TW201905113A - 親水性塗布膜形成用組成物及使用其之親水性塗布膜 - Google Patents
親水性塗布膜形成用組成物及使用其之親水性塗布膜Info
- Publication number
- TW201905113A TW201905113A TW107120480A TW107120480A TW201905113A TW 201905113 A TW201905113 A TW 201905113A TW 107120480 A TW107120480 A TW 107120480A TW 107120480 A TW107120480 A TW 107120480A TW 201905113 A TW201905113 A TW 201905113A
- Authority
- TW
- Taiwan
- Prior art keywords
- coating film
- hydrophilic coating
- forming
- group
- composition
- Prior art date
Links
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
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- 238000001226 reprecipitation Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- SESSOVUNEZQNBV-UHFFFAOYSA-M sodium;2-bromoacetate Chemical compound [Na+].[O-]C(=O)CBr SESSOVUNEZQNBV-UHFFFAOYSA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- OAVPBWLGJVKEGZ-UHFFFAOYSA-N tributoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCCCC)(OCCCC)OCCCC)CCC2OC21 OAVPBWLGJVKEGZ-UHFFFAOYSA-N 0.000 description 1
- UCSBCWBHZLSFGC-UHFFFAOYSA-N tributoxysilane Chemical compound CCCCO[SiH](OCCCC)OCCCC UCSBCWBHZLSFGC-UHFFFAOYSA-N 0.000 description 1
- MMZPUXVBQAQQDQ-UHFFFAOYSA-N triethoxy(2-pyridin-4-ylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC1=CC=NC=C1 MMZPUXVBQAQQDQ-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- UNKMHLWJZHLPPM-UHFFFAOYSA-N triethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CCO[Si](OCC)(OCC)COCC1CO1 UNKMHLWJZHLPPM-UHFFFAOYSA-N 0.000 description 1
- OHKFEBYBHZXHMM-UHFFFAOYSA-N triethoxy-[1-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)C(CCC)OCC1CO1 OHKFEBYBHZXHMM-UHFFFAOYSA-N 0.000 description 1
- SJQPASOTJGFOMU-UHFFFAOYSA-N triethoxy-[1-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)C(C)OCC1CO1 SJQPASOTJGFOMU-UHFFFAOYSA-N 0.000 description 1
- NFRRMEMOPXUROM-UHFFFAOYSA-N triethoxy-[1-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)C(CC)OCC1CO1 NFRRMEMOPXUROM-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- FVMMYGUCXRZVPJ-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CC(CC)OCC1CO1 FVMMYGUCXRZVPJ-UHFFFAOYSA-N 0.000 description 1
- RWJUTPORTOUFDY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCOCC1CO1 RWJUTPORTOUFDY-UHFFFAOYSA-N 0.000 description 1
- CFUDQABJYSJIQY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CC(C)OCC1CO1 CFUDQABJYSJIQY-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DAVVOFDYOGMLNQ-UHFFFAOYSA-N trimethoxy-[1-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)C(C)OCC1CO1 DAVVOFDYOGMLNQ-UHFFFAOYSA-N 0.000 description 1
- FNBIAJGPJUOAPB-UHFFFAOYSA-N trimethoxy-[1-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)C(CC)OCC1CO1 FNBIAJGPJUOAPB-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- ZNXDCSVNCSSUNB-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)CCOCC1CO1 ZNXDCSVNCSSUNB-UHFFFAOYSA-N 0.000 description 1
- HTVULPNMIHOVRU-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CC(C)OCC1CO1 HTVULPNMIHOVRU-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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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
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
本發明提供親水性塗布膜及可得到其的親水性塗布膜形成用組成物,該親水性塗布膜係即使在高溫高濕條件下的保管,親水性、防霧性亦不變差。 該親水性塗布膜形成用組成物含有:具有在含氮雜環構造中的氮原子具有正(+)電荷的甜菜鹼基之如以式[1]所示的矽氧烷單體、與水或有機溶劑。 (R1:碳數1~5的烷基,R2:碳數1~5的烷基等,p:1~3,q:當p為1時表示0~2,當p為2時表示0~1,當p為3時表示0,L:碳數1~20之可具有雜原子之直鏈狀或分枝狀的伸烷基,X:單鍵等,Y:包含含氮雜環的2價有機基,M:碳數1~10之直鏈狀或分枝狀的伸烷基,且與Y中的氮原子鍵結,M及L之任一者藉由與Y中的氮原子之鍵結而形成N+部分,Z:COO-、SO3 -等)。
Description
本發明關於具有將表面親水化及防霧效果之親水性塗布膜形成用組成物以及使用其之親水性塗布膜。
於基材所要求的表面特性中,已知防霧性、抗靜電性、防污性及生物體適合性等。此等之表面特性一般係藉由在基材之表面上,塗布(被覆)親水性被膜等賦予親水性,藉此達成。 作為能將親水性賦予至基板之聚合物,例如已知含有磷醯基的甲基丙烯酸酯之聚合物(參照專利文獻1),或於具有與水的相互作用非常強的甜菜鹼基之化合物,導入有能與無機基材形成共價鍵結之官能基的化合物(參照專利文獻2)等。
然而,此等之材料中有因在高溫高濕條件下的保管,而上述親水性、防霧性等之表面特性徐徐地或急劇地變差之問題。 [先前技術文獻] [專利文獻]
專利文獻1:日本特開平6-313009號公報
[發明所欲解決的課題]
本發明係鑒於如此之點而完成者,本發明之目的在於提供親水性塗布膜形成用組成物及由其所得到的親水性塗布膜,該親水性塗布膜係即使在高溫高濕條件下的保管,親水性、防霧性等的表面特性亦不變差。
[解決課題的手段] 如此地,本發明具有以下之要旨。 [1]一種親水性塗布膜形成用組成物,其含有:具有在含氮雜環構造中的氮原子具有正(+)電荷的甜菜鹼基之矽氧烷單體、與水或有機溶劑。 [2]一種親水性塗層之成膜方法,其係將上述記載之親水性塗布膜形成用組成物塗布於基板上而形成塗膜,將該塗膜乾燥、燒成而得到被膜。 [3]一種親水性塗布膜,其係由上述記載之親水性塗布膜形成用組成物所得。 [發明的效果]
依照本發明,可提供親水性塗布膜形成用組成物及由其所得到的親水性塗布膜,該親水性塗布膜係即使在高溫高濕條件下的保管,親水性、防霧性亦不變差。 由本發明之親水性塗布膜形成用組成物所得之親水性塗布膜,係可供眼鏡、相機等的透鏡、建築物、車等的窗等之防止水滴附著膜、防霧膜等用。
[實施發明的形態]
本發明之親水性塗布膜形成用組成物之特徵為含有:具有在含氮雜環構造中的氮原子具有正(+)電荷的甜菜鹼基之矽氧烷單體(以下,亦稱為特定矽氧烷單體)、與水或有機溶劑。
<特定矽氧烷單體> 本發明之親水性塗布膜形成用組成物具有:具有在含氮雜環構造中的氮原子具有+電荷的甜菜鹼基之矽氧烷單體。 所謂的甜菜鹼,就是在同一分子內的不相鄰位置具有正電荷與負電荷,能解離的氫原子不鍵結於具有正電荷的原子,分子全體不具有電荷之化合物。
特定矽氧烷單體中所含有的甜菜鹼基之正電荷係存在於含氮雜環上的氮原子。作為含氮雜環之例,可例示吡啶、哌啶、咪唑、唑、噻唑、吡唑、咪唑啉、吡、苯并咪唑、喹啉、異喹啉、嘌呤、喹啉等,其中較佳為吡啶或咪唑啉。
特定矽氧烷單體係由以下之通式所示。
上述式[1]中,R1
表示碳數1~5、較佳1~3的烷基。 R2
表示碳數1~5、較佳1~4的烷基、碳數2~5、較佳2~4的烯基、或碳數2~5、較佳2~4的炔基。R2
所具有的任意之氫原子係可被碳數1~5的烷基、氟原子等的鹵素原子、芳香族環或脂肪族環所取代。p表示1~3之整數。q係當p為1時表示0~2之整數,當p為2時表示0~1之整數,當p為3時表示0。
L表示碳數1~20、較佳1~10之可具有雜原子之直鏈狀或分枝狀的伸烷基。該伸烷基的任意之氫原子係可被碳數1~5、較佳1~4的烷基或氟原子等的鹵素原子、芳香族環或脂肪族環所取代。其中,較佳為碳數2~7、更佳2~6之直鏈或分枝狀的伸烷基。此處,所謂的雜原子,就是意指氧、氮、硫或磷,較佳為氧、氮或硫。
X表示單鍵、-O-、-COO-、-OCO-、-CONR3
-、 -NR4
-CO-或-NR5
=NR6
-。R3
、R4
、R5
、R6
各自獨立地表示氫原子或碳數1~4、較佳1~3的烷基。 Y表示含有含氮雜環的2價有機基。作為例子,可例示吡啶、哌啶、咪唑、唑、噻唑、吡唑、咪唑啉、吡、苯并咪唑、喹啉、異喹啉、嘌呤、喹啉等,其中較佳為吡啶或咪唑啉。
M表示碳數1~10、較佳1~8之直鏈狀或分枝狀的伸烷基,伸烷基的任意之氫原子係可被碳數1~5、較佳1~4的烷基或氟原子等之鹵素原子所取代。其中,較佳為碳數2~7、更佳2~6之直鏈或分枝狀的伸烷基。M係與Y所具有的氮原子鍵結,M及L之任一者藉由與Y所具有的氮原子之鍵結而形成N+
部分。 Z表示COO-
、SO3 -
或PO4 -
。從所得之塗布膜的耐久性之觀點來看,較佳為SO3 -
。
以下例示特定矽氧烷單體之具體例,但不受此等所限定。
式中,Me表示甲基,Et表示乙基。關於N+
部分,亦包含互變異構物。 其中,作為特定矽氧烷單體,從單體的安定性、原料取得性之觀點來看,較佳為以下者。
<特定矽氧烷單體之製造方法> 本發明中所用的特定矽氧烷單體,例如當為磺酸末端時,可藉由對於含有含氮雜環構造的矽化合物,使1,3-丙磺內酯或1,4-丁磺內酯、2,4-丁磺內酯等之磺內酯環化合物反應而製造。
當為羧酸末端時,可藉由使含有含氮雜環構造的矽化合物,與β-丙內酯等之內酯環化合物反應而得。又,藉由對於含有含氮雜環構造的矽化合物附加丙烯酸之方法,亦可得到羧酸末端化合物。與單氯乙酸鉀、單氯乙酸鈉、單溴乙酸鉀、單溴乙酸鈉等之鹵乙酸鹼金屬鹽與含有含氮雜環構造的矽化合物在非水系溶劑中進行反應,藉此亦可得到羧酸末端化合物。
作為反應溶劑,可使用水、醇類(甲醇、乙醇、2-丙醇等)、非質子性極性有機溶劑(二甲基甲醯胺、二甲亞碸、二甲基乙醯胺、N-甲基吡咯啶酮等)、醚類(二乙基醚、二異丙基醚、第三丁基甲基醚、環戊基甲基醚、四氫呋喃、二烷等)、脂肪族烴類(戊烷、己烷、庚烷、石油醚等)、芳香族烴類(苯、甲苯、二甲苯、均三甲苯、氯苯、二氯苯、硝基苯、四氫萘等)、鹵素系烴類(氯仿、二氯甲烷、四氯化碳、二氯乙烷等)、低級脂肪酸酯類(乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯等)、腈類(乙腈、丙腈、丁腈等)等。此等之溶劑係可考慮反應的發生容易度等而適宜選擇,可單獨1種或混合2種以上而使用。又,視情況而定,上述溶劑亦可使用適當的脫水劑或乾燥劑,而作為不含水的溶劑使用。 作為較佳的溶劑,可舉出乙腈或四氫呋喃。
反應時間為30分鐘~180小時,較佳為2~120小時,特佳為5~100小時。 原料之含有含氮雜環構造的矽化合物係可使用市售者,或可藉由眾所周知之方法而簡便地獲得。反應溫度較佳為0℃~各溶劑之沸點,更佳為0℃~120℃,特佳為5℃~100℃。
當反應生成物之特定矽氧烷單體析出至反應有機溶劑中時,可藉由進行過濾、乾燥之方法等而高純度化。當始終在均勻系進行反應時,可直接使用所得之反應生成物,但當目的物之特定矽氧烷單體為固體時,可藉由於將反應溶劑濃縮後,添加弱溶劑而造成的晶析或再沉澱等眾所周知之方法,進行單離、純化。
<其他成分> 本發明之親水性塗布膜形成用組成物係除了特定矽氧烷單體、水或有機溶劑,還可含有選自由金屬烷氧化物、金屬烷氧化物寡聚物、金屬烷氧化物聚合物、無機微粒子、調平劑及界面活性劑所成之群組的至少1種以上。
前述金屬烷氧化物係為了提高所形成的塗布膜之機械安定性而含有者,作為金屬烷氧化物之金屬,可舉出矽、鈦、鋁、鉭、銻、鉍、錫、銦、鋅等。此等之中,從取得性之觀點來看,較佳為矽、鈦或鋯。
作為前述金屬烷氧化物,可舉出以下述式(II)或(III)所示者。式(II)中,R2
表示碳數1~5、較佳1~3的烷基或乙醯基。n表示2~5之整數。M1
較佳為矽(Si)、鈦(Ti)、鋯(Zr)或鋁(Al),特佳為矽(Si)或鈦(Ti)。又,n較佳為3或4。
式(III)中,M1
、R2
係如上述式(I)中定義。R3
係氫原子或選自由鹵素原子、乙烯基、苯乙烯基、苯基、萘基、及可被丙烯酸基、甲基丙烯酸基或芳基所取代,且可包含雜原子之碳數1~30的烷基所成之群組的基。x為1~3之整數。此處,雜原子為氧、氮、硫或磷,較佳為氧、氮或硫。
作為以上述式(II)所示的金屬烷氧化物,例如可舉出四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四丁氧基矽烷、四乙醯氧基矽烷等之矽烷氧化物,四乙氧化鈦、四丙氧化鈦、四丁氧化鈦等之烷氧化鈦,四乙氧化鋯、四丙氧化鋯、四丁氧化鋯等之四烷氧化鋯,三丁氧化鋁、三異丙氧化鋁、三乙氧化鋁等之三烷氧化鋁化合物,五丙氧化鉭、五丁氧化鉭等之五烷氧化鉭等。此等係可單獨或組合2種以上使用。
當上述式(III)之M1
為矽且R3
為氫原子時,例如可舉出三甲氧基矽烷、三乙氧基矽烷、三丙氧基矽烷、三丁氧基矽烷等。此等係可單獨或組合2種以上使用。
當上述式(III)之M1
為矽且R3
為有機基時,例如可舉出甲基三甲氧基矽烷、甲基三丙氧基矽烷、甲基三乙醯氧基矽烷、甲基三丁氧基矽烷、甲基三戊氧基矽烷、甲基三戊氧基矽烷、甲基三苯氧基矽烷、甲基三苄氧基矽烷、甲基三苯乙氧基矽烷、環氧丙氧基甲基三甲氧基矽烷、環氧丙氧基甲基三乙氧基矽烷、α-環氧丙氧基乙基三甲氧基矽烷、α-環氧丙氧基乙基三乙氧基矽烷、β-環氧丙氧基乙基三甲氧基矽烷、β-環氧丙氧基乙基三乙氧基矽烷、α-環氧丙氧基丙基三甲氧基矽烷、α-環氧丙氧基丙基三乙氧基矽烷、β-環氧丙氧基丙基三甲氧基矽烷、β-環氧丙氧基丙基三乙氧基矽烷、g-環氧丙氧基丙基三甲氧基矽烷、g-環氧丙氧基丙基三乙氧基矽烷、g-環氧丙氧基丙基三丙氧基矽烷、g-環氧丙氧基丙基三丁氧基矽烷、g-環氧丙氧基丙基三苯氧基矽烷、α-環氧丙氧基丁基三甲氧基矽烷、α-環氧丙氧基丁基三乙氧基矽烷、β-環氧丙氧基丁基三乙氧基矽烷、g-環氧丙氧基丁基三甲氧基矽烷、g-環氧丙氧基丁基三乙氧基矽烷、d-環氧丙氧基丁基三甲氧基矽烷、d-環氧丙氧基丁基三乙氧基矽烷、(3,4-環氧基環己基)甲基三甲氧基矽烷、(3,4-環氧基環己基)甲基三乙氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、β-(3,4-環氧基環己基)乙基三乙氧基矽烷、β-(3,4-環氧基環己基)乙基三丙氧基矽烷、β-(3,4-環氧基環己基)乙基三丁氧基矽烷、β-(3,4-環氧基環己基)乙基三苯氧基矽烷、g-(3,4-環氧基環己基)丙基三甲氧基矽烷、g-(3,4-環氧基環己基)丙基三乙氧基矽烷、d-(3,4-環氧基環己基)丁基三甲氧基矽烷、d-(3,4-環氧基環己基)丁基三乙氧基矽烷、環氧丙氧基甲基甲基二甲氧基矽烷、環氧丙氧基甲基甲基二乙氧基矽烷、α-環氧丙氧基乙基甲基二甲氧基矽烷、α-環氧丙氧基乙基甲基二乙氧基矽烷、β-環氧丙氧基乙基甲基二甲氧基矽烷、β-環氧丙氧基乙基乙基二甲氧基矽烷、α-環氧丙氧基丙基甲基二甲氧基矽烷、α-環氧丙氧基丙基甲基二乙氧基矽烷、β-環氧丙氧基丙基甲基二甲氧基矽烷、β-環氧丙氧基丙基乙基二甲氧基矽烷、g-環氧丙氧基丙基甲基二甲氧基矽烷、g-環氧丙氧基丙基甲基二乙氧基矽烷、g-環氧丙氧基丙基甲基二丙氧基矽烷、g-環氧丙氧基丙基甲基二丁氧基矽烷、g-環氧丙氧基丙基甲基二苯氧基矽烷、g-環氧丙氧基丙基乙基二甲氧基矽烷、g-環氧丙氧基丙基乙基二乙氧基矽烷、g-環氧丙氧基丙基乙烯基二甲氧基矽烷、g-環氧丙氧基丙基乙烯基二乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、g-氯丙基三甲氧基矽烷、g-氯丙基三乙氧基矽烷、g-氯丙基三乙醯氧基矽烷、3,3,3-三氟丙基三甲氧基矽烷、g-巰基丙基三甲氧基矽烷、g-巰基丙基三乙氧基矽烷、β-氰基乙基三乙氧基矽烷、氯甲基三甲氧基矽烷、氯甲基三乙氧基矽烷、N-(β-胺基乙基) g-胺基丙基三甲氧基矽烷、N-(β-胺基乙基) g-胺基丙基甲基二甲氧基矽烷、g-胺基丙基甲基二甲氧基矽烷、N-(β-胺基乙基) g-胺基丙基三乙氧基矽烷、N-(β-胺基乙基) g-胺基丙基甲基二乙氧基矽烷、二甲基二甲氧基矽烷、苯基甲基二甲氧基矽烷、二甲基二乙氧基矽烷、苯基甲基二乙氧基矽烷、g-氯丙基甲基二甲氧基矽烷、g-氯丙基甲基二乙氧基矽烷、二甲基二乙醯氧基矽烷、g-巰基丙基甲基二甲氧基矽烷、g-巰基甲基二乙氧基矽烷、g-脲基丙基三乙氧基矽烷、g-脲基丙基三甲氧基矽烷、g-脲基丙基三丙氧基矽烷、(R)-N-1-苯基乙基-N’-三乙氧基矽基丙基脲、(R)-N-1-苯基乙基-N’-三甲氧基矽基丙基脲、3-異氰酸酯丙基三乙氧基矽烷、三氟丙基三甲氧基矽烷、溴丙基三乙氧基矽烷、二乙基二乙氧基矽烷、二乙基二甲氧基矽烷、三甲基乙氧基矽烷、三甲基甲氧基矽烷等。此等係可單獨或組合2種以上使用。
上述金屬烷氧化物寡聚物、金屬烷氧化物聚合物係為了提高所形成的塗布膜之機械安定性而含有者。作為此等之金屬,可使用矽、鈦、鋁、鉭、銻、鉍、錫、銦、鋅等之單獨或複合氧化物前驅物。作為金屬烷氧化物寡聚物、金屬烷氧化物聚合物,可為市售品,也可為從金屬烷氧化物等的單體,藉由水解等之常見方法而得者。
作為市售品的金屬烷氧化物寡聚物、金屬烷氧化物聚合物之具體例,可舉出COLCOAT公司製矽酸甲酯51、矽酸甲酯53A、矽酸乙酯40、矽酸乙酯48、EMS-485、SS-101等之矽氧烷寡聚物或矽氧烷聚合物、關東化學公司製正丁氧化鈦四聚物等之二茂鈦寡聚物。此等係可單獨或組合2種以上使用。
又,上述調平劑及界面活性劑等係為了提高塗膜均勻性而含有者,可使用眾所周知者,特別地市售品由於容易取得而較宜。 作為上述無機微粒子,較佳為二氧化矽微粒子、氧化鋁微粒子、氧化鈦微粒子、氟化鎂微粒子等,特佳為此等的無機微粒子之膠體溶液。膠體溶液係可為在分散介質中分散有無機微粒子粉者,也可為市售品的膠體溶液。
藉由在本發明之組成物中含有無機微粒子,成為可賦予所形成的硬化被膜之表面形狀或其他的機能。無機微粒子係其平均粒徑較佳為0.001~0.2μm,更佳為0.001~0.1μm。當該平均粒徑超過0.2μm時,有使用所調製的塗布液而形成的硬化被膜之透明性降低之情況。還有,平均粒徑為50%體積平均粒徑(D50)。
作為無機微粒子之分散介質,可舉出水或有機溶劑。作為膠體溶液,從被膜形成用塗布液的安定性之觀點來看,pH或pKa較佳為調整至1~10,更佳為調整至2~7。 作為無機微粒子之分散介質所用的有機溶劑,可舉出甲醇、乙醇、丙醇、丁醇、乙二醇、丙二醇、丁二醇、戊二醇、2-甲基-2,4-戊二醇、二乙二醇、二丙二醇、乙二醇單丙基醚等之醇類;甲基乙基酮、甲基異丁基酮等之酮類;甲苯、二甲苯等之芳香族烴類;二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等之醯胺類;乙酸乙酯、乙酸丁酯、g-丁內酯等之酯類;四氫呋喃、1,4-二烷等之醚類。其中,較佳為醇類或酮類。此等有機溶劑係可單獨或混合2種以上作為分散介質使用。
可含有的其他成分之中,較佳為烷氧基的一部分可被其他的有機基所取代之金屬烷氧化物、金屬氧化物溶膠或金屬烷氧化物寡聚物。 相對於特定矽氧烷單體的100質量份,本發明之組成物中的上述金屬烷氧化物、金屬氧化物溶膠或金屬烷氧化物寡聚物之含量為0.5~100質量份,較佳為1~60質量份。若為如此的範圍,則可更發揮本發明之組成物所具有的親水性及膜安定性。
<親水性塗布膜形成用組成物> 本發明之親水性塗布膜形成用組成物係藉由混合特定矽氧烷單體與水或1種或2種以上的有機溶劑而得之溶液。 作為有機溶劑,可舉出甲醇、乙醇、2-丙醇、丁醇、二丙酮醇、三氟乙醇等之醇類,丙酮、甲基乙基酮、甲基異丁基酮等之酮類,乙二醇、二乙二醇、丙二醇、己二醇等之二醇類,甲基溶纖劑、乙基溶纖劑、丁基溶纖劑、乙基卡必醇、丁基卡必醇、乙二醇單甲基醚、乙二醇二甲基醚、乙二醇正丁基醚、二乙二醇單甲基醚、二乙二醇單丁基醚、二乙二醇二甲基醚、丙二醇單甲基醚、丙二醇單丁基醚等之二醇醚,乙酸甲酯、乙酸乙酯、乳酸乙酯等之酯類,N-甲基-2-吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、g-丁內酯、二甲亞碸、四甲基脲、六甲基磷三醯胺、間甲酚等。 其中,作為有機溶劑,由單體的溶解性之觀點,較佳為甲醇、乙醇、2-丙醇、三氟乙醇等之醇類,乙二醇、丙二醇、己二醇等之二醇類,甲基溶纖劑、乙基溶纖劑、丁基溶纖劑、乙基卡必醇、丁基卡必醇、乙二醇單甲基醚、乙二醇二甲基醚、乙二醇正丁基醚、二乙二醇單甲基醚、二乙二醇單丁基醚、二乙二醇二甲基醚、丙二醇單甲基醚、丙二醇單丁基醚等之二醇醚,或N-甲基-2-吡咯啶酮。
上述溶液中所包含的特定矽氧烷單體係可被水解。於特定矽氧烷單體之水解中,可使用鹽酸、硫酸、硝酸、乙酸、甲酸、草酸、馬來酸等之酸;氨、甲胺、乙胺、乙醇胺、三乙胺等之鹼或鹽酸、硫酸、硝酸等之金屬鹽等觸媒等。 進行水解時,反應溫度較佳為0℃~沸點,更佳為0℃~120℃,特佳為5℃~80℃。反應時間較佳為10分鐘~80小時,更佳為30分鐘~50小時,特佳為30分鐘~2小時。
於本發明中,可將以上述方法所得之溶液直接當作塗布形成用組成物,視需要可將上述方法所得之溶液予以濃縮,或添加溶劑而稀釋或取代成其他溶劑。 此時,所用的溶劑係可為與溶解所用者相同的溶劑,也可為其他的溶劑。此溶劑只要能均勻地溶解矽化合物,則沒有特別的限定,可為一種或複數種,可任意地選擇使用。 本發明之組成物中的特定矽氧烷單體之含量,以SiO2
固體成分換算濃度,較佳為0.005~15質量%,更佳為0.01~12質量%。若為如此的濃度範圍,則可容易以一次的塗布得到所欲的膜厚,容易得到溶液的充分適用期。
<製膜> 本發明之親水性塗布膜形成用組成物係可採用已知的塗布法,於基板上形成塗膜,而成為親水性塗布膜。作為塗布法,例如可使用浸塗法、旋轉塗布法、噴塗法、流塗法、毛刷塗布法、棒塗法、凹版塗布法、輥轉印法、刮刀塗布法、空氣刀塗布法、狹縫塗布法、網版印刷法、噴墨法、柔版印刷法等。其中,較佳為旋轉塗布法、狹縫塗布法、刮刀塗布法、噴塗法或浸塗法。
<基板> 作為基板,可舉出玻璃、塑膠{聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、ABS、聚碳酸酯、聚苯乙烯、環氧樹脂、不飽和聚酯、三聚氰胺、鄰苯二甲酸二烯丙酯、聚醯亞胺、胺基甲酸酯、尼龍、聚乙烯、聚丙烯、環烯烴聚合物、聚氯乙烯、氟樹脂(聚四氟乙烯樹脂、聚氯三氟乙烯樹脂、聚偏二氟乙烯樹脂、聚氟乙烯樹脂、全氟烷氧基氟樹脂、四氟乙烯・六氟丙烯共聚物樹脂、乙烯・四氟乙烯共聚物樹脂、乙烯・氯三氟乙烯共聚物樹脂等)、聚丁二烯、聚異戊二烯、SBR、腈橡膠、EPM、EPDM、環氧氯丙烷橡膠、氯丁二烯橡膠、聚硫化物、丁基橡膠等}、金屬(鐵、鋁、不鏽鋼、鈦、銅、黃銅、此等之合金等)、纖維素、纖維素衍生物、纖維素類似物(幾丁質、幾丁聚醣、紫菜聚醣等)或天然纖維(蠶絲、棉等)等之基板、薄片、薄膜、纖維之表面親水化等。
又,視需要為了提高與基板等的接著性,亦可對於基板,預先進行底漆處理、或真空電漿、大氣壓電漿、電暈放電處理、火焰處理、氣體底漆處理、紫外線照射、臭氧處理等之表面活化處理(提高基材表面的表面能之手法)。
<乾燥> 藉由將基材上所形成的親水性塗布膜形成用組成物之塗膜進行乾燥、燒成,而得到本發明之親水性塗布膜。乾燥步驟較佳為室溫~150℃之溫度範圍,更佳為40~120℃之範圍。又,其時間較佳為30秒~10分鐘左右,更佳為1~8分鐘左右。作為乾燥方法,較佳為使用熱板或熱風循環式烘箱等。
<燒成> 燒成步驟係考慮基材的耐熱性、環境面,較佳為80℃~300℃之溫度範圍,更佳為100℃~250℃之範圍內。其時間較佳為5分鐘以上,更佳為15分鐘以上。作為燒成方法,較佳為使用熱板、熱循環式烘箱、紅外線烘箱等。
以上述方法所得的被膜之厚度係可視需要來選擇。為了容易得到親水性塗布膜的安定性,被膜之厚度較佳為3~150nm,更佳為5~120nm。 實施例
以下,循著實施例來更詳細說明本發明,惟本發明不受此等所限定。 還有,以下中的縮寫符號係如以下。 DHIMES:三乙氧基-3-(2-咪唑啉-1-基)丙基矽烷 p-PyTES:2-(4-吡啶基乙基)三乙氧基矽烷 DMAPS:3-(N,N-二甲基胺基丙基)三甲氧基矽烷 MTES:甲基三乙氧基矽烷 TFE:三氟乙醇
下述合成例中的生成物係藉由1H-NMR分析而鑑定。分析條件係如下述。 裝置:Varian NMR System 400 NB (400MHz) 測定溶劑:CDCl3
、DMSO-d6, 基準物質:四甲基矽烷(TMS)(d0.0ppm for 1H)
<合成例1:A-1之合成>
於反應器中,加入乙腈(398.9g)及DHIMES (199.5g,727mmol),接著於氮氣環境、冰冷條件下,使用滴液漏斗,滴下已溶於乙腈(299.3g)中的1,3-丙磺內酯(97.7g)。 於滴下後,以乙腈(99.8g)沖掉在滴液漏斗上所殘留的殘留分,將反應溫度設為室溫,使其反應18小時。反應結束後,藉由減壓濃縮而使反應容器內的內部總重量成為459g,添加四氫呋喃(1596g)而使結晶析出,進行過濾、乾燥,藉此得到244.0g的A-1(性質形狀:白色結晶)(產率:85%)。1
H-NMR(400MHz) in CDCl3
:0.57-0.61ppm(m, 2H), 1.23ppm(t, J=7.2Hz, 9H), 1.69-1.76ppm(m, 2H), 2.14-2.21 ppm(m, 2H) 2.90ppm(t, J=7.2Hz, 2H), 3.57ppm(t, J=7.2Hz, 2H), 3.78-3.85ppm(m, 8H), 3.93-3.99ppm(m, 4H), 8.82ppm (s, 1H)
<合成例2:A-2之合成> 除了作為矽氧烷單體,使用p-PyTES以外,藉由與合成例1同樣地實施,而得到40.5g的A-2(性質形狀:紅色結晶)(產率74%)。
<合成例3:A-3之合成> 除了作為矽氧烷單體,使用DMAPS以外,藉由與合成例1同樣地實施,而得到49.4g的A-3(性質形狀:白色結晶)(產率82%)。
<合成例4:A-4之合成> 於乙腈(30.1g)中,加入DHIMES(20.0g,72.9mmol),於氮氣環境、室溫條件下,添加1,4-丁磺內酯(11.0g)。接著,將反應溫度設為45℃,使其反應約2日而使原料消失。反應結束後,藉由減壓濃縮而去除溶劑,添加乙酸乙酯(20.0g)與己烷(20.0g)而製作懸浮溶液。於-25℃的冷凍庫,將懸浮液放置一夜藉此使結晶析出,藉由於氮氣環境下過濾而回收結晶。將所得之結晶,以己烷(50.0g)洗淨漿體,進行過濾、乾燥藉此得到20.2g的A-4(性質形狀:淡黃色結晶)(產率:67%)。
<合成例5:A-5之合成> 於乙腈(40.0g)中,加入三乙氧基-3-(2-咪唑啉-1-基)丙基矽烷(20.0g,72.9mmol),於氮氣環境、冰冷條件下,添加2,4-丁磺內酯(10.4g)。接著,將反應溫度設為室溫,使其反應約1日而使原料消失。反應結束後,藉由減壓濃縮而去除溶劑。接著,以乙酸乙酯(80.0g)來稀釋濃縮溶液,添加己烷(80.0g),結果製作出懸浮溶液。於-25℃的冷凍庫,使黏性物質固化,去除上清液。再度添加乙酸乙酯(70.0g)及己烷(70.0g)而製作懸浮液,再度於-25℃的冷凍庫放置,結果結晶析出。於氮氣環境下過濾,以己烷洗淨,進行乾燥藉此得到28.2g的A-5(性質形狀:白色結晶)(產率:94%)。
<調製例1> 於200mL燒瓶中加入39.7g的A-1及36.4g的TFE及攪拌,而溶解A-1。於其中,添加草酸0.3g、水5.4g及TFE 18.2g之混合物,在室溫下攪拌2小時,得到溶液AA。 於500mL燒瓶中,混合溶液AA 2.5g及TFE 297.5g,進而在室溫下攪拌30分鐘,而得到溶液(K1)。
<調製例2> 於200mL燒瓶中加入39.1g的A-2及36.7g的TFE及攪拌,而溶解A-2。於其中,添加草酸0.3g、水5.4g及TFE 18.4g之混合物,在室溫下攪拌2小時,得到溶液AB。 於500mL燒瓶中,混合溶液AB 2.5g及TFE 297.5g,進而在室溫下攪拌30分鐘,而得到溶液(K2)。
<調製例3> 於200mL燒瓶中加入27.8g的A-1、5.3g的MTES、40.8g的TFE及攪拌,而溶解A-1及MTES。於其中,添加草酸0.3g、水5.4g及TFE 20.4g之混合物,在室溫下攪拌2小時,得到溶液AC。 於500mL燒瓶中,混合溶液AC 2.5g及TFE 297.5g,進而在室溫下攪拌30分鐘,而得到溶液(K3)。
<調製例4> 於200mL燒瓶中加入32.9g的A-3及40.9g的TFE及攪拌,而溶解A-3。於其中,添加草酸0.3g、水5.4g及TFE 20.5g之混合物,在室溫下攪拌2小時,得到溶液AD。 於500mL燒瓶中,混合溶液AD 2.5g及TFE 297.5g,進而在室溫下攪拌30分鐘,而得到溶液(K4)。
<調製例5> 於100mL燒瓶中加入16.4g的A-4及14.2g的TFE及攪拌,而溶解A-3。於其中,添加草酸0.1g、水2.2g及TFE 7.1g之混合物,在室溫下攪拌2小時,得到溶液AE。 於500mL燒瓶中,混合溶液AE 2.5g及TFE 297.5g,進而在室溫下攪拌30分鐘,而得到溶液(K5)。
<調製例6> 於100mL燒瓶中加入16.4g的A-5及14.2g的TFE及攪拌,而溶解A-3。於其中,添加草酸0.1g、水2.2g及TFE 7.1g之混合物,在室溫下攪拌2小時,得到溶液AF。 於500mL燒瓶中,混合溶液AF 2.5g及TFE 297.5g,進而在室溫下攪拌30分鐘,而得溶液(K6)。
<製膜法> 以孔徑0.5μm的薄膜過濾器,加壓過濾以上述調製例1~6所得之溶液K1~K6,藉由旋轉塗布法在玻璃基板上成膜。將此基板在70℃的熱板上乾燥3分鐘後,於200℃的熱風循環式烘箱進行30分鐘燒成,而得到親水性被膜。 將以調製例1~3、5~6所分別得到的溶液K1~K3、K5~K6之上述親水性被膜(KL1~KL5)當作實施例1~5。又,將以調製例4所得的溶液K4之上述親水性被膜(KM1)當作比較例1。
對於上述實施例1~3、5~6之被膜(KL1~KL5)及比較例1之被膜(KM1),進行以下的各試驗,於表1中顯示彼等之結果。 <水接觸角> 使用協和界面科學公司製的自動接觸角計CA-Z型,測定滴下1微升的純水時之接觸角。 <高溫高濕試驗> 將上述各被膜(KL1~KL5、KM1)在溫度60℃、相對濕度90%的高溫高濕槽烘箱進行熟化3日。然後,以上述手法測定水接觸角。
<水浸漬試驗> 對於上述各被膜(KL1~KL5、KM1),使用純水,在室溫下進行5分鐘超音波洗淨,接著在80℃的熱風循環式烘箱進行乾燥10分鐘。然後,進行上述高溫高濕試驗。 <呼氣試驗> 對於已進行上述水浸漬試驗及高溫高濕試驗的被膜(KL1~KL5、KM1),吹噴呼氣,將被膜的表面未霧濁之情況當作○,將霧濁之情況當作×,進行各評價。
在實施例1~5之被膜中,即使在高溫高濕試驗及水浸漬試驗後,在維持親水性,還有從呼氣試驗之結果可知,亦維持防霧性。在比較例1之被膜中,因水浸漬試驗,而在高溫高濕3日後,親水性降低,於呼氣試驗中被膜表面亦霧濁,防霧性也降低。 再者,於此引用2017年6月14日申請的日本發明專利申請案2017-117151號之說細書、申請專利範圍、圖式及發明摘要的全部內容,作為本發明之說明書的揭示而併入。
Claims (14)
- 一種親水性塗布膜形成用組成物,其含有:具有在含氮雜環構造中的氮原子具有正(+)電荷的甜菜鹼基之矽氧烷單體、與水或有機溶劑。
- 如請求項1之親水性塗布膜形成用組成物,其中前述矽氧烷單體係以下述式[1]所示;式[1]中,R1 表示碳數1~5的烷基; R2 表示碳數1~5的烷基、碳數2~5的烯基或碳數2~5的炔基,R2 所具有的任意之氫原子係可被碳數1~5的烷基、鹵素原子、芳香族環或脂肪族環所取代;p表示1~3之整數;q係當p為1時表示0~2之整數,當p為2時表示0~1之整數,當p為3時表示0; L表示碳數1~20之可具有雜原子之直鏈狀或分枝狀的伸烷基,伸烷基所具有的任意之氫原子係可被碳數1~5的烷基、鹵素原子、芳香族環或脂肪族環所取代; X表示單鍵、-O-、-COO-、-OCO-、-CONR3 -、-NR4 -CO- 或-NR5 =NR6 -;R3 、R4 、R5 及R6 各自獨立地表示氫原子或碳數1~4的烷基; Y表示具有含氮雜環的2價有機基; M表示碳數1~10之直鏈狀或分枝狀的伸烷基,伸烷基所具有的任意之氫原子係可被碳數1~5的烷基或鹵素原子所取代;M係與Y所具有的氮原子鍵結,M及L之任一者藉由與Y所具有的氮原子之鍵結而形成N+ 部分; Z表示COO- 、SO3 - 或PO4 - 。
- 如請求項1或2之親水性塗布膜形成用組成物,其中前述Y係選自由吡啶、哌啶、咪唑、唑、噻唑、吡唑、咪唑啉、吡、苯并咪唑、喹啉、異喹啉、嘌呤及喹啉所成之群組。
- 如請求項1~3中任一項之親水性塗布膜形成用組成物,其中前述Y係選自由吡啶、咪唑、咪唑啉及苯并咪唑所成之群組。
- 如請求項1~4中任一項之親水性塗布膜形成用組成物,其中前述矽氧烷單體係由下述的化合物所選出的至少1個; 。
- 如請求項1~4中任一項之親水性塗布膜形成用組成物,其中前述矽氧烷單體係由下述的化合物所選出的至少1個;。
- 如請求項1~6中任一項之親水性塗布膜形成用組成物,其中以SiO2 固體成分換算,含有0.005~12質量%的前述具有甜菜鹼基之矽氧烷單體。
- 如請求項1~7中任一項之親水性塗布膜形成用組成物,其進一步含有金屬烷氧化物、金屬烷氧化物寡聚物或金屬烷氧化物聚合物。
- 如請求項1~8中任一項之親水性塗布膜形成用組成物,其進一步含有無機微粒子、調平劑或界面活性劑。
- 一種親水性塗層之成膜方法,其係將如請求項1~9中任一項之親水性塗布膜形成用組成物塗布於基板上而形成塗膜,將該塗膜乾燥、燒成而得到被膜。
- 如請求項10之親水性塗層之成膜方法,其中在室溫至150℃乾燥前述塗膜,在80~300℃燒成。
- 如請求項10或11之親水性塗層之成膜方法,其中前述燒成後的被膜之厚度為3~150nm。
- 一種親水性塗布膜,其係由如請求項1~9中任一項之親水性塗布膜形成用組成物所得。
- 如請求項13之親水性塗布膜,其係防止水滴附著膜或防霧膜。
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JP2005060510A (ja) * | 2003-08-12 | 2005-03-10 | Nof Kansai Marine Coatings Co Ltd | 塗料組成物、防汚塗膜、防汚性水中構造物、及び防汚方法 |
JP2008239949A (ja) | 2007-02-28 | 2008-10-09 | Fujifilm Corp | 親水性膜形成用組成物および親水性部材 |
JP5315787B2 (ja) * | 2008-05-19 | 2013-10-16 | 住友化学株式会社 | イミダゾリウム塩およびそれが固定化された粒子状酸化物 |
WO2011084661A2 (en) * | 2009-12-17 | 2011-07-14 | 3M Innovative Properties Company | Sulfonate-functional coatings and methods |
KR101610562B1 (ko) * | 2011-07-27 | 2016-04-07 | 닛산 가가쿠 고교 가부시키 가이샤 | 액정 배향제, 액정 배향막 및 액정 표시 소자 |
JP6318090B2 (ja) * | 2012-10-19 | 2018-04-25 | シャープ株式会社 | 液晶組成物、液晶表示装置及び液晶表示装置の製造方法 |
-
2018
- 2018-06-11 KR KR1020197036671A patent/KR102611591B1/ko active IP Right Grant
- 2018-06-11 CN CN201880039328.0A patent/CN110741054B/zh active Active
- 2018-06-11 JP JP2019525420A patent/JP7200937B2/ja active Active
- 2018-06-11 WO PCT/JP2018/022268 patent/WO2018230514A1/ja active Application Filing
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JPWO2018230514A1 (ja) | 2020-04-16 |
JP7200937B2 (ja) | 2023-01-10 |
CN110741054B (zh) | 2021-12-21 |
WO2018230514A1 (ja) | 2018-12-20 |
KR102611591B1 (ko) | 2023-12-07 |
KR20200018447A (ko) | 2020-02-19 |
CN110741054A (zh) | 2020-01-31 |
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