TW415923B - Compositions for producing a water-repellent surface on a substrate - Google Patents
Compositions for producing a water-repellent surface on a substrate Download PDFInfo
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- TW415923B TW415923B TW085105930A TW85105930A TW415923B TW 415923 B TW415923 B TW 415923B TW 085105930 A TW085105930 A TW 085105930A TW 85105930 A TW85105930 A TW 85105930A TW 415923 B TW415923 B TW 415923B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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Abstract
Description
經濟.邓中央標準局員工消費合作杜印製 415923 五、發明説明(1 ) 背景 本發明係大致關於表面處理之技術,特別係關於在諸多 底質上產生水相斥表面之技術,且更特別係關於改善此等 水相斥表面之耐久性。 相關技術Economy. Deng Central Bureau of Standards, Consumer Co-operation, Printed by Du 415923. V. Description of the Invention (1) Background The present invention is about the technology of surface treatment, especially the technology of generating water repellent surface on many substrates, and it is more special. It is about improving the durability of these water repellent surfaces. Related technologies
Yoneda等人之美國專利第5,314,731號述及一種具有 至少兩層經處理表面層之表面經處理底質,其中該最外層 係藉化合物處理而得,該化合物係包含至少一種可對水形 成至少70。接觸角之表面之Si-NCO基團;該第二底層係 藉至少一種選自異氰酸酯矽烷化合物及可水解之矽烷化合 物之具反應性矽燒化合物處理而得。Yoneda et al., U.S. Patent No. 5,314,731, describes a surface treated substrate having at least two treated surface layers, wherein the outermost layer is obtained by treating a compound that contains at least one compound that forms at least 70 water. . Si-NCO groups on the surface of the contact angle; the second underlayer is obtained by treating at least one reactive sintered compound selected from the group consisting of an isocyanate silane compound and a hydrolyzable silane compound.
Franz等人之美國專利第4,983,459號及第4,99 7,684 號揭示分別用以提供玻璃上之耐久不沾濕性表面之物件及 方法,該表面係經全氟烷基烷矽烷及氟化烯烴調聚物處理 者。Franz et al., U.S. Patent Nos. 4,983,459 and 4,99 7,684 disclose articles and methods for providing durable non-wetting surfaces on glass, respectively, the surfaces being conditioned by perfluoroalkyl silanes and fluorinated olefins. Polymer processor.
Franz等人之美國專利第5,308,705號述及提供除玻璃 外之底質之不沾濕性表面性質,係藉由全氟烷基烷矽烷及 氟化烯烴調聚物處理者。Franz et al., U.S. Patent No. 5,308,705, describes non-wettable surface properties that provide substrates other than glass and is treated by perfluoroalkylalkanesilane and fluorinated olefin telomers.
Goodwin之美國專利第5,328,768號揭示一種玻璃底 質,其表面係先經矽氧底劑層處理、次經全氟燒基烷矽燒 處理者。 發明概述 本發明係提供一種具高度水相斥性及高潤滑性之底質表 面。底質表面對水之耐久性及污垢相斥性,可藉由於該底 本紙張尺度適用中國國家標準(CNS ) A4規格(2丨0X297公釐) --------ί·裝------訂------涨 ί\ (請先閲讀背面之注意事項再垓寫本頁) 415923 A7 _B7五、發明説明(2 ) 經濟部中央標隼局員工消費合作社印裝 質表面使用全氟烷基烷矽烷化合物及可水解之矽烷或矽氧 燒化合物而改善。該可水解之硬挽或妙氧燒化合物係可水 解冷凝以形成矽氧凝膠、且具完整底劑化合物功能之化合 物。本發明之表面處理係提供增強之對水耐久性及污垢相 斥性表面,而毋需一分離之底劑層。高度水相斥性及潤滑 性係由全氟烷基烷矽烷所提供。該可水解之矽烷或矽氧燒 亦供給該溶劑之反應性乾燥。本發明之全氟烷基烷矽烷及 可水解之矽抗或矽氧烷表面處理亦對該底質表面提供增強 之耐磨損性。可水解冷凝爲矽氧凝膠之矽烷或矽氧烷化合 物可增進對濕度、紫外線輻射及機械磨損之抵抗力。 較佳具體例之敘述 將全氟烷基烷矽烷使用於底質表面所提供之耐雨性及髒 污相斥性,可藉由於使用前混合全氟規基燒碎燒與欢燒、 碎氧烷或矽烷及/或矽氧烷化合物之混合物而使其增強。 根據本發明,係將全氟烷基烷矽烷及矽烷、矽氧烷、或可 水解爲矽氧凝膠之矽膠及/或矽氧烷化合物混合物之混合 物使用於玻璃表面,所形成之塗層與未含碎燒 '珍氧規、 或可水解爲矽氧凝膠之矽氧及/或矽氧烷化合物混合物者 相較,具較佳之耐久性。 將全氟烷基烷矽烷及可水解之矽氧及/或矽氧烷使用於 底質表面而形成之本發明物件,較佳係呈膠狀懸浮液或溶 液,較佳係於非質子性溶劑中,較佳係烷類或烷類混合 物、或氟化溶劑。本發明之溶液可藉由任何習知技術使用 於底質表面上,例如浸泡、垂懸、擦拭或噴濺。該矽烷與 -5- ---------裝------訂------龈 /V (請先閲讀背面之注$項再填冩本頁) 本紙張尺度適用中國國家揉準(CNS ) A4規格(210X297公釐) Α7 Β7 415923 五、發明説明(3 ) 底質表面反應,且除去剩餘溶液後,可提供耐久、不沾 濕、潤滑之表面’並具較佳之抗磨損性。本發明提供底劑 之耐久優點,而免除使用一分離底劑層之多餘步骤。完全 水解之矽烷及/或矽氡烷之用途係可增進該矽烷表面處理 對濕度、紫外線輻射及磨損之抵抗力,可利用Cleveland 凝結棍(Condensing Cabinet),QUV(以 FS40 或 B313 燈)測量,以及利用濕雪撬磨損測試測量,顯示較長之有 用產品使用壽命。 通當之可水解爲矽氧凝膠之矽烷具—般式Si χ4,其中 X係可水解之基困,一般選自鹵素、烷氧基及醯氧基。 較佳之矽烷係其中X較佳爲氣基、溴基 '碘基、甲氧 基 '乙氧基及乙酷氧基。較佳之可水解秒規包括四氣碎 烷、四甲氧矽烷及四乙醯氧矽燒。 適當之矽烷具一般式SiyOzX4y-2z,其中X係選自鹵素、 坡氧基及醯氧基、y係大於或等於二,而z係大於或等於 一,且4y-2z係大於零。較佳之可水解矽氧包括六氣二矽 烷、十氣三矽校,及更高碳數之氯矽咸低聚物。 該可水解之碎坑或碎氧貌係具二功能:其—係成爲塗層 之部分且賦予對老化及磨損之抵抗力;其二係乾燥該溶 劑。典型之烴溶劑可包含50至200 ppm水。其它溶劑可 包含高更多之水含量。舉例而言,溶劑需包含20〇 ppm 水,其水之存在量方足以部分水解0.5重量百分濃度之全 氟烷基烷矽烷。該完全水解之矽烷或矽氧烷可消除或降低 於添加全氟燒*基規碎燒前、溶劑中之水含量。否貝彳,_ > -6- 本紙張尺度適用中國國家標準(CNS > A4規格(2丨0X297公釐) --------二衣------.订------m (請先閲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策 415923 A7 B7_____ 五、發明説明(4 ) 水解之全氟烷基烷矽烷會導致不充分之塗潛沈積或極差之 耐久性。 較佳之全氟烷基烷矽烷具一般式RffiR、siX4-m_n,其中 R係全氟烷基烷基;m—般爲一,11 一般爲零或一,且 m + η係小於4 ; R,係乙烯基或烷基,較佳係甲基、乙基、 乙烯基或丙基;以及X較佳係如鹵素、酿氧基及’或烷氧 基之基團。於全氟烷基烷基中較佳之全氟貌基部份係CF3 至C30F61,較佳’而最佳係C8F17至 C12F25 ;該烷基部份較佳係乙基。較佳係甲基或乙 基。較佳之X基包括可水解之氯基、溴基、碘基、甲氧 基、乙氧基及乙醯氧基。根據本發明,較佳之全氟烷基燒 矽烷包括全氟烷基乙三氣矽烷、全氟烷基乙三甲氧矽烷、 全氟烷基乙三乙醯氧矽烷、全氟烷基乙二氣(甲基)矽烷及 全氟烷基乙二乙氧(甲基)矽垸。 此等較佳之全氟垸基規碎燒似乎會於分子基礎上,與底 質表面上之鍵結位置反應。全氟烷基烷矽烷之強大表面鍵 結產生耐久之底質表面,其對水滴呈現高接觸角,顯示具 高對水相斥性。 適當之溶劑包括已烷、庚烷、礦物精、丙酮、甲苯及石 腦油。較佳之溶劑係烷類或鹵素化烴溶劑,例如三氣三氣 乙燒及亞甲基氣化物,以及全氟化有機化合物,例如全敦 化碳。適宜之矽烷百分比濃度係約0 0〇5至,較佳係约 〇.〇5至5。該溶劑可僅藉由於周園溫度下乾燥而蒸發,或 者剩餘溶液較佳可藉擦拭而移除。 ---------.i--------,1T------^ ί請先閲讀背面之注意事項再读寫本頁) 經濟部中央標準局負工消费合作社印製U.S. Patent No. 5,328,768 to Goodwin discloses a glass substrate whose surface is first treated with a silicon oxide primer layer and then treated with a perfluoroalkylene sintered silicon substrate. SUMMARY OF THE INVENTION The present invention provides a substrate surface with high water repellency and high lubricity. The durability of the surface of the substrate to water and dirt are repellent, because the paper size of the substrate is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) -------- ί ·- ---- Order ------ Zhang Li (Please read the notes on the back before writing this page) 415923 A7 _B7 V. Description of the invention (2) Print quality of employees' cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs The surface is improved by using perfluoroalkyl silane compounds and hydrolyzable silane or siloxane compounds. The hydrolyzable hard-pull or oxo-fired compound is a compound that can be hydrolyzed and condensed to form a siloxane gel, and has the function of a complete primer compound. The surface treatment of the present invention provides an enhanced water durability and dirt repellent surface without the need for a separate primer layer. High water repellency and lubricity are provided by perfluoroalkyl silanes. The hydrolyzable silane or siloxane is also provided for reactive drying of the solvent. The surface treatments of the perfluoroalkylalkanesilane and hydrolyzable silicone or silicone of the present invention also provide enhanced abrasion resistance to the surface of the substrate. Hydrolyzed and condensed silanes or siloxane compounds can increase resistance to humidity, ultraviolet radiation, and mechanical abrasion. The description of the preferred specific examples provides the rain resistance and dirt repellency provided by the use of perfluoroalkylalkane silanes on the surface of the substrate. Or a mixture of silanes and / or siloxane compounds. According to the present invention, a mixture of perfluoroalkylalkane silane and silane, siloxane, or a mixture of siloxane and / or siloxane compounds that can be hydrolyzed into siloxane gels is used on a glass surface. Compared with those that do not contain crushed burner's oxygen gauge, or a mixture of silicone and / or silicone compounds that can be hydrolyzed into a silicone gel, they have better durability. The object of the present invention formed by using perfluoroalkylalkanesilane and hydrolyzable siloxane and / or siloxane on the surface of the substrate is preferably a colloidal suspension or solution, more preferably an aprotic solvent Among them, an alkane or an alkane mixture or a fluorinated solvent is preferred. The solution of the present invention can be applied to the substrate surface by any conventional technique, such as immersion, hanging, wiping or spraying. The silane and -5- --------- install ------ order ------ gingival / V (please read the note on the back before filling this page) This paper size Applicable to China National Standard (CNS) A4 (210X297 mm) A7 B7 415923 V. Description of the invention (3) The surface of the substrate reacts, and after removing the remaining solution, it can provide a durable, non-wet, lubricated surface. Better abrasion resistance. The present invention provides the durability advantages of a primer without the need for an extra step of separating the primer layer. The use of fully hydrolyzed silane and / or silane is to improve the resistance of the silane surface treatment to humidity, ultraviolet radiation and abrasion. It can be measured by Cleveland Condensing Cabinet, QUV (using FS40 or B313 lamp). And the use of wet sled abrasion tests to measure longer useful product life. The general silane that can be hydrolyzed into a siloxane gel has a general formula Si χ4, where X is a hydrolyzable radical, and is generally selected from halogen, alkoxy and fluorenyloxy. Among the preferred silanes, X is preferably a gas group, a bromo group, an iodo group, a methoxy group, an ethoxy group, and an ethoxy group. Preferred hydrolyzable seconds gauges include tetragas, tetramethoxysilane, and tetraethoxysilane. Suitable silanes have the general formula SiyOzX4y-2z, where X is selected from the group consisting of halogen, slope and oxo, y is greater than or equal to two, z is greater than or equal to one, and 4y-2z is greater than zero. Preferred hydrolyzable silicas include hexagas disilane, ten gas trisilicon, and higher carbon number chlorosilicon oligomers. The hydrolyzable pit or broken oxygen appearance has two functions: it is to become a part of the coating and impart resistance to aging and abrasion; the second is to dry the solvent. Typical hydrocarbon solvents may contain 50 to 200 ppm of water. Other solvents may contain higher water content. For example, the solvent needs to contain 20 ppm of water, which is present in an amount sufficient to partially hydrolyze a 0.5% by weight perfluoroalkylalkanesilane. The fully hydrolyzed silane or siloxane can eliminate or reduce the water content in the solvent before the perfluorocarbon * base gauge is added. No 彳, _ > -6- This paper size applies to Chinese national standards (CNS > A4 size (2 丨 0X297 mm) -------- Second Clothing ------. Order- ---- m (Please read the precautions on the back before filling this page) Imprint 415923 A7 B7 _____ of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (4) Hydrolyzed perfluoroalkyl silanes will cause insufficient Latent deposition or extremely poor durability. The preferred perfluoroalkyl alkane silanes have the general formula RffiR, siX4-m_n, where R is a perfluoroalkyl alkyl; m is generally one, and 11 is generally zero or one. And m + η is less than 4; R is vinyl or alkyl, preferably methyl, ethyl, vinyl or propyl; and X is preferably halogen, alkoxy, and 'or alkoxy The preferred perfluoroalkyl group in the perfluoroalkylalkyl group is CF3 to C30F61, more preferably, and the most preferred is C8F17 to C12F25; the alkyl group is preferably ethyl. Methyl or ethyl. Preferred X groups include hydrolyzable chloro, bromo, iodo, methoxy, ethoxy, and ethenyloxy groups. According to the present invention, the preferred perfluoroalkyl silanes include all fluorine Alkyl ethylene trisiloxane, perfluoroalkyl ethylene trimethoxysilane, perfluoroalkyl ethylene triethoxysilane, perfluoroalkyl ethylene disiloxane (meth) silane, and perfluoroalkyl ethylene diethoxy (methyl Silane. These better perfluorofluorene radicals appear to react on a molecular basis with the bonding sites on the substrate surface. The strong surface bonding of perfluoroalkylsilanes produces a durable substrate On the surface, it exhibits a high contact angle to water droplets and shows high repellency to water. Suitable solvents include hexane, heptane, mineral spirits, acetone, toluene and naphtha. Preferred solvents are alkanes or halogenated hydrocarbons. Solvents, such as trigas, trigas, and methylene gaseous compounds, as well as perfluorinated organic compounds, such as perfluorinated carbon. Suitable percentages of silane are from about 0.05 to about 500, and preferably from about 0.05 to 5. The solvent can be evaporated only by drying at ambient temperature, or the remaining solution can preferably be removed by wiping. ---------. I --------, 1T- ----- ^ ί Please read the notes on the back before reading and writing this page)
經濟部中央標準局員工消費合作社印製 415923 at _____B7 五、發明説明(5 ) 該矽虎亦可交聯形成更耐久之塗層。熟化較佳係藉由加 熱該碎烷處理表面而達成。一般而言,較佳之熟化溫度係 至少150°F(約66°C),高於200°F(約93°C)更佳。適當 之熟化周期係於約200 °F(約93 °C )下約3 0分鐘。較高溫 及較短加熱時間可能更有效率。較佳之熟化周期係於約 400至5 00°F(約204。(:至260°C)下約2至5分鐘,於約 470°F(約243 C)下約3分鐘尤佳亦可如美國專利第 5,308,705號所述,將氟化烯烴調聚物併入矽晚组合物 中,該調聚物較佳係具一般式CmF2m+lCH = CH2,其中m 係1至3 0,較佳係1至1 6,更佳係4至1 0。另外,該底質 表面可以汽相形態與全氟烷基烷矽烷接觸。 此處記載之接觸角係藉固定滴法測量,其係使用Lord 製造有限公司所製造之改良附帶泡床指示器,裝有 G a e r t n e r S c i e n t i f i c測角器透鏡。待測量表面係放置於 水平位置,面朝上,並位於光源前。一粒水滴係放置於光 源前、該表面之頂面,以便觀測該固定液滴之外形,並藉 由設有圓形測角器刻度之測角器望遠鏡測量接觸角。 老化室(Weathering chamber)包括 Cleveland 凝結 櫃(Condensing Cabinet)及 QUV 測試器(Q-panei 公 司’ Cleveland, OH之產品)。該CCC室係於蒸汽溫度 140°F(60°C)、室内周圍環境下操作,其造成水固定凝結 於測試表面上。該QUV測試器係於8小時周期之UV (B 3 1 3或F S 4 0燈)' 6 5 - 7 0。。之黑面板溫度及5 0。(:凝結濕 度下操作4小時。 -8- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ίι 裝丨--:---ir------線 (請先閲讀背面之注意事項*:填寫本頁〕 415923 A7 415923 A7 經濟部中央標準局貝工消費合作社印製 __—____B7 五、發明説明(6 ) 藉由以下特定實例之敘述可更進一步暸解本發明。Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 415923 at _____B7 V. Description of the Invention (5) The silicone tiger can also be cross-linked to form a more durable coating. The aging is preferably achieved by heating the crushed alkane-treated surface. In general, the preferred ripening temperature is at least 150 ° F (about 66 ° C), and more preferably above 200 ° F (about 93 ° C). A proper aging cycle is about 30 minutes at about 200 ° F (about 93 ° C). Higher temperatures and shorter heating times may be more efficient. The preferred maturation period is about 400 to 500 ° F (about 204. (: to 260 ° C)) for about 2 to 5 minutes, and about 470 ° F (about 243 C) for about 3 minutes. As described in US Patent No. 5,308,705, a fluorinated olefin telomer is incorporated into a silicon evening composition. The telomer is preferably of the general formula CmF2m + lCH = CH2, where m is 1 to 30, more preferably 1 to 16, more preferably 4 to 10. In addition, the surface of the substrate can be contacted with the perfluoroalkyl silane in the vapor phase form. The contact angle described here is measured by the fixed drop method, which is made by Lord Co., Ltd. made a modified bubble bed indicator equipped with a Gertner Scientific goniometer lens. The surface to be measured is placed in a horizontal position, facing up, and in front of the light source. A drop of water is placed in front of the light source, The top surface of the surface is used to observe the shape of the fixed droplet, and the contact angle is measured by a goniometer telescope equipped with a circular goniometer scale. The Weathering chamber includes a Cleveland Condensing Cabinet and QUV tester (product of Q-panei's Cleveland, OH). The CCC chamber is operated at a steam temperature of 140 ° F (60 ° C) and indoor ambient conditions, which causes water to condense on the test surface. The QUV tester is UV (B 3 1 3 or FS) in an 8-hour cycle 4 0 lights) '6 5-7 0 ... of the black panel temperature and 50 0. (: 4 hours of operation under condensing humidity. -8- This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) ίι Installation 丨-: --- ir ------ line (please read the notes on the back *: fill out this page first) 415923 A7 415923 A7 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs _______B7 5 Explanation of the invention (6) The present invention can be further understood by the description of the following specific examples.
實例I 藉由混合一克四氣珍跪及一克全氟坑基院砂燒於4〇克 四氣三氟乙晞中(Freon® TF溶劑,杜邦公司之產品)而 製備溶液。該全氟烷基烷矽烷包含全氟烷基乙三氣秒燒, 其中該全氟烷基部份主要包含CeFuiCuFu。爲比較起 見’製備一未混有四氣矽坡之對照溶液。將溶液使用於 3.9微米厚之Solex®溶融玻璃(片片堅工業有限公司之產 品)之大氣壓表面上,其下墊有棉墊。取樣管於2〇〇。f(93 C )下熟化一小時。使用溶劑洗滌玻璃表面以移除劑餘之 矽烷。取樣管於CCC及QUV-FS40老化室中使其老化。 利用固定水滴之接觸角測量塗層效率。其結果示於以下之 表0Example I A solution was prepared by mixing one gram of Siqi Zhenqi and one gram of perfluorinated pit base sand in 40 grams of Siqi trifluoroacetamidine (Freon® TF solvent, product of DuPont). The perfluoroalkylalkane silane includes a perfluoroalkylethane trisulfide, wherein the perfluoroalkyl portion mainly includes CeFuiCuFu. For comparison's sake, a control solution was prepared without Siqi slope. The solution was applied to the atmospheric surface of 3.9 micron thick Solex® fused glass (product of Pianjianjian Industry Co., Ltd.) with a cotton pad under it. Sampling tube at 2000. Matured at f (93 C) for one hour. The surface of the glass was washed with a solvent to remove the remaining silane. Sampling tubes were aged in CCC and QUV-FS40 aging chambers. Measurement of coating efficiency using contact angles of fixed water droplets. The results are shown in Table 0 below.
表I CCC 0 U V - F ς η 小時 底劑 無底劑 小時 底劑 無底劑 0 105° 105° 0 107° 106° 496 102° 87。 319 106° 102° 927 67° 60° 1332 91。 89。 1669 49° 40° 2115 83° 79° 2498 78。 70。 2943 72° 57°Table I CCC 0 U V-F η hours Primer No primer No Hour Primer No primer 0 105 ° 105 ° 0 107 ° 106 ° 496 102 ° 87. 319 106 ° 102 ° 927 67 ° 60 ° 1332 91. 89. 1669 49 ° 40 ° 2115 83 ° 79 ° 2498 78. 70. 2943 72 ° 57 °
實例II 製備四種溶液’各有於Isopar L溶劑(Exxon之產品) -9- 本紙張尺度適用中國國家標準(CNS ) A4規格(2丨0X297公釐) (請先閲讀背面之注意事項再填寫本頁) if 1¾. —訂 415923 Λ7 Α7 ---- Β7 五、發明説明(7 ) 中之0_5重量百分比之全氟己基乙三氣矽烷,烷類之混合 物。該溶液分別具〇.〇、0.2、045及0.79重量百分比之 四氯矽烷。添加順序爲IS0par L、四氣矽烷及全氟烷基 乙三氣矽烷,以藉由可水解之四氣矽烷利用該溶劑之反應 性乾燥。此四溶液塗層於0182英吋(46釐米)厚清晰熔 融玻璃之取樣管之錯表面上。於CCC室中測試試樣。藉 由固定水滴之接觸角測量塗層效率。由以下之表顯示,於 此範圍内增加可水解矽燒之濃度,可增進該全氟烷基烷矽 燒表面處面之耐久性。Example II Preparation of four solutions' each in Isopar L solvent (Exxon's product) -9- This paper size applies to China National Standard (CNS) A4 specification (2 丨 0X297 mm) (Please read the precautions on the back before filling (This page) if 1¾. — Order 415923 Λ7 Α7 ---- B7 5. In the description of the invention (7), 0-5 weight percent of perfluorohexylethanetrisiloxane, a mixture of alkanes. The solutions had tetrachlorosilane at 0.0, 0.2, 045 and 0.79 weight percent, respectively. The order of addition was ISOpar L, tetragas silane, and perfluoroalkylethane trigas silane to dry with the reactivity of the solvent by hydrolyzable tetragas silane. The four solution coating was on the wrong surface of a 0182 inch (46 cm) thick clear glass sampling tube. Test specimens in a CCC room. Coating efficiency is measured by the contact angle of a fixed water drop. As shown in the following table, increasing the concentration of hydrolyzable sintered silicon in this range can improve the durability of the surface of the sintered surface of the perfluoroalkyl silane.
表II _CCC接觸角 塵劑濃彦(重量百分比、丨 小時 0. 0.2 0.45 0.79 0 115 115 114 1 14 122 8 1 89 105 10 5 284 54 65 77 8 1 475 3 6 44 58 69 642 • " 實例III -- 47 經濟部中央標準局員工消費合作社印製 II---^-----(ά! (請先閱讀背面之注項再填寫本頁) 製備四種溶液’各有於Fluorinert® FC-77溶劑(3]yj 之產品)中之2·5重量百分比之全氟烷基乙三氣矽烷(如貪 例I中所述者)’及2.5重量百分比之全氟烷基乙締。該凉 液分別具〇.〇、〗.〇、2.0及5.0重量百分比之四氣妙概。 此四溶液塗層於0.1 87英吋(4.7釐米)厚清晰熔融玻璃之 -10· 本紙張尺度適用中國國家標準(CNS ) Α4規格(2 ] 0 X 297公釐) 經濟部中央標準局員工消費合作社印製 415923 A7 _____ B7_五、發明説明(8 ) 取樣管之錫表面上。取樣管於300°F(149°C)下熟化15分 鐘。於C C C及QU VB - 3 1 3室中測試試樣。藉由固定水滴 之接觸角測量塗層效率。結果示於以下之表。 表ΙΠΑ CCC接觸角(°) 底劑濃度(重量百分比) 小時 0 1.0 2.0 5.0 0 113 113 115 114 162 95 1 09 1 14 112 348 73 8 1 98 93 684 3 1 4 1 43 34 表 ΙΙΙΒ QUVB-3 1 3 接觸角 底劑濃度(重量百分比ΐ 小時 0. 1.0 2^0 5.0 0 113 1 14 117 116 566 107 1 1 1 111 109 1375 82 95 95 87 2095 72 80 84 71 實例IV 製備於Isopar L溶劑中包含〇.5重量百分比之全氟烷基 乙三氣矽烷、含或不含0.5重量百分比之四氣矽烷之溶 液。使用三種全氟烷基乙三氣矽烷:1H, 1H,2H,2H- -11 - 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公I ) . -----Γ-^-- (請先閱讀背面之注項再填寫本頁) 、1ΤTable II _CCC Contact Angle Dust Concentrate (weight percent, hour 0. 0.2 0.45 0.79 0 115 115 114 1 14 122 8 1 89 105 10 5 284 54 65 77 8 1 475 3 6 44 58 69 642 • " Example III-47 Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs II --- ^ ----- (ά! (Please read the note on the back before filling out this page) Prepare four solutions' Each of them is in Fluorinert® FC-77 solvent (product of 3] yj) 2.5% by weight of perfluoroalkylethanetrisiloxane (as described in Example I) 'and 2.5% by weight of perfluoroalkylethane. The cooling solution has four kinds of qi, such as 〇.〇, 〇.〇, 2.0 and 5.0% by weight. The four solution coating is -10 of 0.1 87 inches (4.7 cm) thick clear molten glass. This paper size is applicable China National Standard (CNS) Α4 specification (2) 0 X 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 415923 A7 _____ B7_ V. Description of the invention (8) The tin surface of the sampling tube. The sampling tube is at 300 15 minutes at ° F (149 ° C). Test specimens in CCC and QU VB-3 1 3 chambers. Measure by contact angle with fixed water droplets The coating efficiency was measured. The results are shown in the following table. Table III CCC contact angle (°) Primer concentration (% by weight) Hour 0 1.0 2.0 5.0 0 113 113 115 114 162 95 1 09 1 14 112 348 73 8 1 98 93 684 3 1 4 1 43 34 72 80 84 71 Example IV A solution containing 0.5% by weight of perfluoroalkylethanetrisiloxane in Isopar L solvent, with or without 0.5% by weight of tetrakisilane, was used. Three types of perfluoroalkylethane Gas Silane: 1H, 1H, 2H, 2H- -11-This paper size applies to China National Standard (CNS) A4 specification (210X297 male I). ----- Γ-^-(Please read the note on the back first Refill this page), 1T
C 經濟部中央標準局負工消費合作杜印製 415923 A7 1 - ---- B7 五、發明説明(9 ) 十二氟辛基二氣矽烷(簡稱“辛基,,)、1H,ih,% 十七氟癸基三氣矽烷(簡稱“癸基,,),或如實例〖所述之全 氟烷基乙三氣矽烷。於此研究中,使用回火s〇iex<8玻璃 取樣管,及經熱處理模擬爲寶曲圓形(未經嚴重_曲)之清 晰熔融玻璃取樣管。該So lex破璃係〇157英吋(4釐米) 厚、孩清晰熔融玻璃係〇.〇 90英吋(2 3釐米)厚,且該錫 表面係經處理者。於QUVB_313室中及濕雪撬磨損測試 器(Sheen ItiStruments LTD,M〇del 9〇3)上測試試 樣=該濕雪橇磨損測試器係照例以具兩支自動檔風玻璃雨 翼之鋁塊加以改良。具此構造之濕雪撬磨損測試具有異常 高壓之雨刷臂負載,且於部分濕部分乾之情況下操作。這 些雨刷之撞擊力遠較平常用於交通工具者爲強。藉由固定 水滴之接觸角測量塗層效率。於以下之表中,加號“ +,,代 表於該塗層配方中存有四氣發坡。C. Work and Consumer Cooperation of Central Standards Bureau of the Ministry of Economic Affairs, printed 415923 A7 1----- B7 V. Description of the Invention (9) Dodecafluorooctyl digas silane ("Octyl,"), 1H, ih, % Heptafluorofluorodecyltrigassilane ("decyl," for short), or perfluoroalkylethanetrigassilane as described in Example 〖. In this study, tempered soex < 8 glass sampling tubes and clear molten glass sampling tubes that were heat treated to simulate a Baoqu round shape (not severely curved) were used. The So lex broken glass is 0157 inches (4 cm) thick, and the clear glass is 0. 90 inches (23 cm) thick, and the tin surface is treated. Test sample in QUVB_313 room and wet sled abrasion tester (Sheen ItiStruments LTD, Model 903) = The wet sled abrasion tester is conventionally made of an aluminum block with two automatic windshield rain wings Improvement. The wet sledge abrasion test with this structure has an abnormally high pressure wiper arm load, and it is operated with some wet and dry parts. The impact force of these wipers is much stronger than those usually used for transportation. The coating efficiency is measured by the contact angle of a fixed water drop. In the following table, the plus sign "+" indicates that there are four gas slopes in the coating formulation.
表IVA QUVB-313 接觸角 小時 辛基 辛基+ 癸基 癸基+ j昆合物 混合物+ 0 116 112 111 115 111 118 163 102 105 87 112 1 02 116 3 52 95 95 84 107 1 00 111 496 82 8 8 74 102 89 106 659 79 80 66 93 82 99 827 70 85 60 89 82 103 -12- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)Table IVA QUVB-313 contact angle hours octyl octyl + decyl decyl + j quinone mixture + 0 116 112 111 115 111 118 163 102 105 87 112 1 02 116 3 52 95 95 84 107 1 00 111 496 82 8 8 74 102 89 106 659 79 80 66 93 82 99 827 70 85 60 89 82 103 -12- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)
^ q ^ 訂 球 /1^ (請先閲讀背面之注意事項再填寫本頁J 415923 A7 __—_ B7 五、發明説明(1〇 ) 表IVB 濕雪撬磨損接觸海f。、 周期 辛基 辛基+ 癸基 癸基+ 混合物 混合物+ 0 113 117 111 116 115 117 200* 86 104 79 108 86 108 600* 52 99 78 1 06 79 105 5000 3 5 84 47 91 82 92 *200及600周期之數據係以水中之〇5重量百分比之Hi· Sil® 233合成沈澱矽氧之漿液測得;5000周期之數據則 僅使用去離子水而測得。 (請先閱讀背面之注$項再填寫本頁) 經濟部中央標準局員工消費合作社印製 實例V 混合9 5克F C - 7 7溶劑、2 · 5克全氟烷基乙三氣矽烷(全 氟坑基= C6F〖3至C18F37),及2_5克全氟燒乙烯以製備對 照溶液。混合1 8 8克F C - 7 7溶劑、5克全氟烷基乙三氣矽 烷、5克全氟烷基乙缔(全氟烷基= c6F|3至C18F37),及2 克四氯矽烷以製備含底劑溶劑。以1 9 8 · 4克F C - 7 7溶劑及 1.6克四氣矽烷製備僅有底劑之溶液。將這些溶液使用於 4.9微米厚之清熔融玻璃之鍚表面上,其下墊有棉墊。經 選取之取樣管於以底劑溶劑塗層前,先以對照溶液或包含 全氟烷基烷矽烷及四氣矽烷之溶液塗層。取樣管於 300°F(14 9°C)下熟化15分鐘。使用溶劑洗滌以移除玻璃 表面剩餘之矽烷。取樣管於CCC中使其老化。利用固定 水滴之接觸角測量塗層效率a -13- 本紙張尺度遑用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央標準局員工消費合作杜印製 415923 A7 B7 五、發明説明(11 )^ q ^ Order the ball / 1 ^ (Please read the precautions on the back before filling in this page J 415923 A7 __—_ B7 V. Description of the invention (1〇) Table IVB Wet sled wear contact with the sea f., Periodic octylcin Base + decyldecyl + mixture mixture + 0 113 117 111 116 115 117 200 * 86 104 79 108 86 108 600 * 52 99 78 1 06 79 105 5000 3 5 84 47 91 82 92 * 200 and 600 cycle data Measured with 0.05% by weight of Hi · Sil® 233 synthetic precipitated silica slurry in water; 5,000 cycles of data were measured using only deionized water. (Please read the note on the back before filling this page) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V Mixed 9 5g FC-7 solvent, 2.5g perfluoroalkylethanetrisiloxane (perfluorinated base = C6F [3 to C18F37), and 2_5g Perfluorinated ethylene was used to prepare a control solution. Mix 1 8 g of FC-7 solvent, 5 g of perfluoroalkylethanetrisilanes, 5 g of perfluoroalkylethylene (perfluoroalkyl = c6F | 3 to C18F37 ), And 2 grams of tetrachlorosilane to prepare a primer-containing solvent. 198 · 4 grams of FC-7 solvent and 1.6 grams of tetragas silane to prepare a primer-only solution These solutions were used on the surface of the 4.9 micron thick clear molten glass with cotton pads underneath. The selected sampling tubes were coated with a control solution or containing a perfluoroalkyl alkane before coating with a primer solvent. And four gas silane solution coating. The sample tube was aged at 300 ° F (14 9 ° C) for 15 minutes. Wash with solvent to remove the remaining silane on the glass surface. The sample tube was aged in CCC. Use fixed water droplets Contact angle measurement of coating efficiency a -13- This paper size adopts Chinese National Standard (CNS) A4 specification (210X297 mm) Employees' cooperation cooperation of Central Standards Bureau of the Ministry of Economic Affairs 415923 A7 B7 V. Description of invention (11)
表V CCC接觸角(°) 無底劑層 ΜΛΛ 小時 無完整底劑具完整底劑 無完整Mi 具完整底劑 0 114 114 113 1 14 232 116 116 117 115 398 100 110 109 110 590 49 78 75 86 9 18 29 39 3 1 41 無論玻璃是否有預先以矽烷層或可水解矽烷之溶液爲底, 包含可水解爲矽氧之矽烷之溶液皆可導致較耐久之塗層。 上述實例係用以説明本發明。可利用任甸習知技街使 用諸多全氟烷基烷矽烷、可水解矽烷、溶劑及濃度,並於 適當溫度下、經過適切之時間使其最達最適熟化,以於任 何諸種玻璃及塑膠底質,以及其它例如金屬、陶瓷、搪 瓷,及金屬或金屬氧化物薄膜之無機表面上提供耐久性不 潤濕性表面。本發明之經處理底質係特別適合用於汽車及 飛機元件,以及建築部份、鏡片及CRT板上。 此處用於本發明組合物成份之“主要包含”一詞之用以 表示,該化合物並未另外包含會對該等成份所提供之性質 造成反效果之成份。 -14- 本紙張尺度適用中國國家標準(CNS )八私見格(210X297公釐) ^ ^ {,裝-----丨.訂------银-: (請先閲讀背面之注意事項再填寫本頁)Table V CCC contact angle (°) No primer layer ΜΛΛ hours No intact primer with intact primer No intact Mi with intact primer 0 114 114 113 1 14 232 116 116 117 115 398 100 110 109 110 590 49 78 75 86 9 18 29 39 3 1 41 Regardless of whether the glass is pre-based with a silane layer or a hydrolyzable silane solution, solutions containing hydrolyzable silanes can lead to more durable coatings. The above examples are provided to illustrate the present invention. Can use Rendian Xizhi Street to use many perfluoroalkylalkane silanes, hydrolyzable silanes, solvents and concentrations, and at the appropriate temperature and appropriate time to make it the most suitable maturation for any kind of glass and plastic substrate Materials, and other inorganic surfaces such as metals, ceramics, enamels, and metal or metal oxide films provide durable non-wetting surfaces. The treated substrate of the present invention is particularly suitable for use in automotive and aircraft components, as well as building parts, lenses and CRT boards. As used herein, the term "mainly containing" of the ingredients of the composition of the present invention is used to indicate that the compound does not additionally contain ingredients that would adversely affect the properties provided by the ingredients. -14- This paper size is in accordance with Chinese National Standard (CNS) Eight Private Views (210X297mm) ^ ^ {, installed ----- 丨. Order ---- silver-: (Please read the note on the back first (Fill in this page again)
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US46146495A | 1995-06-05 | 1995-06-05 |
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TW085105930A TW415923B (en) | 1995-06-05 | 1996-05-20 | Compositions for producing a water-repellent surface on a substrate |
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JP (1) | JPH08333545A (en) |
KR (1) | KR100194250B1 (en) |
CN (1) | CN1072700C (en) |
CA (1) | CA2175848C (en) |
TW (1) | TW415923B (en) |
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DE19731416C1 (en) * | 1997-07-22 | 1998-09-17 | Vetrotech Saint Gobain Int Ag | Fire protection glazing filled with hardened hydrated alkali poly:silicate avoiding localised delamination in fire |
GB0206930D0 (en) | 2002-03-23 | 2002-05-08 | Univ Durham | Method and apparatus for the formation of hydrophobic surfaces |
JP5343271B2 (en) * | 2003-09-17 | 2013-11-13 | 小川 一文 | Water repellent and oil repellent antifouling glass plate, production method thereof, automobile and electromagnetic cooker using the same |
JP2012097267A (en) * | 2003-09-17 | 2012-05-24 | Kazufumi Ogawa | Water and oil repellency composite film-forming solution, manufacturing method of water and oil repellency composite film using the solution, and water and oil repellency composite film using the method |
CN100396751C (en) * | 2005-06-21 | 2008-06-25 | 广州市白云化工实业有限公司 | Organic silicon fluoro water proofing agent and its preparation method |
US11786036B2 (en) | 2008-06-27 | 2023-10-17 | Ssw Advanced Technologies, Llc | Spill containing refrigerator shelf assembly |
US8286561B2 (en) | 2008-06-27 | 2012-10-16 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
EP2346678B1 (en) | 2008-10-07 | 2017-10-04 | Ross Technology Corporation | Spill resistant surfaces having hydrophobic and oleophobic borders |
MX343584B (en) | 2009-11-04 | 2016-11-10 | Ssw Holding Co Inc | Cooking appliance surfaces having spill containment pattern and methods of making the same. |
CA2796305A1 (en) | 2010-03-15 | 2011-09-22 | Ross Technology Corporation | Plunger and methods of producing hydrophobic surfaces |
BR112013021231A2 (en) | 2011-02-21 | 2019-09-24 | Ross Tech Corporation | superhydrophobic and oleophobic coatings with low voc bonding systems |
EP2791255B1 (en) | 2011-12-15 | 2017-11-01 | Ross Technology Corporation | Composition and coating for superhydrophobic performance |
WO2014003852A2 (en) | 2012-06-25 | 2014-01-03 | Ross Technology Corporation | Elastomeric coatings having hydrophobic and/or oleophobic properties |
CN104829641B (en) * | 2015-05-12 | 2018-01-19 | 傅筠 | A kind of fluorine-containing organic silicon monomer and preparation method thereof |
KR101912605B1 (en) * | 2017-03-10 | 2018-10-30 | 경기대학교 산학협력단 | Super-Hydrophobic Particle and Composite having the Same |
CN108395115B (en) * | 2018-02-01 | 2022-05-13 | 阿尔特汽车技术股份有限公司 | Automobile rear-view mirror |
CN110981225A (en) * | 2019-12-20 | 2020-04-10 | 苏州浩纳新材料科技有限公司 | Hydrophobic rainproof coating for glass, preparation method and application method |
CN111501354B (en) * | 2020-05-23 | 2022-11-04 | 苏州大学 | Oil-proof antifouling self-cleaning functional fabric and preparation method thereof |
CN111849225B (en) * | 2020-08-03 | 2021-11-05 | 中铝瑞闽股份有限公司 | Graphene/alkane composite coating for aluminum alloy plate strip and preparation method thereof |
CN113930155B (en) * | 2021-11-18 | 2022-05-31 | 福耀玻璃工业集团股份有限公司 | Hydrophobic coating liquid, glass and preparation method thereof |
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JPS6051103A (en) * | 1983-08-30 | 1985-03-22 | Shin Etsu Chem Co Ltd | Antifouling treatment |
JPH0759699B2 (en) * | 1987-10-05 | 1995-06-28 | ダイキン工業株式会社 | Water and oil repellent composition |
US5523161A (en) * | 1990-04-03 | 1996-06-04 | Ppg Industries, Inc. | Water repellent surface treatment with integrated primer |
US5308705A (en) * | 1990-04-03 | 1994-05-03 | Ppg Industries, Inc. | Water repellent surface treatment |
JPH04144940A (en) * | 1990-10-05 | 1992-05-19 | Asahi Glass Co Ltd | Water repellent and oil repellent composition |
JP2500149B2 (en) * | 1991-01-23 | 1996-05-29 | 松下電器産業株式会社 | Water- and oil-repellent coating and method for producing the same |
JP2555797B2 (en) * | 1991-05-13 | 1996-11-20 | トヨタ自動車株式会社 | Water repellent glass and method for manufacturing the same |
JP3155025B2 (en) * | 1991-05-17 | 2001-04-09 | 旭硝子株式会社 | Surface-treated building / building article and method of manufacturing the article |
JP2874391B2 (en) * | 1991-06-05 | 1999-03-24 | 日産自動車株式会社 | Manufacturing method of water-repellent glass |
JPH05170486A (en) * | 1991-12-25 | 1993-07-09 | Central Glass Co Ltd | Water repellent for glass surface and water-repellent glass |
JPH06293782A (en) * | 1993-04-07 | 1994-10-21 | Mitsubishi Kasei Corp | Coating composition |
CA2175849C (en) * | 1995-06-01 | 2003-07-15 | George B. Goodwin | Autophobic water repellent surface treatment |
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KR970001503A (en) | 1997-01-24 |
CN1141941A (en) | 1997-02-05 |
CA2175848A1 (en) | 1996-12-06 |
JPH08333545A (en) | 1996-12-17 |
CN1072700C (en) | 2001-10-10 |
CA2175848C (en) | 2000-01-11 |
KR100194250B1 (en) | 1999-06-15 |
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