及二丁基錫雙（1-硫代甘油）。觸媒應該以總組合物之至少〇. 1重量。/。存在。低於〇. 1 %之觸媒金屬經常對於反應無重要影響。一般而言，爲了聚合物之成本及顏色整體，觸媒能夠以0.1至20重量％使用， 0.1至10重量％較佳。 (III) 水水應該佔組合物之99.8至24.9重量。/P。水可以在合併組份 (I)及（II)前添加於（I)或（lip · (IV) 其它成份本水性組合物之較佳pH範圍爲約5·5至8.5，7.0最佳。因而，通常該水性分散液需要亦含少量緩衝劑。能夠使用任何傳統緩衝劑或該技藝中已知此類用劑之混合物，如醋酸鈉及碳酸氩鈉。緩衝劑應該以每100份聚合物約1 〇份重量比存在。此外，本發明之組合物可以包括適量稠化劑（如羧甲基纖維素，甲基纖維素，羥乙基纖維素；聚乙烯醇，聚丙烯酸），填充劑，色素，染料，熱安定劑，防腐劑，滲透劑 (如氨水）及其它一般添加劑。此外，商用水基底聚合物分散液能夠與本發明之水可分散組合物摻合，倘若其不導致不安定性。實例包括傳統已知之水合丙烯酸聚合物，纖維素，胺基塑料，胺酯，聚酯，醇酸，乙氧基系統，矽酮或其混合物。 L----------^-------ITt------^ -- ^ - (請先閲讀背面之注意事項再填寫本頁)RszSn Z 1 / W where R5s = 1 to 8 alkyl radicals or aryl radicals; W = -S- or -0- · 'and -12- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the Shellfish Consumer Cooperative, 406100__B7__ V. Description of the invention (1〇) Z = -CH2CH (CH2OH)-or < Examples are FOMREZ UL-1, UL-22 and UL-32 and dibutyltin bis (1-thioglycerol) taken from Witco. The catalyst should be at least 0.1 weight of the total composition./ Exist. The catalyst metal below 0.1% often has no significant effect on the reaction. Generally speaking, for the cost and color of the polymer as a whole, the catalyst can be used at 0.1 to 20% by weight, and 0.1 to 10% by weight (III) Water should be 99.8 to 24.9% by weight of the composition. / P. Water can be added to (I) or (lip · (IV) other ingredients before the combination of components (I) and (II)) The preferred pH range of the composition is about 5.5 to 8.5, with 7.0 being the best. Therefore, the aqueous dispersion usually needs to also contain a small amount of buffer. Any conventional buffer or the technique can be used Mixtures of such agents are known in the art, such as sodium acetate and sodium bicarbonate. The buffering agent should be present at about 10 parts by weight per 100 parts of polymer. In addition, the composition of the present invention may include a suitable amount of thickener (such as Carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose; polyvinyl alcohol, polyacrylic acid), fillers, pigments, dyes, heat stabilizers, preservatives, penetrants (such as ammonia) and other general additives. In addition, commercial water-based polymer dispersions can be blended with the water-dispersible composition of the present invention as long as they do not cause instability. Examples include conventionally known hydrated acrylic polymers, cellulose, amine-based plastics, amine esters, polymers Esters, alkyds, ethoxy systems, silicones or mixtures thereof. L ---------- ^ ------- ITt ------ ^-^-(please first (Read the notes on the back and fill out this page)

40610ο a7 親水親油平衡（H L B )範圍適於乳化觸媒和/或聚合物之非離子界面活性劑亦可以用於此。視需要之成份可以在任何時候添加，雖然在大部份例中，觸媒應該最後添加。製造方法本發明之組合物係以將觸媒添加於矽燒化聚合物分散液或礼液製備。用以混合這些組份之方法並不嚴苛，任何常用之低切剪設備，如葉片或漿式混合器是適當的。用途/優點該組合物在室溫貯存1 2個月期間不會造粒或凝結。該組合物較佳擱置壽命爲至少24個月本發明之組合物意欲當使用時固化。其可以在各種溫度範圍固化，包括室溫固化或高溫固化。此固化可以以該技藝之標準方法完成。能夠因應各種目的使用該組合物，例如油漆，黏合劑，塗層材料，接合劑及密封劑，並利用上述本發明組合物之優良特徵。該固化組合物形成具優良光澤，耐溶劑性，黏性，硬度，耐磨性及耐損性之塗層。本發明之組合物係形成薄膜，並有益以在各種受質，如金屬，木材，織物，皮革及陶磁上形成保護性和/或防水塗層，一種根據本發明之組合物，取決於色素或其它傳統組份之存在，可以使用作爲底層漆，清澈塗層，印刷骨接合劑，膠劑，塗層或底漆。具良好透明度和耐溶劑性之固化薄膜可以形成且盔表面斑驳。可以產生耐洗塗層。 ’ 乳膠薄膜之MEK雙重磨擦測試，凝膠含量及NMp油漆黏 _ -14 - ——— ____ _ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公f ) L 裝------訂------線 • * J (請先閱讀背面之注意事項再填寫本頁} 經濟部中央標準局員工消費合作杜印製 A7 4〇βι〇〇40610ο a7 Hydrophilic-lipophilic balance (H L B) Nonionic surfactants suitable for emulsifying catalysts and / or polymers can also be used here. The optional ingredients can be added at any time, although in most cases the catalyst should be added last. Manufacturing method The composition of the present invention is prepared by adding a catalyst to a silicon-polymerized polymer dispersion or a gift solution. The method used to mix these components is not critical, and any commonly used low-cut shear equipment such as a blade or paddle mixer is suitable. Uses / Benefits The composition does not granulate or coagulate during storage at room temperature for 12 months. The composition preferably has a shelf life of at least 24 months. The composition of the present invention is intended to cure when used. It can be cured in various temperature ranges, including room temperature or high temperature. This curing can be done in a standard way using this technique. The composition can be used for various purposes, such as paints, adhesives, coating materials, bonding agents, and sealants, and take advantage of the excellent characteristics of the composition of the present invention described above. The cured composition forms a coating having excellent gloss, solvent resistance, viscosity, hardness, abrasion resistance and damage resistance. The composition of the present invention forms a film and is beneficial for forming protective and / or waterproof coatings on various substrates, such as metals, wood, fabrics, leather, and ceramics. A composition according to the present invention, depending on the pigment or The existence of other traditional components can be used as a primer, clear coating, printed bone cement, glue, coating or primer. A cured film with good transparency and solvent resistance can be formed and the surface of the helmet is mottled. Can produce washable coatings. '' MEK double friction test of latex film, gel content and NMp paint adhesion _ -14-——— ____ _ This paper size is applicable to China National Standard (CNS) A4 specification (210X297 male f) L installed ------ Order ------ line • * J (Please read the notes on the back before filling out this page} Staff Consumer Cooperation of the Central Bureau of Standards, Ministry of Economic Affairs Du printed A7 4〇βι〇〇

五、發明説明（12 經濟部中央裙準局員工消费合作社印製性測試説明由本發明中使用之觸媒產生之加強矽氧烷交聯。根據本發明製成之固化組合物在溫和環境下固化短時間後’其MEK耐磨擦力（根據ASTMD 4752-87進行）爲至少2〇 ’至少40較佳。根據沙巴塔（Sabata) et ，黏合劑科技期刊 (JournajM^hesion Science and Technology, 7 (11)，1153. 1170 (1993)中所述之nmp步骤進行，該固化組合物具改良之黏性爲至少10分鐘。至少2〇分鐘較佳，併入本文供參考〇實例以下實例係用以幫助本發明之意•義而非限制本發明。這些實例中所有份數係重量比。 ίΑΙιϋ矣對照實例I-νιιι製備矽烷化聚合物氣備含3 -甲基丙締基氧丙基三異丙氧基梦炫，硬炫a作爲共單體之乙烯丙埽系乳膠。乙酸乙烯酯/丙烯酸丁酯/碎纪單體之莫耳比例分別爲86·3/9_8/3.9。乳膠係以半連續批次方法產生。將419.5份去離子水，26.5份1@6031€八-897，V. Description of the invention (12 Print test of the Consumer Cooperative of the Central Skirt Bureau of the Ministry of Economic Affairs shows that the reinforced siloxane is produced by the catalyst used in the present invention. The curing composition made according to the present invention is cured in a mild environment After a short time, its MEK abrasion resistance (according to ASTMD 4752-87) is preferably at least 20 'and at least 40. According to Sabata et, Journaj Mhhesion Science and Technology, 7 ( 11), 1153. 1170 (1993), the nmp step is performed, and the cured composition has an improved viscosity of at least 10 minutes. At least 20 minutes is preferred, which is incorporated herein by reference. Examples The following examples are for The meaning of the present invention is to help but not limit the present invention. All parts in these examples are weight ratios. ΙΑιϋ 矣 Comparative Example I-νιιια Preparation of a silylated polymer Gas preparation containing 3-methylpropyloxypropyltriiso Propoxy Mengxuan and Dangxuan a as comonomers of ethylene-acrylic acid-based latex. The molar ratios of vinyl acetate / butyl acrylate / broken monomers are 86.3 / 9_8 / 3.9. Continuous batch method is generated. 419.5 parts deionized water, 26.5 parts 1 @ 6031 € Eight-897,

3份 Igepal CA-630，2份碳酸氫鈉及 2.5份 Natrosol 250 MXR 置入裝置塔頂冷凝器及金屬葉片攪拌器之丨公升反應器。以熱罩將系統加熱至65°C並以氮滌氣。然後添加丨8份過疏酸錢及3.6份Alipal EP-110。於1分鐘内添加1〇%單體混合物（以混合385份乙酸乙稀醋，65份丙缔酸丁醋及％份或 4莫耳％ 3-甲基丙烯基氧丙基三異丙氧基矽烷製備將溫度維持低於75°C。添加後，任由反應再持續15分鐘。將攪拌速率保持於150 rpm。以此批次方法製備晶種乳膠後， -15- 本紙張尺度適用中國國家揉準（CNS ) A4規格（2丨0X297公釐）丨裝訂線丨 --詩先閔讀背面之注意事項再ίλ寫本頁}Three parts of Igepal CA-630, two parts of sodium bicarbonate and 2.5 parts of Natrosol 250 MXR were placed in the liter reactor of the tower top condenser and metal blade stirrer. The system was heated to 65 ° C with a hot hood and purged with nitrogen. Then add 8 parts of acid and 3.6 parts of Alipal EP-110. 10% monomer mixture (to mix 385 parts of ethyl acetate, 65 parts of butyric acid vinegar and% parts or 4 mole% of 3-methacryloxypropyltriisopropoxyl) within 1 minute Silane preparation keeps the temperature below 75 ° C. After the addition, the reaction is allowed to continue for another 15 minutes. The stirring rate is maintained at 150 rpm. After preparing the seed latex in this batch method, -15- This paper is applicable to China Knitting accuracy (CNS) A4 specification (2 丨 0X297mm) 丨 Binding line 丨 --Notes on the back of Shi Xianmin before writing this page}

ο C D ) 經濟部中央榡準局員工哺費合作.社印製五、發明説明（13 以容許反應熱被移除之速率，在3小時期間添加剩餘之9〇% 單體混合物，並將溫度維持於75τ ^當單體混合物完全添. 加後，將乳液維持於75130分鐘❶並添加ο」份三級丁基化過氧氩-70(0.1克）。以1小時期間添加乃份2%甲醛次硫酸鈉各液，邊將溫度維持於75°C。反應完全後，以添5%氨溶液將反應溶液之pH調整至7.5。使用不同矽烷單體重複合成含3_甲基丙烯基氧丙基三異丙基矽烷（A)之步驟。這些矽烷單體爲3_甲基丙埽基氧丙基三異丁氧基矽垸（B)，3-甲基丙缔基氧丙基三辛氧基矽烷（c) ，乙烯基三異丁氧基矽烷（D)及乙烯基三特丁氧基矽烷（E) 。變化矽烷單體之用量。在這些實例中，使用介於〇17至 4莫耳％間之矽烷濃度，利用均相方法（將聚合物成核，繼之供料單體），核心-殼技術，或以最後丨〇%聚合作用之延遲矽烷單體添加。固體含量介於44〇/0至56%之間。顆粒大小介於0.1至I微米之間。各單體用以製備矽烷化聚合物之用量列於表I中。作爲對照，重覆這些步驟合成含3_甲基丙烯基氧丙基三甲氧基矽烷（X)，乙烯基三乙氧基矽烷（Y)及無矽烷之乳液來β物β該>5夕淀化聚合物在製備期間含4莫耳％凝膠碎拔^ 含3重量％矽烷γ之矽烷化聚合物得到黏度爲74〇 cp之乳膠。當珍燒Y濃度升至聚合物之7.7 wt %時，該乳膠得到高黏度（5800 cp)，在包圍環境貯存i星期後凝膠。用以製備對照實例所使用聚合物之各單體量列於下表中。 16- 本^氏張尺度適用中國國家標準（CNS > A4钱抵ί 210X297公揍一 .. 裝 .丨訂---7---線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消资合作社印製 406100 B7 五、發明説明（14) 表I 用以製備本發明及對照實例之矽烷化聚合物乳液之單體重量及莫耳％實例醋酸乙烯酯丙烯酸丁酯编敢矽烷重量％莫耳％重量％莫耳°/。重量％莫耳％ 1 A 12.8 3.9 74.6 86.3 12.6 9.8 2 A 1.5 0.40 84.6 89.7 13.9 9.9 Λ A 1.0 0.27 85.0 89.8 14.0 9.9 4 A 10.0 2.85 85.0 93.5 5.0 3.7 5 B 14.3 3.9 73.3 86.3 12.4 9.8 6 B 1.63 0.40 84.5 89.7 13.9 9.9 7 B 1.0 0.24 85.0 89.8 14.0 9.9 8 B 10.0 2.53 85.0 93.8 5.0 3.7 9 C 19.6 3.9 68.8 , 86.3 11.6 9.8 10 C 2.4 0.40 83.9 89.7 13.7 9.9 11 C 1.0 0.17 85.0 89.9 14.0 9.9 12 C 10.0 1.65 85.0 88.5 5.0 9.8 13 D 11.0 3.9 76.2 86.3 12.8 9.8 14 D 1.2 0.4 84.9 89.7 13.9 9.9 15 D 10.0 3.2 85.0 87.1 5.0 9.7 16 E 1 1.0 3.9 76.2 86.3 12.8 9.8 17 E 1.2 0.4 84.9 89.7 13.9 9.9 18 E 10.0 3.2 85.0 87.1 5.0 9.7 對照醋酸乙缔酯丙烯酸丁酯聚合物％编號矽烷重量％莫耳％重量％莫耳％重量％ .莫耳％於乳液中 I X 10.0 3.9 77.0 86.3 13.0 9.8 50.2 II X 1.1 0.4 85.0 89.7 13.9 9.9 50.2 III X 1.0 0.3 7 85.0 89.7 14.0 9.9 50.0 IV X 10.0 3.5 85.0 86.8 5.0 9.7 50.0 V Y 7.9 3.9 78.8 86.3 13.3 9.8 50.2 VI Y 0.84 0.4 85.2 89.7 14.0 9.9 50.2 VII Y 15.4 8.0 71.7 82.1 12.9 9.9 50.2 VIII 無 0.0 0.0 85.0 90.0 15.0 10.0 50.0 ___ -17- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公着） L---------t衣-------------鍊 , - . . (請先閱讀背面之注意事項再¾寫本頁) A7 B7 406100 五、發明説明（15 ) 實例19-31-組合物之搁置安定性以組合物黏度及29Si NMR分光鏡測定含立體阻礙烷氧基之水合聚合物在固化觸媒存在下之攔置壽命安定性。將本發明之觸媒添加於表I中本發明之矽烷化聚合物乳液，並以漿攪拌5分鐘。於表II及III中重複添加於矽烷化聚合物之觸媒形式及份量（重量％)。使用布魯克費得（Brookfield) 黏度計，#3軸，根據ASTMD 2 196-86測定組合物之黏度，以座泊（cp)表示。表II中之實例19-28在2個月期間黏..度僅微量提高。例如 ’實例9中所述之矽烷化聚合物在5重量％ TYZOR 131存在下’於室溫貯存2個月後，黏度僅自960提高至1060 cp。（實例21)。當使用大量無立體阻礙之烷氧矽烷基製備矽烷化聚合物乳液時，該組合物在製備後於短期間内（即1星期）凝膠’即使當無固化觸媒存在時（如同於對照實例ΧΙ_ΧΙΠ 中所述）。含立體阻礙之聚合物乳液在無固化觸媒存在下是安定的，如對照實例IX及X中所示。亦使用29Si分光鏡測定含立體阻礙烷氧矽烷基之聚合物乳液在固化觸媒存在下之安定性。此技術以測量矽烷酯基 [-Si(OR)3]在進行任何交聯或固化反應前後之量，直接測量組合物中發生之固化量。下表m中之實例29_31表示矽燒酯基未進行任何固化，因而在室溫貯存大於4〇天後存在 100%矽物質。當無固化觸媒存在時，先前技藝之乳液是安定的，如對照實例XIV-XVI中所示。各紙張尺度適财S ϋ家標準（CNS ) Α4祕（21Gxl^7公董 I.----------裝-----^丨訂^---7---涑 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央橾準局員工消費合作社印製 406100 a?ο CD) Employees of the Central Government Bureau of the Ministry of Economic Affairs pay for cooperation. Printed by the agency 5. Invention Description (13 At a rate that allows reaction heat to be removed, the remaining 90% monomer mixture is added over a period of 3 hours, and the temperature is Maintained at 75τ ^ when the monomer mixture was completely added. After the addition, the emulsion was maintained at 75130 minutes and ο ″ parts of tertiary butyl peroxy argon-70 (0.1 g) was added. 2% was added over a period of 1 hour. Each solution of sodium formaldehyde sulfoxylate was maintained at a temperature of 75 ° C. After the reaction was completed, the pH of the reaction solution was adjusted to 7.5 by adding a 5% ammonia solution. Repeated synthesis of 3-methacryloxy containing different silane monomers Propyltriisopropylsilane (A). These silane monomers are 3-methylpropanyloxypropyltriisobutoxysilane (B), 3-methylpropyloxypropyltriazine Octyloxysilane (c), vinyltriisobutoxysilane (D) and vinyltriterbutoxysilane (E). The amount of silane monomer is varied. In these examples, a range between 017 to Silane concentration between 4 mol%, using homogeneous method (nucleating polymer followed by monomer supply), core-shell technology, or Addition of delayed silane monomers after 0% polymerization. Solid content is between 44/0 and 56%. Particle size is between 0.1 and 1 micron. The amount of each monomer used to prepare the silane polymer They are listed in Table I. As a control, these steps were repeated to synthesize 3-methacryloxypropyltrimethoxysilane (X), vinyltriethoxysilane (Y), and non-silane-containing emulsions. β > The precipitated polymer containing 4 mole% gel was broken during the preparation ^ The silylated polymer containing 3% by weight of silane γ gave a latex having a viscosity of 74 cp. When the concentration of sintered Y rose to At 7.7 wt% of the polymer, the latex obtained a high viscosity (5800 cp) and gelled after storage for 1 week in a surrounding environment. The amount of each monomer used to prepare the polymer used in the comparative example is listed in the table below. 16- This standard is applicable to Chinese national standards (CNS > A4 money arrives 210X297 public money). Packing. 丨 Order --- 7 --- line (Please read the precautions on the back before filling this page) Ministry of Economic Affairs Printed by the Central Standards Bureau Consumers' Cooperatives 406100 B7 V. Description of Invention (14) Table I is used to prepare the present invention and comparative examples Monomer weight and mole% of the silylated polymer emulsion Example Vinyl acetate butyl acrylate braided silane weight% mole% weight% mole% °% weight mole% 1 A 12.8 3.9 74.6 86.3 12.6 9.8 2 A 1.5 0.40 84.6 89.7 13.9 9.9 Λ A 1.0 0.27 85.0 89.8 14.0 9.9 4 A 10.0 2.85 85.0 93.5 5.0 3.7 5 B 14.3 3.9 73.3 86.3 12.4 9.8 6 B 1.63 0.40 84.5 89.7 13.9 9.9 7 B 1.0 0.24 85.0 89.8 14.0 9.9 8 B 10.0 2.53 85.0 93.8 5.0 3.7 9 C 19.6 3.9 68.8, 86.3 11.6 9.8 10 C 2.4 0.40 83.9 89.7 13.7 9.9 11 C 1.0 0.17 85.0 89.9 14.0 9.9 12 C 10.0 1.65 85.0 88.5 5.0 9.8 13 D 11.0 3.9 76.2 86.3 12.8 9.8 14 D 1.2 0.4 84.9 89.7 13.9 9.9 15 D 10.0 3.2 85.0 87.1 5.0 9.7 16 E 1 1.0 3.9 76.2 86.3 12.8 9.8 17 E 1.2 0.4 84.9 89.7 13.9 9.9 18 E 10.0 3.2 85.0 87.1 5.0 9.7 Control ethylene acetate butyl acrylate polymer% No. Silane Molar% Molar% Molar% by weight. Molar% in emulsion IX 10.0 3.9 77.0 86.3 13.0 9.8 50.2 II X 1.1 0.4 85.0 89.7 13.9 9.9 50.2 III X 1.0 0.3 7 85.0 89.7 14.0 9.9 50.0 IV X 10.0 3.5 85.0 86.8 5.0 9.7 50.0 VY 7.9 3.9 78.8 86.3 13.3 9.8 50.2 VI Y 0.84 0.4 85.2 89.7 14.0 9.9 50.2 VII Y 15.4 8.0 71.7 82.1 12.9 9.9 50.2 VIII None 0.0 0.0 85.0 90.0 15.0 10.0 50.0 ___ -17- This paper size applies to China National Standard (CNS) A4 specification (210X297) L --------- t-shirt ------------- chain, -.. (Please read the precautions on the back before writing this page) A7 B7 406100 V. Description of the invention (15) Example 19-31-Stability of the composition by composition Viscosity and 29Si NMR spectroscope Stability of alkoxy hydrated polymers in the presence of curing catalysts. The catalyst of the present invention was added to the silylated polymer emulsion of the present invention in Table I and stirred for 5 minutes with a slurry. In Tables II and III, the catalyst form and the amount (% by weight) of the silylated polymer were repeatedly added. The viscosity of the composition was measured using a Brookfield viscometer, # 3 axis according to ASTM D 2 196-86, expressed in ber (cp). Examples 19-28 in Table II showed a slight increase in viscosity over a 2 month period. For example, the viscosity of the silylated polymer described in Example 9 was increased from 960 to 1060 cp after storage at room temperature for 2 months in the presence of 5% by weight of TYZOR 131. (Example 21). When a large number of alkoxysilyl groups without steric hindrance are used to prepare the silylated polymer emulsion, the composition gels in a short period of time (ie, 1 week) after preparation, even when no curing catalyst is present (as in the comparative example) (XΙ_ΧΙΠ). The polymer emulsion containing steric hindrance is stable in the absence of a curing catalyst, as shown in Comparative Examples IX and X. The stability of polymer emulsions containing sterically hindered alkoxysilyl groups in the presence of curing catalyst was also measured using a 29Si spectroscope. This technique directly measures the amount of curing that occurs in the composition by measuring the amount of silane ester [-Si (OR) 3] before and after any crosslinking or curing reaction. Examples 29-31 in the following table m indicate that the silicon sintered ester group has not undergone any curing, and therefore 100% silicon substance is present after storage at room temperature for more than 40 days. When no curing catalyst is present, the emulsion of the prior art is stable, as shown in Comparative Example XIV-XVI. Each paper size is suitable for financial standards (CNS) Α4 secret (21Gxl ^ 7 public director I .---------- installation ----- ^ 丨 order ^ --- 7 --- 涑(Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 406100 a?

五、發明説明（16) 表II有無觸媒存在下矽烷化聚合物之黏度由 Λ：.丨城缺 ··* * Υί,Ι 越技音毐 n mn 2 mo. 3 m〇^ m〇营例编號乳液實例觸媒重量％ 0 mo、 2 mo. 3 mo. 6 mo 19 1 TYZOR 131， 5 100 140 -· 20 5 TYZOR 131’ 5 200 280 -- " 21 9 TYZOR 131， 5 960 1060 -- * · 22 13 TYZOR 131， 5 580 840 -- " 23 16 TYZOR 131， 5 1500 1700 -- ~ * 24 2 TYZOR 131， 1 1660 1800 -- *- 25 6 TYZOR 131, 1 1180 1100 -- ·* - 26 10 TYZOR 131, 1 760 1060 -- -- 27 14 TYZOR 131, 1 1520 1800 -- -- 28 17 TYZOR 131, 1 1140 _ 1340 -- -- IX 13 無，0 1140 -- 1180 -- X 14 無，0 2210’ -- -- 2020 XI 1 無，0 膠凝化 XII IV 無，0 膠凝化 XIII VII 無，0 膠凝化 K----------裝-------訂 (請先閱讀背面之注意事項寫本頁) 表III-矽烷化聚合物及對照實例之29Si分析聚合物Si(OR)3 例编號產生乳液之實例觸媒％時間（天）莫耳％ 29 8 TYZOR 131, 5 41 100 30 12 TYZOR 131, 5 52 100 31 15 TYZOR 131,5 47 100 XIV 8 無 120 100 XV 12 無 210 100 XVI 15 無 120 100 聚合物Si(OR)3表示未反應形成矽氧烷鍵或交聯（Si-0-Si)之矽烷基酯量實例32-36-固化組合物之凝膠含量 -19- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐）線經濟部中央標準局員工消費合作社印製 406100 -------—__五、發明説明（17) A7 以薄膜之凝膠含量説明固化觸媒於促進含立體阻礙烷氧矽烷基之聚合物交聯之效果。凝膠含量係藉著將本發明戋對照實例之组合物倒入培養皿中，並任其在室溫固化十天_ 十星期測定。將1克乾燥（固化）薄膜移除並分割爲重量（^) 〈2、=塊’置入纖維素嵌環中並以甲基乙基酮（MEK)溶劑在氮氣壓下使用沙克司列（S〇xhlet)萃取器萃取。萃取後，保留於嵌環中之樣品乾燥，並將剩餘之樣品稱重~,)。以以下方程式測定凝膠含量： _ 凝膠含量（％)=[(WI-W2)/W丨]X100,其节W丨及w2如上。表IV中之數據表示含立體阻礙烷氧矽烷基之聚合物當在觸媒存在下固化時（實例32_35)，其凝膠含量顯著高於當無觸媒存在下固化時（對照實例xvn-xx)高。例如，實例5中敘述之聚合物當在5%TYZ0R 131存在下及無觸媒存在下固化時，其凝膠含量分別爲75.6及49.9。即使長期固化，如在室溫十星期，未產生等高固化程度。因爲聚合物Μ之三級丁氧矽烷基被立體阻礙，所以即使在固化觸媒存在下仍未固化。不含矽烷之對照實例，如對照實例νιπ*所述之聚合物，甚至當任其靜置十星期並未交聯。乾燥聚合物 VIII之凝膠含量爲〇%。 -----裝-----ί訂----:---線 (請先閲讀背面之注意事項界€寫本頁} 經濟部中央標準局員工消費合作社印製 _____________ - 20 - 本3^尺度_ 中國 CNS ) A4規格（210X297公f ) ' —------ A7 B7 406100 五、發明説明（18) 表iv自矽烷化聚合物乳液所鑄薄膜在有無固化觸媒存在下之凝膠含量例編號乳液實例编號觸媒％凝膠含量1 32 1 TYZOR 131，5 25.41 33 5 TYZOR 131, 5 75.61 34 9 TYZOR 131, 5 78.31 35 13 TYZOR 131, 5 53.31 36 16 TYZOR 131, 5 〇1 XVII 1 無 13.12 XVIII 5 無 49.92 XIX 9 無 69.72 XX 13 無 ‘ 23.82 XXI 16 無 0.92 1在室溫固化1 0天 2在室溫固化10星期實例37-42-薄膜品質薄膜品質或外觀相當地視固化觸媒之選擇而定。例如實例37-38中之水溶性觸媒或實例39-42中本發明之乳化觸媒，當與含立體阻礙烷氧矽烷基之聚合劑乳液結合使用時，得到如圖1中所示之平滑且無表面缺陷之固化薄膜，其表示實例37-42’分別爲平板B-G，平板A表示無觸媒存在之平板。所使用觸媒之形式及份量如表V中所示。觸媒乳液係以一相容性乳化劑乳化有機錫觸媒製備，所以形成立即可分散水性系統之安定乳液。觸媒乳液之實例爲 Atochem PE-1013，Witco FOMREZ UL-1 , FOMREZ UL 22及UL-32。於5克各液態觸媒添加7.1克IGEPAL CA-987， 21 - 本紙張尺度適用中國國家標隼（CNS〉A4規格（210X 297公釐） L----------批衣-------.玎------線. - . . , . (請先閲讀背面之注意事項再填寫本頁} 經濟部中夬標準局員工消費合作社印製 406100 A7 B7 五、發明説明（19) 繼之添加7.9克雙重蒸餾水。劇烈攪拌混合物約3〇分鐘。 PE-1013產生安定微乳液。f〇MREZ UL-1，UL-22及 UL-32 形成安定之乳液。於磷酸化不銹鋼板上使用下拉棒鑄製薄膜。乾燥薄膜厚度爲2密耳[50_8微米]。將薄膜在23°C，50%濕度固化7天。當在水合分散液聚合物系統中使用常用以固化溶劑基底或含矽烷基純聚合物之觸媒時，如二烷基錫羧酸酯，胺或鈦酸酯’該固化薄膜含許多缺陷，如表V及圖2中對照實例XXIII-XXVII中所示，其中平板戸_〇相當於對照實例 XXIII-XXVII ’平板A無觸媒。這些•實例及圖説明自本發明所述之基選擇固化觸媒之重要性，以達成均勻固化1無缺陷之薄膜。本發明之組合物實用性係由耐溶劑及固化組合物黏性之改良表示。耐溶劑性係於MEK，重磨擦中測定，如astm D 4752-87中所述。薄膜以焙烤或乾燥固化。焙烤環境爲 121°C20分鐘，繼之在23°C及50%相對濕度7天。表VI中之數據表示本發明之觸媒量對於固化薄膜之耐溶劑性是重要的。含正體阻礙烷氧矽烷基且無觸媒之聚合物薄膜之mek 雙重磨擦僅爲12至22，如對照實例χχχν_χχνιπ中所示。俾若聚合物不含碎炫基，耐溶劑性非常差，ΜΕκ雙重磨擦僅爲5至9。自含立體阻礙縣料基及本發明之觸媒之聚合物乳液轉製之薄膜具良好耐溶劑性。此外，耐溶劑性非常良好，倘若觸媒濃度不太低。例如，自本發明之組合物轉製，且 ^ 裝訂----^---線 (請先W讀背面之注意事項再填寫本頁) 經濟部中央棣準局員工消費合作.社印製 -22- 406100 A7 B7 五、發明説明（20) 其中觸媒濃度爲0.5%或更高之薄膜，其MEK雙重磨擦介於 21及128之間，其中該薄膜係以焙烤或空氣乾燥方法固化，如實例45至50，及53至86中所示。在低觸媒濃度（如 0.05%)，薄膜失去一些耐溶劑性，如實例43，44，5 1及52 中所示。老化本發明之組合物延長擱置壽命對於固化薄膜之耐溶劑性無不良影響。例如，在鋒膜前將組合物老化2 至8星期，得到之耐溶劑性等於或優於自新製組合物鑄製之薄膜，如實例59至78中所示。表V 在本發明及對照實例之水溶啤或水可分散觸媒存在下固化之矽烷化聚合物乳液之塗層薄膜品質 ---------批衣-------'1T------0 - - - > (請先閔讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作杜印製 -23- 實例编號乳液實例編號觸媒％薄膜品質 37 9 TYZOR131,5 平滑薄膜無缺點 38 9 TYZOR LA, 5 平滑薄膜無缺點 39 9 PE-1013,1 平滑薄膜無缺點 40 9 FOMREZUL-1, 1 平滑薄膜無缺點 41 9 FOMREZ UL-22, 1 平滑薄膜無缺點 42 9 FOMREZ UL-32, 1 平滑薄膜無缺點 XXII 9 順丁烯二酸二丁酯，1 白色顆粒 XXIII 9 二月桂酸二丁酯錫，1 薄膜内坑洞 XXIV 9 二乙酸二丁酯錫，1 薄膜内大量坑洞 XXV 9 TYZOR GBA, 5 坑洞且薄膜褪色 XXVI 9 4，巧氧二-2，1-乙烷二基）薄膜内凝結粒子雙嗎17林，1 XXVII 9 無平滑薄膜，無缺點 1 在23°C及50%相對濕度固化7天。本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐）經濟部中央標準局員工消費合作社印製 A7 __ 406100_b7_ 五、發明説明（21 ) 表VI以甲基乙基酮雙重磨擦測定矽烷化聚合物之固化薄膜之耐溶劑性實例聚合物组合物老化 MEK雙重編號乳液觸媒％固化形式 B/f固化（星期）磨擦 43 5 TYZOR 131，0.05 烘烤 0 11 44 5 TYZOR 131, 0.05 乾燥 0 18 45 5 TYZOR 131, 0.5 烘烤 0 31 46 5 TYZOR 131，0.5 乾燥 0 47 47 5 TYZOR 131, 1.0 烘烤 0 37 48 5 TYZOR 131, 1.0 乾燥 0 47 49 5 TYZOR 131, 2.0 烘烤； 0 41 50 5 TYZOR 13 1, 2.0 乾燥 0 50 51 5 TYZOR LA, 0.05 烘烤 0 11 52 5 TYZOR LA, 0.05 乾燥 0 15 53 5 TYZOR LA, 0.5 烘烤 0 21 54 5 TYZOR LA, 0.5 乾燥 0 30 55 5 TYZOR LA, 0.5 烘烤 0 41 56 5 TYZOR LA, 1.0 乾燥 0 33 57 5 TYZOR LA, 2.0 烘烤 0 39 58 5 TYZOR LA, 2.0 乾燥 0 43 59 1 TYZOR 131, 5 烘烤 0 38 60 1 TYZOR 131, 5 烘烤 2 80 61 1 TYZOR 131, 5 烘烤 4 119 62 1 TYZOR 131, 5 烘烤 8 99 -24- n -I.....I 1— - -I - i I 11- .1 i -1 士^II · - - . V—► ·Γ· n n -. i . (請先閱讀背面之注意事項再填寫本頁) 本紙伕尺度適用中國國家標準（CNS ) A4規格（2I0X 297公釐）經濟部中央標準局員工消費合作社印製 A7 406100_B7 五、發明説明（22) 實例聚合物組合物老化 MEK雙重編號乳液觸媒％固化形式 B/f固化（星期）磨擦 63 5 TYZOR 131，5 烘烤 0 50 64 5 TYZOR 131, 5 烘烤 2 97 65 5 TYZOR 131, 5 烘烤 4 97 66 5 TYZOR 131, 5 烘烤 8 125 67 9 TYZOR 131，5 烘烤 0 50 68 9 TYZOR 13 1,5 烘烤 2 81 69 9 TYZOR 131, 5 烘烤 4 103 70 9 TYZOR 131, 5 烘烤 8 128 71 13 TYZOR 131, 5 烘烤 0 38 72 13 TYZOR 131, 5 烘烤： 2 74 73 13 TYZOR 131，5 烘丨烤 4 100 74 13 TYZOR 13 1,5 烘烤 8 97 75 16 TYZOR 13 1,5 烘烤 0 29 76 16 TYZOR 131, 5 烘烤 2 47 77 16 TYZOR 13 1,5 烘烤 4 25 78 16 TYZOR 13 1,5 烘烤 8 67 79 9 FOMREZ-UL-l, 1 烘烤 0 51 80 9 FOMREZ UL-1, 1 乾燥 0 39 81 9 FOMREZ UL-22, 1 烘烤 0 53 82 9 FOMREZ UL-22, 1 乾燥 0 48 83 9 FOMREZ UL-32, 1 烘烤 0 49 -25- 」---------坤衣-------1T (請先閲讀背面之注意事項寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 406100 A7 B7五、發明説明（23 ) 實例聚合物組合物老化 MEK雙重编號乳液觸媒％固化形式 B/f固化（星期）磨擦 84 9 FOMREZ UL-32, 1 乾燥 0 41 85 9 PE-1013, 1 烘烤 0 30 86 9 PE-1013, 1 乾燥 0 22 XXVIII VII 無，〇烘烤 0 5 XXIX VII 無，〇乾燥 0 8 XXX VIII TYZOR 13 1,2 烘烤 0 7 XXXI VIII TYZOR 13 1,2 乾燥 0 7 XXXII VIII TYZOR LA, 2 烘乾 0 7 XXXIII VIII TYZOR LA, 2 乾燥 0 9 XXXIV 1 無埤烤 0 22 XXXV 5 無烘烤 0 27 XXXVI 9 無烘烤 0 19 XXXVII 16 無烘烤 0 12 XXXVIII 2 無烘烤 0 8 XXXIX 6 無烘烤 0 17 XL 10 無烘烤 0 14 XLI 14 無烘烤 0 14 XLII 17 無烘烤 0 7 XLIII VI 無烘烤 0 31 XLIV 5 無烘烤 0 7 XLV 5 無乾燥 0 7 (請先閱讀背面之注意事項再¥'寫本頁) 經濟部中央標準局員工消費合作社印製實例87-91-黏性特徵固化薄膜黏性隨本發明之觸媒濃度提高而改良，如表VII 中所示。本發明之組合物固化薄膜黏性係以NMP油漆黏性測試測定，如上所示。由於TYZOR LA觸媒量自0.05提高至2.0重量％，NMP黏性分別自5.6改良至56，如實例88-91 中所示。 -26- 本紙法尺度適用中國國家標準（CNS ) A4現格（2丨0X 297公釐） 406100 A7 B7五、發明説明（24 ) 表VII-薄膜油漆黏性數據矽烷化聚合物實例编號實例編號觸媒％ NMP油漆黏性，分鐘 87 7 TYZOR 131，0.05 5.5 88 7 TYZOR LA, 0.05 5.6 89 7 TYZOR LA, 0.5 18 90 7 TYZOR LA, 1.0 39 91 7 TYZOR LA, 2.0 56 ----------裝-----1訂--------線 . . m (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 -27- 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨OXW7公釐）V. Description of the invention (16) Table II The viscosity of the silylated polymer in the presence or absence of a catalyst is represented by Λ :. 丨城 * · * * Υί, Ι 越技音毐 n mn 2 mo. 3 m〇 ^ m〇营Example Number Emulsion Example Catalyst Weight% 0 mo, 2 mo. 3 mo. 6 mo 19 1 TYZOR 131, 5 100 140-· 20 5 TYZOR 131 '5 200 280-" 21 9 TYZOR 131, 5 960 1060 -* · 22 13 TYZOR 131, 5 580 840-" 23 16 TYZOR 131, 5 1500 1700-~ * 24 2 TYZOR 131, 1 1660 1800-*-25 6 TYZOR 131, 1 1180 1100- *-26 10 TYZOR 131, 1 760 1060--27 14 TYZOR 131, 1 1520 1800--28 17 TYZOR 131, 1 1140 _ 1340--IX 13 None, 0 1140-1180- -X 14 None, 0 2210 '--2020 XI 1 None, 0 Gelation XII IV None, 0 Gelation XIII VII None, 0 Gelation K ---------- pack- ------ Order (please read the note on the back to write this page) Table III- 29Si analysis polymer Si (OR) of silylated polymer and comparative example 3 case number emulsion example catalyst% time (Days) Mole% 29 8 TYZOR 131, 5 41 100 30 12 TYZOR 131, 5 52 100 31 15 TYZOR 131, 5 47 100 XIV 8 None 120 100 XV 12 None 210 100 XVI 15 None 120 100 Polymer Si (OR) 3 means unreacted to form a siloxane bond or crosslink (Si-0 -Si) Examples of the amount of silyl esters 32-36- Gel content of the cured composition-19- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) Employees of the Central Bureau of Standards of the Ministry of Economic Affairs Printed by the cooperative 406100 ---------__ V. Description of the invention (17) A7 The gel content of the film is used to explain the effect of the curing catalyst in promoting the cross-linking of polymers containing sterically hindered alkoxysilyl groups. The gel content was measured by pouring the composition of the 戋 control example of the present invention into a petri dish and allowing it to cure at room temperature for ten days to ten weeks. 1 gram of dried (cured) film was removed and divided into weights (^) <2, = pieces' were placed in cellulose rings and the use of methyl ethyl ketone (MEK) solvent under nitrogen pressure Soxhlet) extractor. After extraction, the samples retained in the ring are dried, and the remaining samples are weighed ~,). The gel content is determined by the following equation: _ Gel content (%) = [(WI-W2) / W 丨] X100, the sections W 丨 and w2 are as above. The data in Table IV indicates that when the polymer containing sterically hindered alkoxysilyl group is cured in the presence of a catalyst (Examples 32_35), its gel content is significantly higher than when cured in the absence of a catalyst (Comparative Example xvn-xx )high. For example, when the polymer described in Example 5 is cured in the presence of 5% TYZOR 131 and in the absence of a catalyst, its gel content is 75.6 and 49.9, respectively. Even if it is cured for a long time, such as at room temperature for ten weeks, no high degree of curing is produced. Because the tertiary butoxysilyl group of polymer M is sterically hindered, it is not cured even in the presence of a curing catalyst. Comparative examples without silane, such as the polymer described in Comparative Example νιπ *, were left uncrosslinked even when left standing for ten weeks. The gel content of the dried polymer VIII was 0%. ----- Installation ----- Order ----: --- line (Please read the notes on the back of the page first to write this page} Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs _____________-20 -This 3 Dimension _ China CNS) A4 size (210X297 male f) '-------- A7 B7 406100 V. Description of the invention (18) Table iv. The presence or absence of curing catalyst for the film cast from the silylated polymer emulsion Existing gel content Example number Emulsion example number Catalyst% Gel content 1 32 1 TYZOR 131, 5 25.41 33 5 TYZOR 131, 5 75.61 34 9 TYZOR 131, 5 78.31 35 13 TYZOR 131, 5 53.31 36 16 TYZOR 131, 5 〇1 XVII 1 None 13.12 XVIII 5 None 49.92 XIX 9 None 69.72 XX 13 None '23.82 XXI 16 None 0.92 1 Cured at room temperature 1 0 days 2 Cured at room temperature for 10 weeks Example 37-42-Film quality Film quality Or the appearance depends on the choice of curing catalyst. For example, the water-soluble catalyst in Examples 37-38 or the emulsifying catalyst of the present invention in Examples 39-42, when used in combination with a polymerizer emulsion containing a sterically hindered alkoxysilyl group, a smoothness as shown in FIG. 1 is obtained. And for the cured film without surface defects, the examples 37-42 'are respectively flat plate BG, and flat plate A is a flat plate without catalyst. The form and weight of the catalyst used are shown in Table V. The catalyst emulsion is prepared by emulsifying the organotin catalyst with a compatible emulsifier, so as to form a stable emulsion of an immediately dispersible aqueous system. Examples of catalyst emulsions are Atochem PE-1013, Witco FOMREZ UL-1, FOMREZ UL 22 and UL-32. Add 7.1 grams of IGEPA CA-987 to 5 grams of each liquid catalyst, 21-This paper size is applicable to Chinese national standard (CNS> A4 specification (210X 297 mm) L ---------- batch clothing- ------. 玎 ------ line.-..,. (Please read the notes on the back before filling out this page} Printed by the Employees Cooperative of the China Standards Bureau of the Ministry of Economic Affairs 406100 A7 B7 V. Description of the invention (19) 7.9 g of double distilled water is added. The mixture is stirred vigorously for about 30 minutes. PE-1013 produces a stable microemulsion. FMREZ UL-1, UL-22 and UL-32 form a stable emulsion. In phosphoric acid The stainless steel plate was cast with a pull-down rod. The thickness of the dried film was 2 mils [50_8 microns]. The film was cured at 23 ° C and 50% humidity for 7 days. When used in a hydrated dispersion polymer system, it is commonly used to cure Solvent-based or silane-based pure polymer catalysts, such as dialkyltin carboxylates, amines, or titanates' The cured film contains many defects, as shown in Table V and Comparative Examples XXIII-XXVII in Figure As shown in the figure, the flat plate 戸 _〇 is equivalent to the comparative example XXIII-XXVII 'Flat plate A without catalyst. These examples and diagrams are explained from the present invention. The importance of the curing catalyst is selected to achieve uniform curing of the 1 defect-free film. The practicality of the composition of the present invention is expressed by the improvement of solvent resistance and the viscosity of the cured composition. Solvent resistance is measured during MEK and heavy friction As described in astm D 4752-87. The film is cured by baking or drying. The baking environment is 121 ° C for 20 minutes, followed by 23 ° C and 50% relative humidity for 7 days. The data in Table VI indicate the touch of the present invention. The amount of solvent is important for the solvent resistance of the cured film. The mek double friction of the polymer film containing ortho-blocking alkoxysilyl group and no catalyst is only 12 to 22, as shown in the comparative example χχχν_χχνιπ. If the polymer Contains no broken base, very poor solvent resistance, MEEκ double friction is only 5 to 9. The film converted from the polymer emulsion containing three-dimensional hindered material base and the catalyst of the present invention has good solvent resistance. In addition, Solvent is very good, if the catalyst concentration is not too low. For example, converted from the composition of the present invention, and ^ binding ---- ^ --- line (please read the precautions on the back before filling this page) Economy Central Government Provincial Bureau Staff Consumption Printed by the agency-22- 406100 A7 B7 V. Description of the invention (20) The film with the catalyst concentration of 0.5% or higher has a MEK dual friction between 21 and 128, where the film is baked or The air drying method cures, as shown in Examples 45 to 50, and 53 to 86. At low catalyst concentrations (such as 0.05%), the film loses some solvent resistance, as shown in Examples 43, 44, 5 1 and 52 Aging the composition of the present invention to extend the shelf life has no adverse effect on the solvent resistance of the cured film. For example, the composition is aged for 2 to 8 weeks before the front film, and the solvent resistance obtained is equal to or better than that of a film cast from a fresh composition, as shown in Examples 59 to 78. Table V The coating film quality of the silylated polymer emulsion cured in the presence of the water-soluble beer or water-dispersible catalyst of the present invention and comparative examples --------- batch --------- ' 1T ------ 0---> (Please read the notes on the reverse side before filling out this page) Staff Cooperation Cooperation, Central Standards Bureau, Ministry of Economic Affairs, Du printed -23- Instance No. Emulsion Instance No. Catalyst% Film quality 37 9 TYZOR131,5 Smooth film without defects 38 9 TYZOR LA, 5 Smooth film without defects 39 9 PE-1013,1 Smooth film without defects 40 9 FOMREZUL-1, 1 Smooth film without defects 41 9 FOMREZ UL-22, 1 Smooth film without defects 42 9 FOMREZ UL-32, 1 Smooth film without defects XXII 9 Dibutyl maleate, 1 White particles XXIII 9 Dibutyl tin dilaurate, 1 Pit inside the film XXIV 9 Diacetic acid Dibutyltin, 1 a large number of pits in the film XXV 9 TYZOR GBA, 5 pits and the film faded XXVI 9 4, oxydi-2,1-ethanediyl) condensed particles in the film Shuangma 17 Lin, 1 XXVII 9 No smooth film, no defect 1 Cured at 23 ° C and 50% relative humidity for 7 days. This paper size is applicable to Chinese National Standard (CNS) A4 (210 × 297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 __ 406100_b7_ V. Description of the invention (21) Table VI Determination of silane by double rubbing of methyl ethyl ketone Solvent resistance of cured films of polymerized polymers Example of polymer composition aging MEK double number emulsion catalyst% curing form B / f curing (week) friction 43 5 TYZOR 131, 0.05 baking 0 11 44 5 TYZOR 131, 0.05 drying 0 18 45 5 TYZOR 131, 0.5 baking 0 31 46 5 TYZOR 131, 0.5 drying 0 47 47 5 TYZOR 131, 1.0 baking 0 37 48 5 TYZOR 131, 1.0 drying 0 47 49 5 TYZOR 131, 2.0 baking; 0 41 50 5 TYZOR 13 1, 2.0 Dry 0 50 51 5 TYZOR LA, 0.05 Bake 0 11 52 5 TYZOR LA, 0.05 Dry 0 15 53 5 TYZOR LA, 0.5 Bake 0 21 54 5 TYZOR LA, 0.5 Dry 0 30 55 5 TYZOR LA, 0.5 baking 0 41 56 5 TYZOR LA, 1.0 drying 0 33 57 5 TYZOR LA, 2.0 baking 0 39 58 5 TYZOR LA, 2.0 drying 0 43 59 1 TYZOR 131, 5 baking 0 38 60 1 TYZOR 131, 5 Bake 2 80 61 1 TYZOR 131, 5 Bake 4 119 62 1 TYZOR 131, 5 Bake 8 99 -24- n -I ..... I 1—--I-i I 11- .1 i -1 士 II ·--. V—► · Γ · nn-. i. (Please read the notes on the back before filling out this page) The dimensions of this paper are applicable to China National Standard (CNS) A4 specifications (2I0X 297 mm) Printed by A7 406100_B7, Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Description of the Invention (22) Example Polymer Composition Aging MEK Double Number Emulsion Catalyst% Cured Form B / f Cured (Week) Friction 63 5 TYZOR 131,5 Bake 0 50 64 5 TYZOR 131, 5 Bake 2 97 65 5 TYZOR 131, 5 Bake 4 97 66 5 TYZOR 131, 5 Bake 8 125 67 9 TYZOR 131, 5 Bake 0 50 68 9 TYZOR 13 1,5 Bake 2 81 69 9 TYZOR 131, 5 Bake 4 103 70 9 TYZOR 131, 5 Bake 8 128 71 13 TYZOR 131, 5 Bake 0 38 72 13 TYZOR 131, 5 Bake: 2 74 73 13 TYZOR 131, 5 Bake 丨 Bake 4 100 74 13 TYZOR 13 1,5 Bake 8 97 75 16 TYZOR 13 1,5 Bake 0 29 76 16 TYZOR 131, 5 Bake 2 47 77 16 TYZOR 13 1,5 Bake 4 25 78 16 TYZOR 13 1,5 Bake 8 67 79 9 FOMREZ-UL -l, 1 baking 0 51 80 9 FOMREZ UL-1, 1 dry 0 39 81 9 FOMREZ UL-22, 1 baked 0 53 82 9 FOMREZ UL-22, 1 dry 0 48 83 9 FOMREZ UL-32, 1 baked 0 49 -25- '' --------- Kunyi ------- 1T (Please read the notes on the back to write this page) This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) 406100 A7 B7 V. Description of the invention (23) Example polymer composition aging MEK double number emulsion catalyst% curing form B / f curing (week) friction 84 9 FOMREZ UL-32, 1 drying 0 41 85 9 PE-1013, 1 Bake 0 30 86 9 PE-1013, 1 Dry 0 22 XXVIII VII None, 〇 Bake 0 5 XXIX VII None, 〇 Dry 0 8 XXX VIII TYZOR 13 1,2 Bake 0 7 XXXI VIII TYZOR 13 1,2 Dry 0 7 XXXII VIII TYZOR LA, 2 Dry 0 7 XXXIII VIII TYZOR LA, 2 Dry 0 9 XXXIV 1 No grilling 0 22 XXXV 5 No baking 0 27 XXXVI 9 No baking 0 19 XXXVII 16 No baking 0 12 XXXVIII 2 No baking 0 8 XXXIX 6 No baking 0 17 XL 10 No baking 0 14 XLI 14 No baking 0 14 XLII 17 No baking 0 7 XLIII VI No baking 0 31 XLIV 5 No baking 0 7 XLV 5 No drying 0 7 (Please read the precautions on the back before ¥ 'write this page) Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 87-91-Viscosity characteristics Cured film with the touch of the present invention The vehicle concentration increased and improved as shown in Table VII. The viscosity of the cured film of the composition of the present invention is determined by the NMP paint adhesion test, as shown above. As the amount of TYZOR LA catalyst was increased from 0.05 to 2.0% by weight, the NMP viscosity was improved from 5.6 to 56, respectively, as shown in Examples 88-91. -26- The paper scale is applicable to the Chinese National Standard (CNS) A4 (2 丨 0X 297 mm) 406100 A7 B7 V. Description of the invention (24) Table VII-Film paint viscosity data Silane polymer Example number No. Catalyst% NMP paint viscosity, minutes 87 7 TYZOR 131, 0.05 5.5 88 7 TYZOR LA, 0.05 5.6 89 7 TYZOR LA, 0.5 18 90 7 TYZOR LA, 1.0 39 91 7 TYZOR LA, 2.0 56 ----- ----- install ----- 1 order -------- line: .m (Please read the notes on the back before filling this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-27 -This paper size is applicable to China National Standard (CNS) A4 (2 丨 OXW7mm)

Claims

公第8H2 712號專利申請案、口中文申請_爾(87_ A8 B8 C8 D8 丨年 ,τ :.:..-/:.1:質内k 經濟部中央榡準局貝工消費合作杜印製六、申請專利範圍 1. 一種可固化组合物，包括： (a) —安足水可分散或可乳化之可固丨聚合*，佔總組合物又0.1至75重量％，其含立體阻礙烷氧化矽烷基，具有結構爲R3SiR2a(〇Rl)3_a，其中Rl爲直鏈= 支鏈構造之立體阻礙4至01()烷基；R2爲具1至1〇個碳原子足一價烴基；R3爲伸烷基，伸芳基，伸芳烷基或孩聚合物主體本身，條件爲該SiR3係經由鍵結合於聚合物；"a I，爲數値〇，i或2 ; (b) 水可分散或水溶性水解安定性有機金屬觸媒，佔總組合物t 〇·1至10重量％，其中該觸媒之化學式爲： R4bMLc，其中μ爲過渡金屬離子；R4爲具1至1〇個碳原子I一價烴基；L可以各爲共價或配位鍵結於金屬離子之相同或不同配位子；b爲〇至4之整數；c 爲1至6之數値，條件爲b+c係介於2及6之間；及 (c) 水’佔總組合物之99.8至24.9重量。/〇。 2_根據申請專利範園第1項之組合物，其中M僅可以選自：鈦，錫，鋁或锆。 3.根據申請專利範圍第2項之組合物，其中觸媒僅可以選自：二羥基雙[2-羥丙酸根（2_)_〇1，〇2]鈦酸鹽，混合之鈦原酸酯錯合物，乙醯丙酮酸鹽螯合物，雙（乙基_3_氧代丁醇基-O1，。3) ’雙（2-丙醇基）鈦及鈦之烷醇胺錯合物。 4·根據申请專利範園第2項之组合物，其中觸媒僅可以選自：具Sn-S或Sn=S任一鍵結之巯醇，硫醇或硫化物形式之二有機錫。 5.根據申請專利範圍第1項之组合物，其中該組合物之搁本紙張尺度適用中關家標準（ CNS )八4胁（210X297公釐） A8 B8 C8 D8 406100 申請專利範圍置壽命爲至少12個月。 6·=據申請專利範圍第丨项之組合物，其額外包括一缓衡浏，量足以使組合物之pH維持介於55及85之間。 7_種由固化根據申請專利範圍第i項之組合物產生之薄膜。 8.根據申請專利範圍第i項之組各物，其中Rl具低於5個碳原子且爲支鏈。根據申请專利範圍第8項之组合物，其中Rl僅可以選自’異丁基’二級丁基，異丙基及二級戊基。 10·根據申請專利範圍第〖項之組合物，其中該水可分散或了乳化可固化聚合物係分子量介於1,000及三百萬間之石夕娱•化乙烯丙烯酸聚合物。 1L —種製造可固化组合物之方法，包括混合： (a)—安定水可分散或可乳化之可固化聚合物，佔總組合物之0.1至75重量％，其含立體阻礙烷氧化矽烷基，具有結構爲R3SiR2a(〇Rl)3_a，其中Rl爲直鏈或支鏈化之立體阻礙(：3至(：：1()烷基；R2爲具1至個碳原子之一價烴基；R3爲伸烷基，伸芳基，伸芳烷基或該聚合物主體本身，條件爲該siR3係經由Si_c鍵結合於聚合物；"a "爲數値〇，1或2 ; 0)水可分散或水溶性水解安定性有機金屬觸媒，佔總组合物之〇. 1至10重量％，其中該觸媒化學式爲： R4bMLc ’其中μ爲過渡金屬離子；R4爲具1至10個碳原予之—價烴基；L可以各爲共價或配位鍵結於至屬離子之相同或不同配位子；b爲0至4之數値；c -2- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ----------裝----— 1丨訂~----„線 ** (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印装 A8 B8 C8 D8 406100 六、申請專利範園爲1至6之數値，條件爲b+c係介於2及6之間；及 (c)水，佔總組合物之99.8至24.9重量％。 12.根據申請專利範圍第i !項之方法，其中M僅可以選自：鈥，錫，鋁或锆。 13_根據申請專利範圍第1 2項之；法，其中觸媒僅可以選自：二羥基雙[2-羥丙酸根（2-)-0^ Ο2]鈦酸鹽，混合之鈥原酸酯錯合物，乙醯丙酮螯合物，雙（乙基_3_氧代丁醇基-Ο1, 03) ’雙（2-丙醇基）鈦及鈦之烷醇胺錯合物。 14. 根據申請專利範圍第1 2項之組合物，其中觸媒僅可以選自：具Sn-S或Sn=S任一鍵結之鲩醇，硫醇或硫化物形式 …之二有機錫。 15. 根據申請專利範圍第1 1項之方法，其中該組合物之擱置奇命爲至少1 2個月。 16. 根據申請專利範圍第1 1項之方法，其額外包括一緩衝劑，：量足以使組合物之pH維持介於5.5及8.5之間。 Π.根據申請專利範圍第1 i項之方法，其額外包括固化該可固化组合物。 18.根據申請專利範圍第1 1項之方法，其中R1具低於5個碳原子且爲支鏈化者。 19_根據申請專利範圍第1 8項之方法·，其中R1係選自由異丁基，二級丁基，異丙基及二級戊基所组成之群。 20.根據申請專利範圍第1 i項之方法，其中該水可分散或可乳化可固化聚合物係分子量介於1，000及三百萬間之欢燒化乙缔丙缔酸聚合物。 -3- 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） ----------裝-----|、玎7---——1^ (請先閔讀背面之注意事項再填寫本頁〕經濟部中央標準局具工消費合作社印製No. 8H2 712 patent application, oral Chinese application_ 尔 (87_ A8 B8 C8 D8 丨 year, τ:.: ..- / :. 1: Quei K. Central Ministry of Economic Affairs, Central Bureau of Quasi Bureau, Shellfish Consumer Cooperation Du Yin System VI. Application for Patent Scope 1. A curable composition, including: (a)-Anzu water dispersible or emulsifiable curable 丨 polymerization *, which accounts for 0.1 to 75% by weight of the total composition, which contains steric hindrance An alkoxysilane group having a structure of R3SiR2a (〇R1) 3_a, where R1 is a sterically hindered 4 to 01 () alkyl group with a straight chain = branched structure; R2 is a monovalent hydrocarbon group having 1 to 10 carbon atoms; R3 is an alkylene group, an arylene group, an aralkylene group, or the polymer itself, provided that the SiR3 is bonded to the polymer via a bond; " a I, which is a number 値〇, i or 2; (b) Water-dispersible or water-soluble hydrolytically stable organometallic catalyst, which accounts for t 〇 · 1 to 10% by weight of the total composition, wherein the chemical formula of the catalyst is: R4bMLc, where μ is a transition metal ion; R4 is 1 to 1 0 carbon atoms I monovalent hydrocarbon group; L may each be the same or different ligand covalently or coordinately bonded to the metal ion; b is an integer from 0 to 4; c Is a number from 1 to 6, provided that b + c is between 2 and 6; and (c) water 'accounts for 99.8 to 24.9 weight of the total composition. The composition of item, wherein M can only be selected from: titanium, tin, aluminum or zirconium. 3. The composition according to item 2 of the patent application scope, wherein the catalyst can only be selected from: dihydroxybis [2-hydroxypropionate (2 _) _ 〇1, 02] titanate, mixed titanate complex, acetamidine pyruvate chelate, bis (ethyl-3-oxobutanol-O1, .3 ) 'Bis (2-propanol-based) titanium and alkanolamine complex of titanium. 4. The composition according to item 2 of the patent application garden, wherein the catalyst can only be selected from: Sn-S or Sn = S Any of two bonded tins in the form of mercaptan, thiol or sulfide. 5. The composition according to item 1 of the scope of patent application, wherein the paper size of the composition applies the Zhongguanjia Standard (CNS) 8 4 Threat (210X297 mm) A8 B8 C8 D8 406100 The life span of the patent application is at least 12 months. 6 · = According to the composition of the scope of patent application, item 丨, it additionally includes a slow balance, the amount is sufficient to make the combination The pH of the product is maintained between 55 and 85. 7_ Films produced by curing the composition according to item i of the scope of the patent application. 8. According to the group of items i of the scope of the patent application, R1 has a value lower than 5 carbon atoms and is branched. According to the composition of the scope of application for item 8, R1 can only be selected from 'isobutyl' secondary butyl, isopropyl and secondary pentyl. 10. According to the patent application The composition according to the scope of the item, wherein the water-dispersible or emulsifiable curable polymer is a Shi Xiyu • Ethylene Acrylic Polymer with a molecular weight between 1,000 and 3 million. 1L—a method for manufacturing a curable composition, comprising mixing: (a) —a water-dispersible or emulsifiable curable polymer, which accounts for 0.1 to 75% by weight of the total composition, and contains a stereo-blocking alkoxysilane group With a structure of R3SiR2a (〇Rl) 3_a, where R1 is a linear or branched steric hindrance (: 3 to (:: 1 () alkyl; R2 is a monovalent hydrocarbon group having 1 to 1 carbon atom; R3 Is an alkylene, an aryl, an aralkyl or the polymer itself, provided that the siR3 is bound to the polymer via a Si_c bond; " a " is a number of 値〇, 1 or 2; 0) water Dispersible or water-soluble hydrolytically stable organometallic catalyst, which accounts for 0.1 to 10% by weight of the total composition, wherein the chemical formula of the catalyst is: R4bMLc 'wherein μ is a transition metal ion; R4 has 1 to 10 carbons Originally-valent hydrocarbon group; L can be each covalent or coordinated to the same or different ligands of the ions; b is a number from 0 to 4; c -2- This paper size applies to Chinese national standards (CNS) A4 specification (210X297 mm) ---------- installation ------ 1 丨 order ~ ---- „line ** (Please read the precautions on the back first (Fill in this page again) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed A8 B8 C8 D8 406100 6. The number of patent application parks is 1 to 6, provided that b + c is between 2 and 6; and (c) Water, which accounts for 99.8 to 24.9% by weight of the total composition. 12. The method according to item i! of the scope of patent application, wherein M can only be selected from the group consisting of: tin, aluminum or zirconium. 13_ According to the scope of patent application Item 12 of the method, wherein the catalyst can only be selected from the group consisting of: dihydroxybis [2-hydroxypropionate (2-)-0 ^ Ο2] titanate, mixed with orthoester complexes, acetamidine Acetone chelate, bis (ethyl_3_oxobutanol-O1, 03) 'bis (2-propanol) titanium and alkanolamine complex of titanium. 14. According to the scope of patent application, the first The composition of item 2, wherein the catalyst can only be selected from the group consisting of fluorenol, thiol or sulfide, which has any of Sn-S or Sn = S bonding. 15. Organic tin. 15. According to item 11 of the scope of patent application Method, wherein the composition has a shelf life of at least 12 months. 16. The method according to item 11 of the scope of patent application, which additionally includes a buffer, in an amount sufficient to make the composition The pH is maintained between 5.5 and 8.5. Π. The method according to item 1 i of the patent application scope, which additionally includes curing the curable composition. 18. The method according to item 11 of the patent application scope, wherein R1 has a low At 5 carbon atoms and branched. 19_ Method according to item 18 of the scope of patent application, wherein R1 is selected from the group consisting of isobutyl, secondary butyl, isopropyl and secondary pentyl Group. 20. The method according to item 1i of the scope of patent application, wherein the water-dispersible or emulsifiable curable polymer is a flame-retardant ethylene-acrylic acid polymer having a molecular weight between 1,000 and 3 million. -3- This paper size adopts China National Standard (CNS) A4 specification (210X297 mm) ---------- installation ----- |, 玎 7 ------- 1 ^ (please Please read the notes on the back of the book before filling in this page] Printed by the Industrial Standards Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs