TW396197B - A stable aqueous dispersion, a method of preparing a fast-setting coating on a substrate and the coated material - Google Patents

A stable aqueous dispersion, a method of preparing a fast-setting coating on a substrate and the coated material Download PDF

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TW396197B
TW396197B TW087107885A TW87107885A TW396197B TW 396197 B TW396197 B TW 396197B TW 087107885 A TW087107885 A TW 087107885A TW 87107885 A TW87107885 A TW 87107885A TW 396197 B TW396197 B TW 396197B
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polymer
group
aqueous dispersion
stable aqueous
substrate
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John K Harris
Gene D Rose
Donald L Schmidt
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/63—Macromolecular compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/923—Ethylenic monomers containing at least one salt group

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Description

A7 ________B7_ 五、發明説明（1 ) 本發明係關於當施用於適當基質時可形成耐水快速硬 化塗層之穩定水性分散液。 塗層通常用於提供防護遮蔽層用於例如地板'汽車、 房屋外至及内室及塗布地面。例如地板之保護性塗層由 1950年中葉以來已知。多種早期塗布材料係使用以石油或 環烷烴為主的溶劑施用但因溶劑之毒性及可燃故不合所需 以水為主之合成乳液組合物如苯乙烯樹脂乳液，苯乙 烯-丙烯酸酯共聚物樹脂乳液及丙烯酸酯乳液於丨969年中 期開發缓慢替代以有機溶劑為主的組合物。雖然以水為主 的組合物比以有機溶劑為主的组合物對安全及環保因素而 β為較佳，但以水為主的組合物製備的塗層需要長期乾燥 時間。乾燥過程中塗層對多種情況影響而造成缺陷塗層例 如滴落，陷凹及流失。此外至塗層硬化為止易受灰塵或水 接觸污染也導致塗層不良。此等影響可使用揮發性助溶劑 輔助乾燥過程減少，但助溶劑重新造成以水為主的系統希 望解決的環保問題。 經濟部中央襟準局員工消費合作社印⑨ (請先閱讀背面之注意事項再填寫本頁) 除環保考量外，仍有一種挑戰為需要開發於室溫聚結 不會留下沾黏面之膠乳。 鑑於業界的缺陷，希望提供一種塗層其對髒亂、瑕疵 及乾燥過程的污染有抗性，且使用穩定水性分散液而無需 環保無法接受的助溶劑或交聯硬化劑。 .I »-- - 本發明經由提供製備接觸基質時可快速硬化的塗層而 解決業界需求。如此-個態樣中本發明為一種經塗布材料 本紙張尺反^中國國家標準（fNS ) Α4規格（21〇χ297公釐了 -4- A7 B7 化 經 濟 中 央 標 準 局 員 工 合 作 社 印 製 五、發明説明（ 包含一種基質其有一個表面及表面上之一層塗層，其中該 塗層係經由下列任一步驟製備： a) 基質表面與穩定水性分散液接觸，該分散液含有具 有旁出強陽離子基及旁出弱酸基之聚合物；或 b) 基質表面與含具有旁出強陽離子基之第一聚合物之 穩定水性分散液，及含具有旁出弱酸基之第二聚合物之穩 定水性分散液接觸，聚合物與表面之接觸係以任一種順序 或同時進行； 但當塗層係藉方法（a)製備時，基質表面足夠鹼性或經處 理變成足夠鹼性，故穩定水性分散液於少於僅含旁出強陽 離子基或含旁出弱酸基之膠乳硬化所需時間更短的時間硬 態樣中，本發明為一種於具有一個表面之基材上 製備快速硬化塗層之方法，包含下列步驟： a) 基質表面與穩定水性分散液接觸，該分散液含有具 有旁出強陽離子基及旁出弱酸基之聚合物；或 b) 基質表面與含具有旁出強陽離子基之第一聚合物 穩定水性分散液，及含具有旁出弱酸基之第二聚合物之德 定水性分散液接觸，聚合物與表面之接觸係以任—種順序 或同時進行； 但當快速硬化塗層係藉方法（a)製備時，基f表面足约驗 性或經處理變成；1夠鹼性，故敎水性分散糾少於僅含 旁出強陽離子基或含旁出弱酸基之膠乳硬化所需時間更短 的時間硬化。 第 之 穩 訂 本纸張尺度適用中國國家標準（CNS ) A4規格（加^公釐y. -5- A7 A7
愁俅1f 本發明為一種穩定水性分散液包含 經濟部中央標準局員工消費合作社印製 '，奶f八〇泠 住 聚合物具有強陽離子基，弱酸基及由非干擾單體聚合形成 的結構單位，其中由非干擾可聚合單體聚合形成的結構單 位對強陽離子基及弱酸基之比為7〇:3〇至99:1，但強陽離 子基係聯結非鹼性相對離子。 本發明之快速硬化塗層材料可經由基質與穩定水性分 散液接觸製備’該分散液含有—種聚合物具有結構單位係 經由：a)可聚合強陽離子單體及…可聚合弱酸單體聚合形 成之結構單位。本發明之此態樣t，基材充分驗性或被處 理而變成充分鹼性，故穩定水性分散液於少於僅含旁出強 陽離子基或旁出弱酸基之㈣硬化所需時間更短之時間硬 化。 足夠鹼性」一詞表示含足量鹼化及鹼性強度。塗層 .硬化」或¥形成具有足夠機械完整性之表皮時「觸感乾 燥」故以手指輕輕接觸時並無任何表皮部分被去除，且當 於溫和水流沖洗下沒有任何部分由基材被沖掉。 如此處使用「可聚合強陽離子單體」一詞表示單體含 有烯屬未飽和及陽離子基，其價數與pH無關。同理「可 聚合弱酸單體」-詞表示單體含有稀屬未飽和基及酸基具 有pKaK2至ίο之範圍。「由聚合形成之结構1單位」可以 如下實例舉例說明： HO—C—CH=CH2
Cib HO!
-----Γ/'.^--- (請先閱讀背面之注意事項再填寫本頁) ->1 . 訂
本紙張尺度ϋ财®财縣（eNS) 44祕（21Gx297公釐） -6 - 經濟、部中央標準局員工消費合作社印製 A7 B7 五、發明説明（4 ) 除了由可聚合強陽離子單體及可聚合弱酸單體聚合形成之 結構單位外’聚合物較佳包括由可聚合㈣擾單體聚合形 成結構單位。「可聚合料鮮體」—詞詩此處表示對 由聚合物之穩定水性分散液製備塗層之快速硬化性質無不 良影響的單體。 適合製備穩定水性分散液用於製備耐水性快速硬化塗 層之可聚合弱酸單體包括烯屬未飽和化合物含有羧酸，盼 系，硫酚系或膦基官能基。較佳可聚合弱酸單體包括丙稀 酸，甲基丙烯酸，衣康酸丙烯酸沒-羧乙酯（通常為丙烯酸 低I物混合物），乙烯基苯甲酸及2_丙稀酸：2_甲基_，（經 膦基）甲基酯。丙稀酸及甲基丙稀酸為更佳弱酸單體。 可聚合強陽離子單體聯結非驗性相對離子例如為鹵陰 離子如氯離子，溴離子或碘離子以及硝酸根或硫酸根。此 處使用「非鹼性相對離子」一詞表示不會造成弱酸充分離 子化而使穩定水性分散液變成不安定之相對離子。如此若 叛酸為弱酸則竣酸氣根相對離子不適合，原因為此種相對 離子於足量時會升高穩定水性分散液之pH至不穩定程度 。例如對各含2.3莫耳％第四銨鹽及羧酸之穩定水性分散 液而言，存在有足量碳酸氫根相對離子升高膠乳pH至高 於5.5將使分散液變不安定。 適當可聚合強陽離子單體包括具有第四铵，續鐵，環 狀環鏘及鱗官能基之烯屬未飽合化合物鹽。具有第四銨官 月包基之適當單體範例包括烯屬未飽和三烧基鞍鹽如氯化或 漠化乙烯基爷基三-CVC4·烧基鍵；三燒基鍵烧基丙烯酸 本紙張尺度適用中國國家標準（CNS ) A<4規格（2丨OX297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝. 訂 經濟部中央標準局員工消費合作社印製 Λ7 B7五、發明説明（5 ) 酯類或甲基丙烯酸酯類如氣化2-[(甲基丙烯醯氧）乙基]-三 甲基銨及甲基硫酸N，N-二乙基-N-甲基-2-[(l-氧基-2-丙烯 基）氧]乙銨（Chem. Abstracts Reg. No. 45076-54-8);及三 烷基銨烷基]丙烯醯胺類如氯化N,N，N-三甲基-3-[(2-甲基· 1-氧基-2-丙烯基）胺基]-1-丙敍](Chem. Abstracts Reg. No. 51441-64-6)及氣化 N，N-二甲基-N-[3-[(2-曱基-1-氧基-2-丙 烯基）胺基]丙基]-苯甲敍（Chem. Abstracts Reg. No. 122988-32-3)。較佳可聚合第四銨鹽為氣化2-[(甲基丙烯 醯氧）乙基]三甲基銨。 可聚合未飽和磺鏘鹽範例包括二烷基磺鏘鹽如溴化 [4-乙氧-3-(乙氧羰基）-2-亞甲基-4-氧基丁基]二曱基磺鏘 (Chem_ Abstracts Reg. No. 63810-34-4);及乙浠基卡基二 烷基磺燔鹽如氣化乙烯基苄基二甲基磺鏘。可聚合環狀磺 鏘鹽範例包括氣化1-[4-[(乙烯基苯基）曱氧]苯基]四氫-2H-硫哌喃鏘（Chem_ Abstract Reg. No_ 93926-67-1)及氯化乙 烯基苄基四氫嘍吩鏘，其可經由乙烯基苄基氯與四氫噻吩 反應製備。 可聚合鱗鹽範例包括2-甲基丙烯醯氧乙基三-CpC^-烷基-，芳烷基-或芳基鱗鹽如2-甲基丙烯醯氧乙基三-正-十八基鎮鹵化物（Chem· Abstracts Reg. No. 166740-88-1); 三-C「C18-烧基-，芳烧基-或芳基-乙烯基卡基鱗鹽如氯化 三辛基-3-乙烯基苄基鱗，氣化三辛基-4-乙烯基苄基鱗 (Chem_ Abstracts Reg. No_ 15138-12-4)，氣化三丁基-3-乙 烯基爷基鱗，氯化三丁基-4-乙浠基千基鱗（C hem. Abstracts (請先閱讀背面之注意事項再填寫本頁)
iT 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（6 ) Reg. No. 149186-03-8)，氯化三苯基-3-乙烯基苄基鱗及氣 化三苯基-4-乙浠基午基鱗（Chem. Abstracts Reg. No. 145425-78-1) ; C3-C18-烯基三烷基-，芳烷基-或芳基鎮鹽 如演化7-辛烯基三苯基-鱗（Chem. Abstracts Reg· No. 82667-45-6);及參（羥甲基）（1-羥-2-丙烯基）鱗鹽（Chem_ Abstracts Reg. No. 73082-48-1)。 含弱酸基及強陽離子基之可聚合單體範例為氯化Ν-Ο-羧）苄基-N,N-二曱基-2-[(2-甲基-1-氧基-2-丙烯基）-氧] 乙銨。 可添加強陽離子官能基至製妥的聚合物。例如含弱酸 基之可聚合單體可與含親電子基之可聚合非干擾單體如乙 烯基苄基齒或甲基丙烯酸縮水甘油酯共聚合生成具有弱酸 基及親電子基之聚合物。然後此種聚合物可與親核基團如 第三胺或二烷基硫化物後反應，然後置換鹵陰離子基或環 氧丙烷基形成苄基鏘鹽如下示： 聚合物主鏈 (請先閱讀背面之注意事項再填寫本頁) 装. .訂
其~中A為旁出弱酸基；Ar為芳族基較佳苯基；L為離去基 較佳_陰離子基，更佳氯陰離子基；及Nu較佳為二烷基 硫化物如二甲基硫化物及二乙基硫化物；環狀硫化物如四 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9- ΑΊ Β7 五、發明説明（ 氫塞吩’或第三胺如三甲基胺’三乙基胺，三丙基胺，三 丁基胺及三乙醇胺。 添加強陽離子官能基至製妥之聚合物之另一實例中， 3旁出酸基及第二胺或硫陰離子之聚合物主鍵可與適當烧 化反應劑如烷基齒後反應形成含酸基及強陽離子基之聚合 物： 聚合物主鏈
-RL- A Nu—R· L* 此處RL為燒化劑。 ；-辑 經濟部中央標準局員工消費合作社印製 非干擾可聚合單艘範例包括丙稀酸醋類如丙烯酸甲醋 ，丙稀酸乙酯’丙烯酸丁酯，丙烯酸2-羥乙酯，丙烯酸2_ 羥丙酯’丙烯酸縮水甘油酯及丙烯酸烯丙酯；甲基丙稀酸 酯類如曱基丙烯酸甲酯，甲基丙烯酸乙酯，甲基丙烯酸丁 酯，甲基丙烯酸烯丙酯，甲基丙烯酸縮水甘油酯，曱基丙 烯酸2-羥乙酯及甲基丙烯酸2-羥丙酯；烯基芳族烴類如4-曱基丙烯醯氧-2-羥-二笨曱酮及2-(2’-羥-5-曱基丙烯醯氧 乙基苯基）-2H-苯駢三唑；及CrC4-烷基-或烯基-取代苯乙 烯類，較佳苯乙烯，α -甲基苯乙烯，乙烯基甲苯及乙烯 基苄基氣。其它非干擾物種範例包括C3-C18·全氟烷基甲 基丙烯酸酯如甲基丙烯酸2-(全氟辛基）乙酯；C3-C18-全氟 烷基丙烯酸酯類如2-丙烯酸2-[乙基[(十七氟辛基）磺醯基] 胺基]乙酯；及C3-C18-全氟-烷基乙烯基苯類。（參見美國 -10- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 Λ7 B7 五、發明説明（8 ) 專利4,929,666第4欄第54至68行及第5攔第1至30行）。 旁出弱酸基對旁出強陽離子基之比係與用途有關但通 常於4:1至1:4之範圍。由可聚合非干擾單體聚合形成的結 構單位對弱酸基及強陽離子基之比隨穩定水性分散液之％ 固體而定’但較佳不低於70:30，較佳不低於8〇:2〇，更佳 不低於90:10及最佳不低於94:6 ;及較佳不大於99.5: 0.5， 更佳不大於99:1及最佳不大於98:2。 通常固趙含量愈尚則需要形成快速硬化塗層所需總離 子物種濃度愈低。穩定水性分散液之固體含量與用途有關 但較佳不低於10 ’更佳不低於2〇及最佳不低於3〇重量％及 較佳不大於60,更佳不大於55及最佳不大於50重量％。 穩定水性分散液可藉任一種適當手段製備，較佳藉下 列步驟製備：1)製備晶種膠乳；2)以水稀釋晶種膠乳；3) 接觸稀溶液與基團引發劑，可聚合非干擾單體，可聚合弱 酸單體及強陽離子單體；及4)於可形成具有非干擾基，旁 出強陽離子基及旁出弱酸基之穩定水性分散液條件下聚合 步驟3所得溶液。 晶種膠乳較佳於批次製成，使用陽離子界面活性劑藉 乳液聚合反應製備。晶種膠乳作為隨後單體加成聚合反應 位置’故新顆粒的形成減少，於終產物可達成粒子大小分 布之更高均勻度。如此用於製備晶種膠乳之單體選擇可形 成對隨後加入之單體具有親和力之顆粒，故偏好於晶種膠 乳顆粒上進行聚合反應。於步驟2，晶種膠乳之稀釋程度 係由最終膠乳之期望顆粒大小及％固體決定，易由業界人 本紙張尺度適用中國國家標準（CNS ) A4規格< 210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 策· 訂 -11 - 經濟部中央標準局員工消費合作社印製 A7 —_____B7 五、發明説明（9 ) ^ 士決定。 也可由預先形成的聚合物製備穩定水性分散液。預先 形成的聚合物可溶解於適當溶劑，然後藉任一種適方方法 分散於水。然後去除溶劑及固體含量經調整而形成所謂之 人工膠乳。 穩定水性分散液選擇性含有填充劑，顏料，染料，殺 真菌劑，殺菌劑，增稠劑，聚結助劑及消泡劑，其不會造 成分散液之過早凝固。填充劑包括黏土，矽氧，陶究類及 其它穩定水性分散液》 當含有具有強陽離子基，弱酸基及選擇性由可聚合非 干擾單體聚合形成的結構單位之聚合物之穩定水性分散液 接觸具有接觸面之基材’該接觸面為或已經處理成為足夠 驗性故穩定水性分散液於短於僅含旁出強陽離子基或旁出 弱酸基（但非二者）之膠乳硬化所需時間，較佳於5分鐘内 ’更佳於3分鐘内及最佳於1分鐘内硬化，可製備快速硬化 塗布材料。使分散液快速硬化所需基材鹼度依據聚合物之 弱酸基之pKa決定。弱酸之pKa愈低’則引起快速硬化所需 鹼愈弱。鹼愈強及鹼濃度愈高則硬化愈快速。 雖然不欲受理論所限但相信快速觸感乾燥塗層可經由 聚結過程形成。此過程中鹼性基材作為質子阱，由弱酸基 抽取質子形成共軛鹼，然後共軛鹼與強陽離子基不可逆快 速結合形成不可逆交聯網路。相信此種交聯網路於硬化後 呈現塗層。 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ297公釐） (請先閱讀背面之注意事項再填寫本買)
-12- 五、發明説明（10 ) A7 B7
經濟部中央標準爲員工消費合作社印製 上示中，B_為輿基材聯藉之鹼性部分^ BH為B-之共 軛酸較佳具有比弱酸更高的pKa(說明例中為羧酸基）^但 無須為此種情況。例如若基材存在有足量B·，則共輛酸BH 實際具有卩心等於或低於弱酸pKa，推定原因為一旦質子被 B·拔取則過程可逆。 例如經由基材表面接觸水濕潤性pH紙可提供表面鹼 度指呆。又使聚結所需pH隨弱酸之pKa而定；對含旁出羧 酸基單位之聚合物而言（舉例），接觸基材之水pH不低於6 ，更佳不低於8及最佳不低於1〇。 基材可為鹼性特質。此種基材包含含水泥材料如卜特 蘭水泥，含礬土水泥，無機砂漿或含水泥纖維板。基材即 使非鹼性特質也可處理變成具足夠鹼性而使塗布材料可快 速硬化。例如基材表面可與具1)11大於弱酸pKa之水溶液於 施用聚合物穩定水性分散液至基材表面前或同時處理。此 種鹼性水溶液包括但非限於鹼金屬及鹼土金屬磷酸鹽類， 碳酸鹽類，碳酸氫鹽類及氫氧化物類。較佳可以鹼處理之 基材包括金屬，玻璃，紙，塑膠，布，木材及皮革。基材 可具有特定形狀，例如手形狀供製造膠乳手套。 基材也可包括填充材料，其使基材表面具足夠鹼 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公楚） (請先閱讀背面之注意事項再填寫本頁) 装- 訂 -13- 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（11 ) 使聚合物之穩定水性分散液可形成快速硬化塗層。石灰及 碳酸鈣為此種填充材料之例。 本發明之另一具體例中，快速硬化塗層可經由基材接 觸第一穩定水性分散液且含有一種聚合物具有由可聚合強 陽離子單體聚合形成之結構單位；及與第二穩定水性分散 液其含有一種聚合物具有由弱酸單體聚合形成的結構單位 接觸製備。穩定水性分散液可以任一種順序或大體同時， 較佳同時接觸基材，出乎意外地基材無須為鹼性或變成鹼 性。第二穩定水性分散液較佳於陰離子界面活性劑如硫酸 鹽包括月桂基硫酸鈉或DOWFAX EB界面活性劑（得自陶 氏化學公司）存在下安定化◊硫酸鹽也可呈端基存在於陰 離子膠乳聚合反應過程中使用過硫酸鹽引發劑生成的聚合 物鏈上。第一及第一穩定水性分散液較佳使用多成分式噴 麗器施用於基材。 第一及第二穩定水性分散液較佳具有由可聚合非干擾 單體聚合反應形成的結構單位。由強陽離子單體於聚合物 第一穩定水性分散液聚合形成之結構單位之莫耳百分比較 佳不低於0.5，更佳不低於1及最佳不低於2莫耳％及較佳 不大於20，更佳不大於1〇及最佳不大於5莫耳％，以強陽 離子單體及非干擾單體之總莫耳百分比為準。由聚合物第 二穩定水性分散液之弱酸單體聚合形成的結構單位之莫耳 百分比也較佳不低於0_5，更佳不低於丨及最佳不低於2莫 耳％，及較佳不大於20，更佳不大於1〇及最佳不大於今莫 耳％，係以強陽離子單體及非干擾單體之總莫耳百分比為 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閲讀背面之注意事項再填寫本頁)
、1T -14- 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（12 ) 準。 本發明之塗布材料具有廣泛用途包括塗布混凝土路面 ，此處快速硬化塗層可於無溶劑或交聯硬化劑存在下單純 施用聚合物之穩定水性分散液之路面製備。其它用途包括 灰泥房舍或含水泥纖維板。水性分散液也可用於塗布固化 或未固化水泥來減少水分蒸發因而改良最终混凝土的物理 性質。分散液也可藉將原形或模具浸潰於穩定水性分散液 使分散液快速硬化於模型上用來製備膠乳手套或保險套。 最佳配方中，用於製備塗層材料之穩定水性分散液具 有儲存安定性至少6個月較佳至少一年。配方也含有添加 劑如顏料、染料、殺真菌劑及殺菌劑。 下列實例僅供舉例說明之用而非限制本發明之範圍。 實例1 -快速硬化透明塗層之製備 穩疋水性分散液係以二步驟式方法製借。首先經陽離 子界面活性劑穩定化之聚苯乙烯晶種膠乳使用批次法製備 β其次部分晶種膠乳用於連續添加過程製備含羧酸及第四 銨官能單體之第二種層膜膠乳。 陽離子膠乳晶種係以下述方式製備。於配備有氮氣入 口，回流冷凝器附有氮氣出口及機械攪拌器之丨升3頸玻璃 反應瓶内加入苯乙嫦（100克），ARQUAD 18-50氣化十八基 三甲基銨界面活性劑（AkzoNobel商品名，20克活性），過 氧化氫（3.3克，1.0克活性），水（2〇〇克）及硫酸鐵溶液（〇 25 克於100克水）。燒瓶於氮下加熱至7〇 歷2小時伴以授拌 ，隨後中止攪拌及去除加熱源。膠乳晶種於燒瓶内放置隔 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） --------f 裝------訂-----/ ， v · ' 〆 (請先閱讀背面之注意事項再填寫本頁) -15- A7 B7 五、發明説明（13 ) 夜。獲得不透明高黏度分散液含35.8%固體。顆粒大小為 407埃（平均值）及393埃（中間值）。 層膜膠乳係由陽離子晶種膠乳使用連續加成聚合法製 備。注射泵用作連續加成控制裝置。於配備有氮氣入口， 附有氮氣出口之回流冷凝器及機械攪拌器之2升3頸玻璃反 應瓶内加水（452.3克）及陽離子晶種膠乳（8.8克）。燒瓶加 熱至60°C及攪拌。表1顯示未連續添加製備之溶液。 表1 流 成分 量 1 丙烯酸丁酯 176克 曱基丙烯酸甲酯 124克 甲基丙烯酸 5.3克 2 M-Quata 17.3克(12.8克活性） 3 第三丁基過氧氫 1.8克(1.3克活性） 4 甲醛次硫酸鈉 0.96克於10毫升水 a氣化2-[(甲基丙烯醯氧）乙基]三甲基銨係呈74%水溶液得自 Bimax公司，馬里蘭州21225巴爾的摩恰斯巴克大道717號）。 由四流所得成分係於聚合反應之前4個小時添加。添 加完成後聚合反應於60°C持續0.5小時。所得膠乳經過濾 而具固體含量37.0%。表II顯示膠乳組成。
表II ---------水------訂------^ 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 單體 重量％ 莫耳％ 分子量克/莫耳 丙烯酸丁酯 55.3 50.2 128.1 曱基丙烯酸甲酯 39.0 45.3 100.1 甲基丙烯酸 1.7 2.3 86.1 M-Quat 4.0 2.3 207.7 粒徑為1550埃（平均）及1450埃（中間）。 使用塗漆刷施用膠乳塗層至含水泥纖維板製備透明快 速硬化塗層。樣本係於22.4°C及65%相對濕度觀察。施用 膠乳後30秒，經塗層之含水泥纖維板置於流動水下。塗層 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16- 五、發明説明（l4 A7 B7 未顯不瀋出，跑動或任何不利影響。施用之2〇分鐘内膠乳 乾燥成透明膜。 實例2 _快速硬化含顏料塗層之製備 一氧化鈦顏料漿液用於製備含顏料膠乳塗層而驗証使 用添加顏料之塗層配方可於鹼性表面上獲得快速硬化塗層 。二氧化鈦顏料漿液組成示於表π ^ 表III - 成分 數量(重量％) 水 - 31.0 Ή-Pure R-9000二氡兑鈦》 66.5 KHGDAQUAT M242C/26 陽離子 界面活性劑b 2.20 FOAMASTER V非離子界面活性劑<= 如 /入幻龙* 〇 A \------1 0.30 b(隆寶蘭商品i) e(亨克商品名） (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印袋 二氧化鈦顏料漿液係經由將二氧化鈦於高速剪力下$ 合入含水界面活性劑形成平順黏稠分散液。玻離瓶内加〉 29.4克漿液然後加入5,5克去離子水。稀漿液經混合形月 均勻懸浮液。膠乳具有表II所示組成及總固體含量37.4 ^ 量4與漿液於約350 rpm混合3分鐘。所得分散液具有全导 稍度及色彩。分散液塗層以塗漆刷施於含水泥纖維板上。 Ϊ分鐘後板上塗層置於流動水流下方。並無任何顏料損身 指示或對塗層造成之不良影響。約1〇毫升含顏料膠乳移與 至喷霧瓶’以氮氣加壓至約30 psig (0.2 MPa)。小量添办 顏料之膠乳噴霧於含水泥纖維板上。獲得含水泥纖維板之 均勻塗層。再度約1分鐘後塗層板置於流動水流下。未見 任何顏料損失或塗層之不利影響。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17- A7 B7 五、發明説明（15 )
Ml-於經鹼處理之濾紙上形成快速硬化塗層 瓦特曼1號定性濾紙直徑9 · 〇厘米圓切割成5 7厘米χ 7.0厘米矩形然、後沿各緣貼於玻璃板上。紙張浸泡飽和氮 鈉溶液，然後以紙巾吸潰去除過量流體。據表示組成 之穋乳塗層展布於塗層紙上。於紙張上膠乳膜之快速硬化 於15秒内顯現。約兩分鐘後塗層觸感全然乾燥。三分鐘後 一滴水滴於塗層紙上形成水珠而未見瀋出。此種水滴試驗 重複數次所得結果相同。 .實包4 '於經鹼處理之報紙上形成快速硬化塗層 11吋X 17吋（28厘米Χ43厘米）紙張懸吊於罩斗内且略 微喷霧1 _0%固體含量碳酸氫鈉溶液然後任其乾燥隔夜。 次曰樣品塗布具表Π所示組成之膠乳薄層。塗層於丨〇秒内 硬化；未見瀋入紙中，產生光澤面。 經濟部中央楼準局員工消費合作衽印t (請先閱讀背面之注意事項再填寫本頁) -於經鹼處理之布上形成快速硬化塗層 一塊常用布材料（60%棉’ 40%聚酯）浸沒於1 .〇%重量 比碳酸氫鈉水溶液然後浸泡5分鐘。取出布塊，盡可能擠 乾及貼至玻璃板。然後使用8密耳之下拉桿將具有表Η指 示組成之膠乳樣本展布於布片上。膠乳於1〇秒内觸感乾燥 ° 2分鐘内使用高壓層合塑踢輥由塗層材料擠壓去除過量 水。30分鐘内膠乳乾燥成透明撓性塗層略有光澤。 复遇以鹼性材料喷灑多重成分
Binks Mach 1 PCX多成分塗料噴霧器用於施用表π所 示組成膠乳與3.0%重量比構酸氫二鉀溶液之攙混流至橡 木層板樣本。霧化壓力設定為約72 psig (0.50 Mpa)儲存容 本紙張尺度通用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（16 ) 器設定為約35 psig(0.24 MPa)。塗層快速（少於30秒）變成 觸感乾燥。兩條鋁條（Q-panel公司）也塗布而獲得類似結果 。霧化壓力降至45 psig (0.31 Mpa)儲存容器壓力降至10 psig (0.07 MPa)。重複該過程。塗層觸感變乾燥之速率不 受影響，但塗層表面改良。冷軋鋼條（Q-panel)也容易使用 相同操作條件塗層且獲得類似結果。 實例7 -使用陰離子膠乳之多重成分噴霧 實例6所述塗料噴霧器用於施用具表II所示組成及具 表IV所示組成之陰離子膠乳之攙混流。 (請先閱讀背面之注意事項再填寫本頁) 装· 表IV 單體 重量％ 莫耳％ 丙烯酸丁酯 50.5 43.9 甲基丙烯酸甲酯 43.0 47.9 甲基丙烯酸 5.95 7.7 甲基丙烯酸烯丙酯 0.52 0.46 霧化壓力設定為40 psig (0.30 MPa)及儲存容器壓力設定為 7.5 psig (0.05 MPa)。喷霧施用於玻璃板，所得塗層於30 秒以内硬化。 實例8 -使用陰離子材料之多重成分喷霧 使用實例6所述塗料喷霧器施用具有表II所示組成膠 乳及陰離子防蝕水溶液[含4.45%重量比MIRANOL CS(隆 寶蘭公司製造）]之攙混流。霧化壓力為35 psig (0.24 MPa) 及儲存容器壓力設定為5 psig (0.03 MPa)。塗層施用於未 經處理之鋁條，前處理鋁條（Q-panel公司）及PTO前處理樣 本。喷霧形成可接受的塗層且於全部三塊試驗板上皆於30 秒以内硬化。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐）
、1T -19- 396197 A7 B7五、發明説明（17 ) 實例9 -使用陽離子膠乳及陰離子膠乳之多重成分喷霧 實例6所述塗料喷霧器用於施用具表V所示組成之陽 離子膠乳及具表IV所示組成之陰離子膠乳之攙混流。霧 化壓力設定為35 psig (0.24 Mpa)及儲存容器壓力設定為10 psig。塗層施用至未經處理玻璃板。喷霧形成可接受的塗 層及於20秒以内聚結。於少於30秒内硬化。1分鐘後板置 於流動水下方對塗層未造成不利影響。兩條鋁條亦經塗布 ，其中一條事先使用填酸鹽（Q-panel公司）處理。噴霧於試 驗片上於15秒内形成可接受之塗層及聚結。 (請先聞讀背面之注意事項再填寫本頁) 装. 表V 單體 重量％ 莫耳％ 丙烯酸丁酯 56.2 51.3 甲基丙烯酸甲酯 39.7 46.5 M-Quat 4.1 2.3 訂 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） -20-

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  1. 太1 396197
    申請專利範圍 第87107885號專利申請案申請專利範圍修正本 修正曰期：89年2月 (請先閲讀背面之注意Ϋ項再填寫本頁) 1. 一種經塗布之材料，其包含具有一表面及表面上之一 層塗層之基質，其中該塗層係經由下列任一步驟製備： .a)基質表面與穩定水性分散液接觸，.讓.分散應含 有具有旁直陽艙土基及旁串弱酸基之聚合物；或 b)基質表面與含具有旁出強陽離子基之第一聚合 物之穩定水性分散液，及含具有旁出弱酸基之第二聚 合物之穩定水性分散液接觸，聚合物與表面之接觸係 以任一種順序或同時進行； 訂 但當重〜層―係藉方法⑷製備時，基質表面足夠鹼性或經 處理變成足夠驗性，故穩定水性分散液於少於华含旁 出強腸離子基或含旁出弱酸基之膠乳硬化所需時間更 ，短的時間硬化。 2. 如申請專利範圍第1項之塗布材料，其係經由基材表面 與含強陽離子基及弱酸基之聚合物之穩定水性分散液 接觸製備》_ 經 濟 部 智 慧 財 產 局 員 工 消 合 作 社 印 製 3. 如申請專利範圍第1或2項之塗布材料，其中該聚合物 又具有由非干擾可聚〜合〜單體聚合形成的結構單位。 4. 如申請專利範圍第3項之塗布材料，其中該非干擾可聚 合單體為丙稀酸曱輯，.丙稀酸乙醋，丙稀酸丁醋，丙 烯酸2-羧乙酯’丙烯酸2-羥丙酯，丙烯酸烯丙酯，丙 烯酸縮水甘油酯’曱基丙烯酸曱酯，甲基丙稀酸乙酯 ’甲基丙埽酸、X酯’曱基丙烯酸烯丙酯，甲基丙稀酸 -21 - Α8 Β8 C8 D8 396197 K、申請專利範圍 縮水甘油酯，甲基丙烯酸2-羥乙酯，甲基丙烯酸2_經 丙酯’甲基丙稀酸C3-C18-全氟烷酯，丙烯酸C3-C18-禽 敗烧輯’ Cs-Cw全氣烧基乙稀基苯，苯乙烯，α-甲.基 笨乙烯或乙烯基甲苯或其組合。 5·如申請專利範圍第1，2或4項之塗布材料，其史該弱蒇 棊係由丙稀酸，曱基丙烯酸，衣康酸，丙稀酸叛乙 酯，乙烯基苯甲酸，乙烯基氣酚，乙烯基溴#，乙稀 基碌两屠酸：2_甲基-，(經膦基）曱基酯或其組 合形成 6V如,锖專利範圍第l，2或4項之塗本材料，其中該強強 陽離子基係由下列任一種方法形成.： a) 三烷基銨烷基丙烯酸醋;三烷基銨烷基甲基丙 稀酸酿；三烧基錢燒基丙稀酿胺；二院基磧’錄，鹽，节 基確鎮盥’環狀橫鐵鹽’2,甲基丙基酿氧乙基三_(^_(^2〇-烷基··鱗聲，2-甲基丙烯醯氧乙基三_(^_匚2〇_芳烷基鱗 鹽’ 2,甲基丙稀酿氣乙基三-CrC：2。-芳基-鱗鹽，三_cr Cu-院基-乙稀基千基鎮鹽三_crc18-芳烷基·乙烯基 节秦：·_鹽’三-c丨-cls-芳基-乙烯基苄基鱗鹽，c3_Ci8_ 稀基二燒基-麟犟’ c^-c,8-芳院基·鱗鹽或c3_c18_芳基_ 鱗壅聚合；或 b) 可聚合第三胺或硫化物聚合接著與烷化劑尽應 形成第四銨鹽或磺鏘鹽；或 c) 含親電子基之可聚合單趙聚合接著與第三胺或 碌化物反應-妙成第四―錄I或績鐵鹽。 (請先閲讀背面之注項再填寫本頁) 人 訂 經濟部智慧財產局員工消費合作社印製 -22- 39S197
    經濟部智慧財產局員工消費合作社印製 .^申請專利範圍第4項之塗布材料，其中該非千擾可聚 合單體為甲基丙烯酸甲酯’丙烯酸丁酯，苯乙烯，甲 基丙燥魏4·甲基丙烯㈣·2卷二苯甲綱或 2-(2’-臬:5-曱基㈣醯氧_乙基笨基)_2Η-苯耕$雇或其 組合。 8:如申請專利範圍第4項之塗布材料4中由.啡干擾可聚 合單體形成之結構單位對強陽離子基及弱酸基之比 90:10至99.5:0.5，及其中強陽離子基龟經由與氣陰離 子，溴陰離子，確農根或硫酸根相對離子結合之烯屬 未飽和第四銨鹽聚合反應生成。 〜 9.如申請專利範圍第8項之塗布材料，其中該第坪銨鹽為 氣化2-[(甲基丙婦酿氧）乙基]三甲基録；弱酸基係由丙 烯酸或曱基丙烯酸或其組合聚合形成；及非干擾可聚 合單體為苯乙烯，甲基丙烯酸甲酯或丙埤酸丁酯或其 組合。 1〇.如穿請專利範圍第1 ’ 2, 4, 7, 8或9項之塗布材杯'， 某中該基質為歐化卜特蘭水泥，未固化卜特蘭水泥， 食礬土水泥，無機砂漿或含水泥纖維板或經處理變成 岭性且為金遂’玻璃，紙，塑膠，布，木材或皮革。 11‘如申請專利範圍第1 ’ 2，4，7，8或9項之塗布材料， 其中該基材表面接觸含具有強陽離子基之第一聚合物 之穩定水性分散液及含弱酸基之第二聚合物之穩定水 性分散液，聚合物與表面之接觸係以任一種順序或同 時進行’及其中該第一或-第二穩定水性分散液的pH值 本纸用中國國家樣準（CNS ) A4iUS· ( 2_10X297公釐) ------- -23 - • n f— n n n I I— ^ n n . (請先閱讀背面之注^h項再填寫本頁) 訂 396137 A8 B8 C8 D8 六、申請專利範園 至少為5 » 12. 如申請專利範圍第u項之塗布材料，其中該第一聚今 物又具有弱酸基》 13. —，種於具有一個表面之基材上製備快速硬化塗屠之方 法，包含下列步驟： a)基質表面與穩定水性分散液接觸，該分散液含 有具有旁出強陽離子基及旁出弱酸基之聚合物；或 -b)基質表面與含具有旁出強陽雜子基之第一聚合 物.之穩定水性分散液，及含具有旁出—弱酸基之第二聚 合物之穩定水怪分散液接觸，聚合物與表面之接觸係 以择一種順序或同時進行； 快速硬化塗層應藉方法⑷製備時，基質表面足夠' 鹼性〜或經-處理變成足夠驗性，故穩定水性分散液於少 於麥含旁出*強陽離子基或含旁出弱酸基之膠乳硬化所 需時間更短的時間硬化。 14. 一種用於如申請專利範圍第1項之經塗布材料的穩定 水性分散液’其包含一具有一種強陽雜子基，弱酸基 及古典干擾m合形成之結構單位的聚合物，其中 由非之擾可聚合單體聚合形成的結構單位對強陽離子 基及氮酸基之比為70:30至99:1，但強陽離子基係聯转 非鹼性相對離子。 本紙》尺度逋用中國國家梂準（CNS ) Α4規格（210X297公嫠） (請先閱讀背面之注意事項再填寫本頁) ，ΤΓ 經濟部智慧財產局員工消費合作社印製 -24-
TW087107885A 1997-05-23 1998-05-21 A stable aqueous dispersion, a method of preparing a fast-setting coating on a substrate and the coated material TW396197B (en)

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DE69815843T2 (de) 2003-12-24
WO1998052698A1 (en) 1998-11-26
DE69815843D1 (de) 2003-07-31
CA2290573A1 (en) 1998-11-26
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US6251485B1 (en) 2001-06-26
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