JP2021123678A - Water-repellent coating composition - Google Patents
Water-repellent coating composition Download PDFInfo
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- JP2021123678A JP2021123678A JP2020019656A JP2020019656A JP2021123678A JP 2021123678 A JP2021123678 A JP 2021123678A JP 2020019656 A JP2020019656 A JP 2020019656A JP 2020019656 A JP2020019656 A JP 2020019656A JP 2021123678 A JP2021123678 A JP 2021123678A
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- Prior art keywords
- water
- repellent coating
- coating composition
- alkylsilane
- durability
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- 239000005871 repellent Substances 0.000 title claims abstract description 24
- 239000008199 coating composition Substances 0.000 title claims abstract description 19
- 150000001343 alkyl silanes Chemical class 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 9
- 150000004756 silanes Chemical class 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 238000012360 testing method Methods 0.000 description 25
- BSYQEPMUPCBSBK-UHFFFAOYSA-N [F].[SiH4] Chemical compound [F].[SiH4] BSYQEPMUPCBSBK-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- -1 nbutanol Chemical compound 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- NOGBEXBVDOCGDB-NRFIWDAESA-L (z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-].CCOC(=O)\C=C(\C)[O-] NOGBEXBVDOCGDB-NRFIWDAESA-L 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- VFRLODREAFCRFF-UHFFFAOYSA-K C(C)(=O)[O-].C(C)CC(=O)[O-].C(C)CC(=O)O.C(C)CC(=O)[O-].[Al+3] Chemical compound C(C)(=O)[O-].C(C)CC(=O)[O-].C(C)CC(=O)O.C(C)CC(=O)[O-].[Al+3] VFRLODREAFCRFF-UHFFFAOYSA-K 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- IJROHELDTBDTPH-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F IJROHELDTBDTPH-UHFFFAOYSA-N 0.000 description 1
- BVQYIDJXNYHKRK-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BVQYIDJXNYHKRK-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は撥水性コーティング組成物に関し、更に詳細には、アルキルシランを含み、撥水性及び耐久性に優れた撥水性コーティング組成物に関する。 The present invention relates to a water-repellent coating composition, and more particularly to a water-repellent coating composition containing alkylsilane and having excellent water repellency and durability.
従来、シリコーンオイル、フッ素シラン、又はアルキルシランを主剤とし、これに酸触媒又はアルカリ触媒を配合し、更に水及びアルコール類を配合してなる撥水性コーティング組成物が知られている。このような撥水性コーティング組成物をガラス等の対象物の表面に塗布することより、耐久性を有する撥水塗膜が該表面に形成される。 Conventionally, a water-repellent coating composition is known in which silicone oil, fluorine silane, or alkylsilane is used as a main component, an acid catalyst or an alkali catalyst is blended therein, and water and alcohols are further blended. By applying such a water-repellent coating composition to the surface of an object such as glass, a durable water-repellent coating film is formed on the surface.
例えば、特許文献１には、フッ素シラン又はアルキルシランである主剤と、金属アルコキシド又はキレート化合物からなる安定化剤と、を含むガラス用撥水性コーティング組成物が開示されている。特許文献２には、炭素数１〜８の有機基を含むオルガノシランとオルガノポリシロキサンとを共縮合させたコーティング組成物が開示されている。 For example, Patent Document 1 discloses a water-repellent coating composition for glass containing a main agent of fluorine silane or alkylsilane and a stabilizer composed of a metal alkoxide or a chelate compound. Patent Document 2 discloses a coating composition in which an organosilane containing an organic group having 1 to 8 carbon atoms and an organopolysiloxane are co-condensed.
撥水塗膜による撥水性を維持するには、該塗膜の耐久性が優れていることが求められる。特許文献１記載のガラス用撥水性コーティング組成物により、撥水塗膜の耐久性が向上するが、より一層耐久性を向上させることが求められている。 In order to maintain the water repellency of the water-repellent coating film, the durability of the coating film is required to be excellent. The water-repellent coating composition for glass described in Patent Document 1 improves the durability of the water-repellent coating film, but is required to further improve the durability.
本発明は上記の事情に鑑みなされたものであり、耐久性及び撥水性に優れた撥水塗膜を形成することができる撥水性コーティング組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a water-repellent coating composition capable of forming a water-repellent coating film having excellent durability and water repellency.
本発明の撥水性コーティング組成物（以下、「本組成物」という。）は、主剤として、一般式Ｒ４−ｎＳｉ（ＯＲ’）ｎ（式中、Ｒは炭素数９以上の炭化水素基であり、Ｒ’は炭素数１〜５のアルキル基である。ｎは１〜３の整数である。）で表されるアルキルシランを、少なくとも水を含む溶媒中に含む。 The water-repellent coating composition of the present invention (hereinafter referred to as "the present composition") has a general formula R 4-n Si (OR') n (in the formula, R is a hydrocarbon group having 9 or more carbon atoms) as a main agent. R'is an alkyl group having 1 to 5 carbon atoms. N is an integer of 1 to 3), and an alkylsilane represented by () is contained in a solvent containing at least water.
本組成物では、主剤として一般式Ｒ４−ｎＳｉ（ＯＲ’）ｎで表されるアルキルシランを含む。ここで、「主剤として」とは、「塗膜を形成する成分として」の意味であり、含有量及び含有割合とは関連がない。例えば、本組成物が、「塗膜を形成する成分」として、前記アルキルシランと他のシラン系化合物を１種以上含む場合、前記アルキルシランの配合量が前記他のシラン系化合物の配合量より少なくても、「主剤として」の要件を満たす。 In this composition, an alkylsilane represented by the general formula R4-n Si (OR') n is contained as a main agent. Here, "as a main agent" means "as a component forming a coating film" and is not related to the content and the content ratio. For example, when the present composition contains one or more of the alkylsilane and other silane-based compounds as "components forming a coating film", the blending amount of the alkylsilane is larger than the blending amount of the other silane-based compound. At a minimum, it meets the requirements of "as a main ingredient".
前記アルキルシラン中のＲは、炭素数９以上、好ましくは９〜２０の炭化水素基である。前記炭化水素基は直鎖状でも分岐状でもよい。また、前記炭化水素基は飽和炭化水素基でもよく、１以上の不飽和結合（二重結合及び／又は三重結合）を含んでいてもよい。 R in the alkylsilane is a hydrocarbon group having 9 or more carbon atoms, preferably 9 to 20 carbon atoms. The hydrocarbon group may be linear or branched. Further, the hydrocarbon group may be a saturated hydrocarbon group, or may contain one or more unsaturated bonds (double bond and / or triple bond).
前記アルキルシラン中のＲ’は、炭素数１〜５のアルキル基である。該アルキル基として具体的には、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、及びｔ−ブチル基が挙げられる。 R'in the alkylsilane is an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group.
前記アルキルシランは、１種単独で用いてもよく、２種以上を併用してもよい。 The alkylsilane may be used alone or in combination of two or more.
本組成物中の前記アルキルシランの含有量には特に限定はない。該含有量として好ましくは０．０５〜１２質量部、好ましくは０．０５〜１０質量部、更に好ましくは０．１〜７質量部である。含有量が前記範囲内であると、撥水性を発揮するのに十分な撥水塗膜を形成することができ、経済的であることから好ましい。 The content of the alkylsilane in the composition is not particularly limited. The content is preferably 0.05 to 12 parts by mass, preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 7 parts by mass. When the content is within the above range, a water-repellent coating film sufficient to exhibit water repellency can be formed, which is economical, which is preferable.
前記溶剤は、少なくとも水を含み、且つ前記アルキルシランを溶解させることができる限り、その種類には特に限定はない。前記溶剤は水のみで構成されていてもよく、水と１以上の他の溶媒との混合溶剤でもよい。前記溶剤として好ましくは、水とアルコールとの混合溶媒である。前記水は水道水等の通常の水でもよく、脱塩素水及び超純水でもよい。 The type of the solvent is not particularly limited as long as it contains at least water and can dissolve the alkylsilane. The solvent may be composed only of water, or may be a mixed solvent of water and one or more other solvents. The solvent is preferably a mixed solvent of water and alcohol. The water may be ordinary water such as tap water, dechlorinated water or ultrapure water.
前記アルコールとしては、メタノール、エタノール、イソプロピルアルコール、ｎブタノール、イソブタノール、オクタノール、ｎ−プロピルアルコール等、またグリコール誘導体としては、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノｎ−ブロピルエーテル、エチレングリコールモノｎ−ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。特にはメタノール、エタノール、イソプロピルアルコール等のアルコールが取り扱い性、保存安定性の点で好ましい。 Examples of the alcohol include methanol, ethanol, isopropyl alcohol, nbutanol, isobutanol, octanol, n-propyl alcohol and the like, and examples of glycol derivatives include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monon. -Bropyl ether, ethylene glycol monon-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, Examples thereof include propylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate. In particular, alcohols such as methanol, ethanol and isopropyl alcohol are preferable in terms of handleability and storage stability.
前記水とアルコール類との混合比には特に限定はない。該混合比は通常、０．１：９９．９〜１０：９０の重量比で、好ましくは１：９９〜５：９５の重量比である。混合比が前記範囲であると、前記アルキルシランを溶解させて良好な塗膜を形成できることから好ましい。 The mixing ratio of the water and alcohols is not particularly limited. The mixing ratio is usually 0.1: 99.9 to 10:90, preferably 1:99 to 5:95. When the mixing ratio is in the above range, the alkylsilane can be dissolved to form a good coating film, which is preferable.
本組成物は更にフッ素シランを含めることができる。フッ素シランを含むことにより、塗膜の耐熱性を高めることができるので好ましい。前記フッ素シランの構造には特に限定はない。前記フッ素シランとして、例えば、炭素数３〜１０のフッ素シランを用いることができる。また、前記フッ素シランの含有量は、必要に応じて適宜の範囲とすることができる。前記フッ素シランの含有量は０．０５〜３質量部、好ましくは０．１〜１質量部、より好ましくは０．１〜０．５質量部とすることができる。更に、前記アルキルシランと前記フッ素シランの割合（重量比）は１：（０．１〜３０）、好ましくは１：（０．３〜１０）、更に好ましくは１：（０．１〜５）とすることができる。 The composition can further include fluorinated silane. It is preferable to include fluorine silane because the heat resistance of the coating film can be improved. The structure of the fluorine silane is not particularly limited. As the fluorine silane, for example, a fluorine silane having 3 to 10 carbon atoms can be used. In addition, the content of the fluorine silane can be set to an appropriate range, if necessary. The content of the fluorine silane can be 0.05 to 3 parts by mass, preferably 0.1 to 1 part by mass, and more preferably 0.1 to 0.5 part by mass. Further, the ratio (weight ratio) of the alkylsilane to the fluorine silane is 1: (0.1 to 30), preferably 1: (0.3 to 10), and more preferably 1: (0.1 to 5). Can be.
本組成物は、必要に応じて他の成分を含んでいてもよい。前記他の成分として例えば、本組成物のゲル化又は沈殿の発生を抑制するための安定化剤が挙げられる。前記安定化剤としては、例えば、金属アルコキシド又はキレート化合物が挙げられる。前記金属アルコキシドを構成する金属としては、例えば、アルミニウム、ジルコニウム、及びチタニウムが挙げられる。前記安定化剤は１種単独で用いてもよく、２種以上を併用してもよい。 The composition may contain other components, if desired. Examples of the other component include a stabilizer for suppressing the occurrence of gelation or precipitation of the present composition. Examples of the stabilizer include metal alkoxides and chelating compounds. Examples of the metal constituting the metal alkoxide include aluminum, zirconium, and titanium. The stabilizer may be used alone or in combination of two or more.
前記安定化剤として具体的には、例えば、アルミニウムトリス（アセチルアセトネート）、アルミニウムビス（エチルアセトアセテート）モノ（アセチルアセトネート）、ジルコニウムテトラキス（アセチルアセトネート）、チタニウムテトラキス（アセチルアセトネート）、チタニウムビス（イソプロポキシ）ビス（エチルアセチルアセテート）、トリエトキシアルミニウム、トリ−イソ−プロキシアルミニウム、テトラ−イソ−プロキシチタン、テトラ−イソ−プロポキシジルコニウム、テトラ−イソ−ブトキシジルコニウム、アルミニウムトリス（エチルアセトアセテート）、チタニウムビス（イソプロポキシ）ビス（トリエタノールアミン）、チタニウムビス（イソプロポキシ）ビス（アセトアセトネート）、ジルコニウムトリス（ｎ−ブトキシ）モノ（アセチルアセトネート）、ジルコニウムビス（ｎ−ブトキシ）ビス（アセチルアセトネート）が挙げられる。 Specifically, as the stabilizer, for example, aluminum tris (acetylacetonate), aluminum bis (ethylacetoacetate) mono (acetylacetonate), zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), etc. Titanium bis (isopropoxy) bis (ethylacetylacetate), triethoxyaluminum, tri-iso-proxylanium, tetra-iso-proxititanium, tetra-iso-propoxyzirconium, tetra-iso-butoxyzirconium, aluminum tris (ethylacetate) Acetate), Titanium Bis (Isopropoxy) Bis (Triethanolamine), Titanium Bis (Isopropoxy) Bis (Acetoacetate), Zirconium Tris (n-Butoxy) Mono (Acetylacetate), Zirconium Bis (n-Butoxy) Bis (acetylacetonate) can be mentioned.
前記安定化剤の含有量は必要に応じて適宜選択することができる。該含有量は通常、前記主剤１００質量部に対して０．１〜１００質量部である。前記含有量が上記範囲であると、本組成物のゲル化、沈殿の発生を十分に抑制することができ、且つ経済的であることから好ましい。 The content of the stabilizer can be appropriately selected as needed. The content is usually 0.1 to 100 parts by mass with respect to 100 parts by mass of the main agent. When the content is in the above range, gelation and precipitation of the present composition can be sufficiently suppressed and it is economical, which is preferable.
前記安定化剤以外の前記他の成分として具体的には、例えば、凍結防止剤、ｐＨ調整、紫外線吸収剤、及び赤外線吸収剤が挙げられる。 Specific examples of the other components other than the stabilizer include an antifreeze agent, a pH adjuster, an ultraviolet absorber, and an infrared absorber.
本組成物の適用対象は、撥水性が求められる限り特に限定はない。該適用対象としては例えば、ガラスが挙げられる。よって、本組成物は、ガラス用撥水性コーティング組成物として用いることができる。 The application target of this composition is not particularly limited as long as water repellency is required. Examples of the application target include glass. Therefore, this composition can be used as a water-repellent coating composition for glass.
以下、実施例により本発明を具体的に説明する。尚、本発明は、実施例に示す形態に限定されない。本発明の実施形態は、目的及び用途に応じて、本発明の範囲内で種々変更することができる。また、実施例における結果に対する考察は、全て発明者の見解に過ぎず、何ら本発明を定義付ける趣旨の説明ではないことを付言する。 Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to the embodiments shown in the examples. The embodiments of the present invention can be variously modified within the scope of the present invention according to the purpose and use. In addition, it should be added that all the considerations regarding the results in the examples are merely the views of the inventor and do not explain the purpose of defining the present invention.
（１）組成物の調製
以下の成分を用いて、実施例１〜１７及び比較例１〜５の撥水性コーティング組成物を調製した。実施例１〜１７及び比較例１〜５の組成を表１及び表２に示す。表１及び表２において、各成分の数値は質量部である。
アルコール；イソプロピルアルコール
添加剤；アルミニウムキレート化合物
Ｃ４フッ素シラン；トリメトキシ（１Ｈ，１Ｈ，２Ｈ，２Ｈノナフルオロヘキシル）シラン
Ｃ６フッ素シラン；トリメトキシ（１Ｈ，１Ｈ，２Ｈ，２Ｈ−トリデカフルオロ−ｎ−オクチル）シラン
Ｃ８アルキルシラン；トリメトキシ−ｎ−オクチルシラン
Ｃ１０アルキルシラン；デシルトリメトキシシラン
Ｃ１２アルキルシラン；ドデシルトリメトキシシラン
Ｃ１６アルキルシラン；ヘキサデシルトリメトキシシラン
Ｃ１８アルキルシラン（Ｉ）；オクタデシルトリメトキシシラン
Ｃ１８アルキルシラン（ＩＩ）；オクタデシルトリエトキシシラン
(1) Preparation of Composition The water-repellent coating compositions of Examples 1 to 17 and Comparative Examples 1 to 5 were prepared using the following components. The compositions of Examples 1 to 17 and Comparative Examples 1 to 5 are shown in Tables 1 and 2. In Tables 1 and 2, the numerical values of each component are parts by mass.
Alcohol; Isopropyl Alcohol Additives; Aluminum Chelate Compound C4 Fluorosilane; Trimethoxy (1H, 1H, 2H, 2H Nonafluorohexyl) Silane C6 Fluorosilane; Trimethoxy (1H, 1H, 2H, 2H-Tridecafluoro-n-octyl) Silane C8 alkylsilane; trimethoxy-n-octylsilane C10 alkylsilane; decyltrimethoxysilane C12 alkylsilane; dodecyltrimethoxysilane C16 alkylsilane; hexadecyltrimethoxysilane C18alkylsilane (I); octadecyltrimethoxysilane C18 alkylsilane (II); octadecyltriethoxysilane
（２）初期接触角及び初期転落角の測定
実施例１〜１７及び比較例１〜５の撥水性コーティング組成物を手塗りでガラス表面に塗布し、風乾後、７０℃で３０分間加熱して試験片を調製した。該試験片を用いて、２μＬの水滴をガラス表面に滴下し、液適法により初期接触角（°）を、５０μＬの水滴をガラス表面に滴下し、滑落法により初期転落角（°）を測定した。結果を表１及び表２に併記する。
(2) Measurement of initial contact angle and initial fall angle The water-repellent coating compositions of Examples 1 to 17 and Comparative Examples 1 to 5 are manually applied to the glass surface, air-dried, and then heated at 70 ° C. for 30 minutes. Specimens were prepared. Using the test piece, 2 μL of water droplets were dropped on the glass surface, the initial contact angle (°) was measured by the liquid method, and 50 μL of water droplets were dropped on the glass surface, and the initial fall angle (°) was measured by the sliding method. .. The results are shown in Tables 1 and 2.
（３）耐久性試験（Ｉ）（研磨剤法）
炭化ケイ素及び珪藻土を１：１（重量比）で混合し、水で１３．５倍に希釈して研磨液（１５ｇ）を調製した。前記研磨液を用いて、以下の条件で前記試験片の研磨を行った。その後、（２）と同じ方法により、接触角（°）及び転落角（°）を測定した。結果を表１及び表２に併記する。
試験機；摩擦耐久性試験機（自社製）
試験片のサイズ；７５ｍｍ×１５０ｍｍ
摩擦子；ウレタンスポンジ
荷重；４００ｇ
試験回数；１５０往復
(3) Durability test (I) (abrasive method)
Silicon carbide and diatomaceous earth were mixed at a ratio of 1: 1 (weight ratio) and diluted 13.5 times with water to prepare a polishing solution (15 g). The test piece was polished under the following conditions using the polishing liquid. Then, the contact angle (°) and the fall angle (°) were measured by the same method as in (2). The results are shown in Tables 1 and 2.
Testing machine; Friction durability testing machine (manufactured in-house)
Specimen size; 75 mm x 150 mm
Friction; Urethane sponge Load: 400g
Number of tests; 150 round trips
（４）耐久性試験（ＩＩ）（ワイパー法）
前記試験片を７５ｍｍ×２５ｍｍのサイズにカットした。次いで、以下の条件で前記試験片のワイパー摩擦を行った。その後、（２）と同じ方法により、接触角（°）及び転落角（°）を測定した。結果を表１及び表２に併記する。
試験機；ワイパー摩擦耐久性試験機（自社製）
試験片のサイズ；７５ｍｍ×２５ｍｍ
摩擦子；ワイパー（長さ１５ｍｍ）
荷重；２０ｇ
試験回数；１０００往復
(4) Durability test (II) (wiper method)
The test piece was cut into a size of 75 mm × 25 mm. Then, the wiper friction of the test piece was performed under the following conditions. Then, the contact angle (°) and the fall angle (°) were measured by the same method as in (2). The results are shown in Tables 1 and 2.
Testing machine; wiper friction durability testing machine (manufactured in-house)
Specimen size; 75 mm x 25 mm
Friction; wiper (length 15 mm)
Load; 20g
Number of tests; 1000 round trips
（５）耐熱性試験
前記試験片を７５ｍｍ×２５ｍｍのサイズにカットした。次いで、該試験片を恒温槽中で１００℃、１２０時間の条件で加熱した。その後、（２）と同じ方法により、接触角（°）及び転落角（°）を測定した。結果を表１及び表２に併記する。
(5) Heat resistance test The test piece was cut into a size of 75 mm × 25 mm. Then, the test piece was heated in a constant temperature bath at 100 ° C. for 120 hours. Then, the contact angle (°) and the fall angle (°) were measured by the same method as in (2). The results are shown in Tables 1 and 2.
（６）結果
実施例１〜４では、耐久性試験及び耐熱性試験後の接触角及び転落角の変化が小さく、耐久性及び耐熱性に優れている。一方、比較例３（Ｃ８アルキルシラン）は、耐熱性は同等である反面、耐久性試験（Ｉ）及び（ＩＩ）後の接触角の変化が大きく、耐久性に劣ることが分かる。また、比較例１及び２（フッ素シラン）は、耐熱性は向上しているが、比較例３と同様に、耐久性試験（Ｉ）及び（ＩＩ）後の接触角の変化が大きく、耐久性に劣ることが分かる。
(6) Results In Examples 1 to 4, the changes in the contact angle and the falling angle after the durability test and the heat resistance test are small, and the durability and the heat resistance are excellent. On the other hand, it can be seen that Comparative Example 3 (C8 alkylsilane) is inferior in durability due to a large change in the contact angle after the durability tests (I) and (II), although the heat resistance is the same. Further, although the heat resistance of Comparative Examples 1 and 2 (fluorine silane) is improved, the change in the contact angle after the durability tests (I) and (II) is large and the durability is similar to that of Comparative Example 3. It turns out that it is inferior to.
実施例５は初期接触角が大きく、また、耐久性試験及び耐熱性試験後の接触角の低下の割合も低く、耐久性及び耐熱性に優れている。一方、比較例５（溶媒に水を含まない）は、実施例５と比べて初期接触角が小さく、また、耐久性試験及び耐熱性試験後の接触角の低下の割合も高く、耐久性及び耐熱性に劣ることが分かる。 Example 5 has a large initial contact angle, a low rate of decrease in the contact angle after the durability test and the heat resistance test, and is excellent in durability and heat resistance. On the other hand, in Comparative Example 5 (the solvent does not contain water), the initial contact angle is smaller than that in Example 5, and the rate of decrease in the contact angle after the durability test and the heat resistance test is also high, so that the durability and durability are improved. It can be seen that the heat resistance is inferior.
実施例１〜４（Ｃ１０〜Ｃ１８アルキルシラン）と実施例５〜１７（Ｃ１０〜Ｃ１８アルキルシラン＋フッ素シランを含む。）とを対比すると、実施例５〜１７は、実施例１〜４よりも耐熱性試験後の接触角が大きい。一方、上記のように、比較例１及び２（フッ素シラン）では、耐久性試験（Ｉ）及び（ＩＩ）後の接触角の変化が大きいのに対し、実施例５〜１７ではこの変化が小さい。よって、フッ素シランを含むことにより、耐久性を維持しつつ、塗膜の耐熱性を向上させることができる。 Comparing Examples 1 to 4 (C10 to C18 alkylsilane) with Examples 5 to 17 (including C10 to C18 alkylsilane + fluorine silane), Examples 5 to 17 are more than Examples 1 to 4. The contact angle after the heat resistance test is large. On the other hand, as described above, in Comparative Examples 1 and 2 (fluorine silane), the change in the contact angle after the durability tests (I) and (II) was large, whereas in Examples 5 to 17, this change was small. .. Therefore, by containing fluorine silane, the heat resistance of the coating film can be improved while maintaining the durability.
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| JPH06248259A (en) * | 1993-03-01 | 1994-09-06 | Shin Etsu Chem Co Ltd | Silicone-based waterproofing treatment agent and method for waterproofing treatment with the same |
| JP2002038092A (en) * | 2000-07-27 | 2002-02-06 | Cci Corp | Water-repellent coating composition for glass |
| JP2015145463A (en) * | 2014-02-03 | 2015-08-13 | 旭硝子株式会社 | Substrate with water repellent film, composition for forming water repellent layer and article for transportation equipment |
| JP2018076434A (en) * | 2016-11-09 | 2018-05-17 | 旭硝子株式会社 | Composition, two-pack type composition, article and method for producing article |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06248259A (en) * | 1993-03-01 | 1994-09-06 | Shin Etsu Chem Co Ltd | Silicone-based waterproofing treatment agent and method for waterproofing treatment with the same |
| JP2002038092A (en) * | 2000-07-27 | 2002-02-06 | Cci Corp | Water-repellent coating composition for glass |
| JP2015145463A (en) * | 2014-02-03 | 2015-08-13 | 旭硝子株式会社 | Substrate with water repellent film, composition for forming water repellent layer and article for transportation equipment |
| JP2018076434A (en) * | 2016-11-09 | 2018-05-17 | 旭硝子株式会社 | Composition, two-pack type composition, article and method for producing article |
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