JP4840899B2 - Hydrophilic antifouling coating composition, film forming method using the same and use thereof - Google Patents
Hydrophilic antifouling coating composition, film forming method using the same and use thereof Download PDFInfo
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- JP4840899B2 JP4840899B2 JP2005088716A JP2005088716A JP4840899B2 JP 4840899 B2 JP4840899 B2 JP 4840899B2 JP 2005088716 A JP2005088716 A JP 2005088716A JP 2005088716 A JP2005088716 A JP 2005088716A JP 4840899 B2 JP4840899 B2 JP 4840899B2
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- silica sol
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- 230000003373 anti-fouling effect Effects 0.000 title claims description 71
- 239000008199 coating composition Substances 0.000 title claims description 65
- 238000000034 method Methods 0.000 title claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 62
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- 239000003021 water soluble solvent Substances 0.000 claims description 49
- 150000001412 amines Chemical class 0.000 claims description 31
- 229910021529 ammonia Inorganic materials 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 21
- 238000009835 boiling Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 20
- 239000003945 anionic surfactant Substances 0.000 claims description 18
- 239000002736 nonionic surfactant Substances 0.000 claims description 16
- 125000000129 anionic group Chemical group 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 12
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 12
- -1 glycol ethers Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000005357 flat glass Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000012190 activator Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 229940093475 2-ethoxyethanol Drugs 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- NCHBYORVPVDWBJ-UHFFFAOYSA-N 2-(3-methylbutoxy)ethanol Chemical compound CC(C)CCOCCO NCHBYORVPVDWBJ-UHFFFAOYSA-N 0.000 description 1
- INFFATMFXZFLAO-UHFFFAOYSA-N 2-(methoxymethoxy)ethanol Chemical compound COCOCCO INFFATMFXZFLAO-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
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- 230000000007 visual effect Effects 0.000 description 1
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- Paints Or Removers (AREA)
Description
本発明は、親水防汚コーティング組成物に関する。さらに詳しくは、本発明は、水の接触角が１０°以下の親水防汚コーティング組成物に関し、ガラス、ミラー、タイル、衛生陶器、金属などの比較的親水性な基材表面に塗布することによって、被塗物の表面を水の接触角が１０°以下の親水表面に変え、水滴跡の付着を防止したり、油性汚れをとれやすくする親水防汚コーティング組成物、それを用いた被膜の形成方法及びその用途に関する。 The present invention relates to a hydrophilic antifouling coating composition. More specifically, the present invention relates to a hydrophilic antifouling coating composition having a water contact angle of 10 ° or less, and is applied to a surface of a relatively hydrophilic substrate such as glass, mirror, tile, sanitary ware, or metal. , Hydrophilic antifouling coating composition for changing the surface of an object to be a hydrophilic surface with a water contact angle of 10 ° or less to prevent adhesion of water droplets or to easily remove oily dirt, and formation of a film using the same It relates to a method and its use.
雨水、水道水などの水がかかる物品の表面には、水が乾いた跡に汚れが残ることが多く、車両や窓ガラスの表面など汚れが目立つ箇所においては、都度洗浄しなければ美観を維持することが出来なかった。
水がかかった後に汚れが残る原因としては、水の中に溶けていた不揮発性の成分（シリカ、炭酸カルシウム、その他無機塩類などの溶解性物質又は不溶性懸濁物質）が、水が蒸発した跡に残ることがあげられ、特に水滴が残る撥水性表面、例えば図１に示すように撥水処理した車両の塗装面では、雨などの水滴が乾燥すると水滴部分に汚れが残る現象が起きる。
近年、光触媒やその他親水性をもたらすコーティング材料が開発され、水滴を形成しないようにすることによって、このような汚れの付着を防止する技術が開発されている。
光触媒は、一般的には太陽光の紫外線による励起エネルギーを利用して親水化したり、有機質汚れを分解するため、防汚塗膜としての利用価値は高いと考えられているが、光があたらない箇所では効果が弱く、施工後すぐに親水性を発現できないなどの課題があった。
その他の親水性材料としては、シルカゾルが従来より使用されてきたが、単独では、基材との密着性が不十分であったり、厚膜になると透明性が低下したり、膜強度が脆くなったりして、結果的に実用的な皮膜は得られなかった。
The surface of articles that are exposed to water such as rainwater and tap water often remains on the traces of water drying, and in places where dirt is conspicuous, such as the surface of vehicles and window glass, the aesthetics are maintained unless they are washed each time. I could not do it.
The reason why dirt remains after water is applied is that the non-volatile components dissolved in water (soluble substances such as silica, calcium carbonate, and other inorganic salts or insoluble suspended substances) have been evaporated. In particular, on a water-repellent surface where water droplets remain, for example, on a painted surface of a vehicle subjected to water-repellent treatment as shown in FIG.
In recent years, photocatalysts and other coating materials that bring about hydrophilicity have been developed, and techniques for preventing such adhesion of dirt by preventing formation of water droplets have been developed.
Photocatalysts are generally considered to have high utility value as antifouling coatings because they are hydrophilized using the excitation energy of sunlight by ultraviolet rays and decompose organic stains, but do not receive light There was a problem that the effect was weak at the location and hydrophilicity could not be expressed immediately after construction.
As other hydrophilic materials, silica sol has been used in the past, but by itself, the adhesion to the substrate is insufficient, the transparency decreases when the film becomes thick, and the film strength becomes brittle. As a result, a practical film could not be obtained.
一方、他の造膜性や基材との密着性に優れた材料をシリカゾル（コロイダルシリカ分散液）と組み合わせたコーティング組成物が知られている。
コロイダルシリカに、４官能性アルコキシシランを加水分解重縮合させて得られるシリコーンレジンを組み合わせて、耐久性を付与した親水性無機塗料組成物が提案されている（特許文献１）。この組成物は、親水性、密着性に優れ、極めて利用価値が高いものであるが、溶剤がアルコールなどの非水溶剤に限定されるため、非水溶剤が使用できない用途にはそぐわないという問題があった。
これは、４官能性アルコキシシランが加水分解による重縮合反応を起こすため、希釈溶剤が水である場合、重縮合反応が進みすぎて、ゲル化や沈殿形成を起こし、液の保存安定性を維持することが困難になるためと考えられる。
A hydrophilic inorganic coating composition imparted with durability by combining colloidal silica with a silicone resin obtained by hydrolytic polycondensation of a tetrafunctional alkoxysilane has been proposed (Patent Document 1). This composition is excellent in hydrophilicity and adhesion, and has a very high utility value, but since the solvent is limited to non-aqueous solvents such as alcohol, there is a problem that it is not suitable for applications in which non-aqueous solvents cannot be used. there were.
This is because the polyfunctional alkoxysilane undergoes a polycondensation reaction by hydrolysis, so if the diluent solvent is water, the polycondensation reaction proceeds too much, causing gelation and precipitation, and maintaining the storage stability of the liquid This is thought to be difficult.
このように前記従来のシリカゾルを利用した親水性組成物は、単独では基材との密着性が不十分であったり、厚膜になると透明性が低下したり、膜強度が脆くなったりして、結果的に実用的な皮膜は得られず、４官能性アルコキシシランを加水分解重縮合させて得られるシリコーンレジンと組み合わせると、基材との密着性は向上するものの溶剤が非水溶剤に限定されるなどの問題があった。
本発明は、かかる事情に鑑みなされたものであって、シリカゾルの親水性を最大限に発揮させ、かつ、引火性や吸引毒性を有する非水溶剤を用いず、最も安全な水を主溶剤として用いることができ、さらに、必要に応じて膜の耐久性をさらに向上させることができる、親水防汚コーティング組成物及びその耐久性を向上させる膜の形成方法を提供することを目的とする。
これによって、様々な基材表面を、安全にかつ簡単に、超親水性のコーティング被膜で保護することができるため、基材表面に雨跡などの汚れ付着がなくなり、長期にわたって、洗浄作業が大幅に軽減される。
As described above, the hydrophilic composition using the conventional silica sol alone has insufficient adhesion to the base material, and when it becomes a thick film, the transparency is lowered or the film strength is fragile. As a result, a practical film cannot be obtained, and when combined with a silicone resin obtained by hydrolytic polycondensation of a tetrafunctional alkoxysilane, the adhesion to the substrate is improved, but the solvent is limited to a non-aqueous solvent There were problems such as being.
The present invention has been made in view of such circumstances, and maximizes the hydrophilicity of silica sol, and does not use a non-aqueous solvent having flammability and suction toxicity, and uses the safest water as the main solvent. It is another object of the present invention to provide a hydrophilic antifouling coating composition that can be used and further improve the durability of the film as required, and a method for forming a film that improves the durability.
As a result, various substrate surfaces can be protected safely and easily with a super-hydrophilic coating film, so that dirt such as rain marks will not adhere to the substrate surface, and cleaning operations will be drastically performed over a long period of time. To be reduced.
本発明者らは、鋭意研究した結果、特定の水分散性シリカゾル、水溶性の陰イオン及び
又は非イオン界面活性剤及び特定の水溶性溶剤を組み合わせることにより目的が達成でき
ることを見出した。
すなわち、
本発明は、アンモニア又は揮発性アミンで中和した水分散性シリカゾルと、水溶性の陰イオン及び／又は非イオン界面活性剤と、水溶性溶剤とを含み、シリカゾル中の酸化ナトリウム含有量が０．２質量％より小さく、水溶性溶剤の沸点が１２０℃以上であり、かつ、水溶性溶剤が、２０℃の粘性率が１０ｍＰａ・ｓ以下であり、かつ、２５℃の表面張力が４０ｍＮ／ｍより小さいことを特徴とする親水防汚コーティング組成物である。
また本発明の親水防汚コーティング組成物においては、アンモニア又は揮発性アミンで中和した水分散性シリカゾルのシリカ平均粒子径が５〜５０ｎｍとすることができる。
さらに、本発明の親水防汚コーティング組成物においては、アンモニア又は揮発性アミンで中和した水分散性シリカゾルの固形分濃度が０．０１〜２．０質量％の範囲とすることができる。
また本発明の親水防汚コーティング組成物においては、界面活性剤の濃度が、０．０１〜０．５質量％の範囲であり、かつ、水溶性の陰イオン及び／又は非イオン界面活性剤の０．１質量％水溶液の２５℃における表面張力が３５ｍＮ／ｍより小さくすることができる。
さらに、本発明の親水防汚コーティング組成物においては、沸点が１２０℃以上の水溶性溶剤がグリコールエーテルから選ばれた１種又は２種以上を含むことができる。
また、本発明は、アンモニア又は揮発性アミンで中和した水分散性シリカゾルと、水溶性の陰イオン及び／又は非イオン界面活性剤と、水溶性溶剤とを含み、シリカゾル中の酸化ナトリウム含有量が０．２質量％より小さく、水溶性溶剤の沸点が１２０℃以上であり、かつ、水溶性溶剤が、２０℃の粘性率が１０ｍＰａ・ｓ以下であり、かつ、２５℃の表面張力が４０ｍＮ／ｍより小さいことを特徴とする親水防汚コーティング組成物を、被塗布物上に塗布した後、乾燥させる被膜の形成方法である。
またさらに本発明の被膜の形成方法においては、親水防汚コーティング組成物を上記の親水防汚コーティング組成物とすることができる。
さらに、本発明は、アンモニア又は揮発性アミンで中和した水分散性シリカゾルと、水溶性の陰イオン及び／又は非イオン界面活性剤と、水溶性溶剤とを含み、シリカゾル中の酸化ナトリウム含有量が０．２質量％より小さく、水溶性溶剤の沸点が１２０℃以上であり、かつ、水溶性溶剤が、２０℃の粘性率が１０ｍＰａ・ｓ以下であり、かつ、２５℃の表面張力が４０ｍＮ／ｍより小さいことを特徴とする親水防汚コーティング組成物を、被塗布物上に塗布した後、４官能性アルキルアルコキシシランを含む反応性希釈液を塗布し反応させる親水防汚コーティング膜の耐久性を向上させる被膜の形成方法である。
また、本発明の親水防汚コーティング膜の耐久性を向上させる被膜の形成方法においては、親水防汚コーティング組成物が、上記の親水防汚コーティング組成物とすることが出来る。
さらに、本発明の被膜の形成方法では、被塗布物が、車両の車体、車両又は建築物の窓ガラス、ミラー、タイル、衛生陶器、流台のステンレス部位、メッキ部位とすることが出来る。
As a result of intensive studies, the present inventors have found that the object can be achieved by combining a specific water-dispersible silica sol, a water-soluble anionic and / or nonionic surfactant, and a specific water-soluble solvent.
That is,
The present invention includes a water-dispersible silica sol was neutralized with ammonia or volatile amine, a water-soluble anionic and / or nonionic surfactants, and a water-soluble solvent, the sodium oxide content in the
Moreover, in the hydrophilic antifouling coating composition of this invention, the silica average particle diameter of the water dispersible silica sol neutralized with ammonia or the volatile amine can be 5-50 nm.
Furthermore, in the hydrophilic antifouling coating composition of the present invention, the solid content concentration of the water-dispersible silica sol neutralized with ammonia or a volatile amine can be in the range of 0.01 to 2.0% by mass.
In the hydrophilic antifouling coating composition of the present invention, the concentration of the surfactant is in the range of 0.01 to 0.5% by mass, and the water-soluble anionic and / or nonionic surfactant is used. The surface tension of a 0.1 mass% aqueous solution at 25 ° C. can be made smaller than 35 mN / m.
Furthermore, in the hydrophilic antifouling coating composition of the present invention, the water-soluble solvent having a boiling point of 120 ° C. or higher can contain one or more selected from glycol ethers.
Further, the present invention is ammonia or a water-dispersible silica sol is neutralized with volatile amine comprises a water-soluble anionic and / or nonionic surfactant, a water-soluble solvent, sodium oxide content in the silica sol Is less than 0.2% by mass, the boiling point of the water-soluble solvent is 120 ° C. or more, the viscosity of the water-soluble solvent is 10 mPa · s or less, and the surface tension at 25 ° C. is 40 mN. It is a method for forming a film in which a hydrophilic antifouling coating composition characterized by being less than / m is applied onto an object to be coated and then dried.
Furthermore, in the method for forming a film of the present invention, the hydrophilic antifouling coating composition can be the above-mentioned hydrophilic antifouling coating composition.
Furthermore, the present invention includes ammonia or a water-dispersible silica sol is neutralized with volatile amine comprises a water-soluble anionic and / or nonionic surfactant, a water-soluble solvent, sodium oxide content in the silica sol Is less than 0.2% by mass, the boiling point of the water-soluble solvent is 120 ° C. or more, the viscosity of the water-soluble solvent is 10 mPa · s or less, and the surface tension at 25 ° C. is 40 mN. Durability of hydrophilic antifouling coating film in which a hydrophilic antifouling coating composition characterized by being less than / m is applied onto an object to be coated and then reacted by applying a reactive diluent containing a tetrafunctional alkylalkoxysilane. It is the formation method of the film which improves property.
Moreover, in the formation method of the film which improves the durability of the hydrophilic antifouling coating film of the present invention, the hydrophilic antifouling coating composition can be the above-mentioned hydrophilic antifouling coating composition.
Furthermore, in the method for forming a coating film of the present invention, the object to be coated can be a vehicle body, a window glass of a vehicle or a building, a mirror, a tile, a sanitary ware, a stainless part of a flow platform, or a plating part.
本発明の親水防汚コーティング組成物は、表２の結果から明らかなように、被膜の親水性に優れ、親水効果を一定期間持続させることができるとともに、被膜が残っている間は被塗物表面の雨跡汚れなどの付着を防止でき、かつ、水を主溶剤として選択できるために、作業者や地球環境に安全なコーティング組成物であり、様々な用途に利用できる利便性を兼ね備えているという極めて有用な効果をもたらした。
As is apparent from the results in Table 2, the hydrophilic antifouling coating composition of the present invention is excellent in the hydrophilicity of the film, can maintain the hydrophilic effect for a certain period, and is coated while the film remains. It is a coating composition that is safe for workers and the global environment, and can be used for various purposes because it can prevent the adhesion of rain marks on the surface and water can be selected as the main solvent. It brought about an extremely useful effect.
本発明の親水防汚コーティング組成物において用いる、水分散性シリカゾルは、アンモニア又は揮発性アミンで中和した水分散性シリカゾルであれば何でも良いが、とくに、
シリカ平均粒子径５〜５０ｎｍのものが好ましく用いられる。とくに好ましくは、５〜２０ｎｍである。シリカゾルのシリカ平均粒子径が５ｎｍより小さいと造膜した際の膜厚が小さくなりすぎて、親水性能が低下する。また、市販品がなく、製造コストがかかる。シリカゾルのシリカ平均粒子径が５０ｎｍより大きいと、膜の透明性及び強度が低下する。また、シリカゾルの固形分濃度としては、親水防汚コーティング組成物の０．０１〜１．０質量％の範囲であることが好ましく、より好ましくは、０．０５〜０．５質量％である。シリカゾルの固形分濃度が０．０１質量％より低いと親水性が低下する。シリカゾルの固形分濃度が１．０質量％より大きいと、膜厚が大きくなりすぎて干渉縞（虹色）が目立ち、外観が悪くなる。また、膜が割れやすく、強度が低下する。
またさらに、図２に示すように、ゾル中のシリカ微粒子はアルカリの存在下で電気二重層を形成して、安定化している。そして、被膜ではゲル化が起こる。このときアルカリとして、ナトリウムが存在しているとナトリウム塩となり、蒸発しない為、被膜に残留し、汚れの原因になる。
このため、本発明では、市販の水分散性シリカゾルは、ナトリウム中和型、アンモニア中和型、非中和酸型の３種類に大別されるが、このうちの、アンモニア中和型又は揮発性アミン中和型に限定する。
本発明では、不純物として存在するナトリウムの目安として、シリカゾル中の酸化ナトリウムに換算した含有量が０．２質量％以下のものを用いると良く、より好ましくは、０．１質量％以下である。
酸化ナトリウムの含有量が０．２質量％より大きいナトリウム中和型を用いると、造膜成分がシリカゾルのナトリウム塩となり、耐久性が低下することを確認した。また、ｐＨが比較的高く、ガラス質と一体化しやすく、基材表面にシミを形成しやすい。非中和酸型を用いると本発明実施例とほぼ同等の塗膜性能が得られるが、酸性溶液となり、安全に使用できるとは言い難く、また、長期の保存安定性を得難い。
アンモニア中和型の水分散性シリカゾルは、成膜後にアンモニアが揮発してシラノール基に富むコロイダルシリカの凝集膜を形成する。超微粒子であるために表面エネルギーが大きく、水素結合により比較的強固な膜となり、強力な親水性を発現する。また、水溶液のｐＨは８〜１０の弱アルカリ性領域で安定化させることができるため、比較的安全な水溶液とすることができる。アンモニアはトリエチルアミンなどの揮発性アミン類であってもほぼ同様な効果が得られる。このようなアンモニア中和型の水分散性シリカゾルは市販されており、スノーテックスＮ（日産化学工業株式会社製）、ルドックスＡＳ（グレースジャパン株式会社製）、カタロイドＳ−２０Ｌ（触媒化成工業株式会社製）、アデライトＡＴ−２０Ｎ（旭電化工業株式会社製）などが挙げられる。
水分散性シリカゾルのＴＥＭ写真を図３に示す。
The water-dispersible silica sol used in the hydrophilic antifouling coating composition of the present invention may be any water-dispersible silica sol neutralized with ammonia or a volatile amine,
A silica having an average particle diameter of 5 to 50 nm is preferably used. Especially preferably, it is 5-20 nm. When the silica average particle diameter of the silica sol is smaller than 5 nm, the film thickness when the film is formed becomes too small, and the hydrophilic performance is lowered. Moreover, there is no commercial item and manufacturing cost starts. When the silica average particle diameter of the silica sol is larger than 50 nm, the transparency and strength of the film are lowered. Moreover, as solid content concentration of a silica sol, it is preferable that it is the range of 0.01-1.0 mass% of a hydrophilic antifouling coating composition, More preferably, it is 0.05-0.5 mass%. When the solid content concentration of the silica sol is lower than 0.01% by mass, the hydrophilicity is lowered. When the solid content concentration of the silica sol is larger than 1.0% by mass, the film thickness becomes too large, interference fringes (rainbow colors) are conspicuous, and the appearance is deteriorated. Further, the film is easily broken and the strength is lowered.
Furthermore, as shown in FIG. 2, the silica fine particles in the sol are stabilized by forming an electric double layer in the presence of alkali. Then, gelation occurs in the coating. At this time, if sodium is present as an alkali, it becomes a sodium salt and does not evaporate, so it remains on the film and causes contamination.
For this reason, in the present invention, commercially available water-dispersible silica sols are roughly classified into three types: sodium neutralized type, ammonia neutralized type, and non-neutralized acid type. To neutral amine neutralization type.
In the present invention, as a measure of sodium present as an impurity, a content of 0.2% by mass or less, preferably 0.1% by mass or less, may be used in terms of sodium oxide in silica sol.
It was confirmed that when a sodium neutralization type having a sodium oxide content greater than 0.2% by mass was used, the film-forming component became a sodium salt of silica sol, and the durability was lowered. Moreover, pH is comparatively high, it is easy to integrate with glassy substance, and it is easy to form a spot on the base-material surface. When the non-neutralized acid type is used, the coating film performance almost equivalent to that of the examples of the present invention can be obtained. However, it is difficult to say that it becomes an acidic solution and can be used safely, and long-term storage stability is difficult to obtain.
The ammonia-neutralized water-dispersible silica sol forms an agglomerated film of colloidal silica rich in silanol groups by evaporation of ammonia after film formation. Since it is an ultrafine particle, it has a large surface energy, becomes a relatively strong film by hydrogen bonding, and exhibits strong hydrophilicity. Moreover, since pH of aqueous solution can be stabilized in the weak alkaline area | region of 8-10, it can be set as a comparatively safe aqueous solution. Even if ammonia is a volatile amine such as triethylamine, substantially the same effect can be obtained. Such ammonia-neutralized water-dispersible silica sol is commercially available, Snowtex N (manufactured by Nissan Chemical Industries, Ltd.), Ludox AS (manufactured by Grace Japan Co., Ltd.), Cataloid S-20L (Catalyst Chemical Industries, Ltd.) And Adelite AT-20N (manufactured by Asahi Denka Kogyo Co., Ltd.).
A TEM photograph of the water-dispersible silica sol is shown in FIG.
本発明で用いる界面活性剤は、水溶性の陰イオン及び又は非イオン界面活性剤ものであればどのような物でも使える。
コーティング組成物の表面張力を低下させ、基材表面に均一に塗布するための必須成分である。界面活性剤の種類は、陰イオン界面活性剤、非イオン界面活性剤の中から自由に選択できるが、表面張力低下能に優れ、使用又は保管する温度範囲においても安定した性能を発揮するものの中から選ばれる。
界面活性剤の表面張力低下能は、０．１％水溶液の表面張力が３５ｍＮ／ｍより小さいことが好ましく、より好ましくは、３０ｍＮ／ｍより小さいことである。界面活性剤の０．１％水溶液の表面張力が３５ｍＮ／ｍより大きいと、基材に対する濡れ性が低下し、均一に塗布することが困難となる。界面活性剤の濃度は０．０１％〜０．５％の範囲が好ましく、より好ましくは０．０５％〜０．２％である。界面活性剤の濃度が０．０１％より低いと表面張力低下能が低くなり、基材に対する濡れ性が悪くなる。界面活性剤の濃度が０．５％より高くなると界面活性剤自身の残渣が目立ち、外観が悪くなるとともに膜の強度が低下する。
As the surfactant used in the present invention, any water-soluble anionic and / or nonionic surfactant can be used.
It is an essential component for reducing the surface tension of the coating composition and applying it uniformly to the substrate surface. The type of surfactant can be freely selected from anionic surfactants and nonionic surfactants, but it has excellent surface tension reducing ability and exhibits stable performance even in the temperature range of use or storage. Chosen from.
The surface tension reducing ability of the surfactant is preferably such that the surface tension of the 0.1% aqueous solution is less than 35 mN / m, more preferably less than 30 mN / m. When the surface tension of a 0.1% aqueous solution of a surfactant is greater than 35 mN / m, the wettability with respect to the substrate is lowered, and it becomes difficult to apply uniformly. The concentration of the surfactant is preferably in the range of 0.01% to 0.5%, more preferably 0.05% to 0.2%. When the concentration of the surfactant is lower than 0.01%, the ability to lower the surface tension is lowered and the wettability with respect to the substrate is deteriorated. When the concentration of the surfactant is higher than 0.5%, the residue of the surfactant itself is noticeable, the appearance is deteriorated and the strength of the film is lowered.
本発明で用いる沸点が１２０℃以上の水溶性溶剤としては、沸点が１２０℃以上である水溶性のグリコールエーテルから選ばれた１種又は２種以上を挙げることが出来る。
本発明において沸点が１２０℃以上の水溶性溶剤を用いることにより、親水防汚コーティング組成物の造膜性を向上させることができ、外観良く、均一に塗布することができる。沸点が１２０℃以下では、造膜性を向上させる効果が低下する。
本発明で用いる沸点が１２０℃以上の水溶性溶剤の具体例としては、２−メトキシ−エタノール、２−エトキシ−エタノール、２−（メトキシメトキシ）エタノール、２−イソプロポキシエタノール、２−ブトキシエタノール、２−イソペンチルオキシエタノール、フルフリルアルコール、テトラヒドロフルフリルアルコール、エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコールブチルエーテル、プロピレングリコールメチルエーテル、プロピレングリコールブチルエーテル、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、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、１−メトキシ−２−プロパノール、１−エトキシ−２−プロパノール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノメチルエーテルなどが挙げられる。
さらに、本発明で用いる水溶性溶剤は、水溶性溶剤の沸点が１２０℃以上であることに加えて、２０℃の粘性率が１０ｍＰａ・ｓ以下であり、かつ、２５℃の表面張力が４０ｍＮ／ｍより小さいことが望ましい。
２０℃の粘性率が１０ｍＰａ・ｓを超え、かつ、２５℃の表面張力が４０ｍＮ／ｍを超えると、均一な被膜を形成することが困難になり、望ましい親水防汚コーティング組成物を得られない。
この条件を満たすために、上記に挙げた水溶性溶剤を組み合わせて、この条件を満足させることが出来る。
Examples of the water-soluble solvent having a boiling point of 120 ° C. or higher used in the present invention include one or more selected from water-soluble glycol ethers having a boiling point of 120 ° C. or higher.
By using a water-soluble solvent having a boiling point of 120 ° C. or higher in the present invention, the film-forming property of the hydrophilic antifouling coating composition can be improved, and it can be uniformly applied with good appearance. When the boiling point is 120 ° C. or lower, the effect of improving the film forming property is lowered.
Specific examples of the water-soluble solvent having a boiling point of 120 ° C. or higher used in the present invention include 2-methoxy-ethanol, 2-ethoxy-ethanol, 2- (methoxymethoxy) ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-isopentyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1- Butoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether.
Further, the water-soluble solvent used in the present invention has a boiling point of 120 ° C. or higher, a viscosity at 20 ° C. of 10 mPa · s or less, and a surface tension at 25 ° C. of 40 mN / s. Desirably smaller than m.
When the viscosity at 20 ° C. exceeds 10 mPa · s and the surface tension at 25 ° C. exceeds 40 mN / m, it becomes difficult to form a uniform film, and a desirable hydrophilic antifouling coating composition cannot be obtained. .
In order to satisfy this condition, this condition can be satisfied by combining the water-soluble solvents listed above.
本発明の親水防汚コーティング組成物は、成膜後に適当な反応性架橋剤を用いることによって、被膜強度を向上させることができる。
即ち、本発明組成物である水分散性シリカゾルの被膜形成直後の水分がわずかに残存している状態で、４官能性アルキルアルコキシシランを含む反応性希釈液を塗布することによって、コロイダルシリカ表面のシラノール基、ガラス表面に残存するシラノール基等と４官能性アルキルアルコキシシランが縮合反応し、コロイダルシリカの粒子同士の結合がより強固になり、膜強度を増大させることができる。このような４官能性アルキルアルコキシシランの例としては、テトラメトキシシラン、テトラエトキシシランなどが挙げられ、これらは水分と反応するためにアルコール等の有機溶剤に適量希釈し、反応性希釈剤として用いることができる。
さらに、本発明の親水防汚コーティング組成物には、必要に応じて性能に影響を及ぼさない範囲内で、液の腐敗を防ぐための防腐剤、乾燥性を速めるための沸点が１００℃以下のアルコール類、シリカゾルの保存安定性を向上させるためのｐＨ調整用アンモニア又は揮発性アミン類、香料、着色料などを配合することができる。
本発明の組成物は、通常、スプレー、ハケ塗り、ディッピング等の方法によって塗布される。塗布後は自然乾燥により成膜し、特別な乾燥設備は必要としないが、必要に応じて強制的に加熱乾燥させても良い。
塗膜が汚れたり、損傷したり、必要がなくなった場合は、ウエス等で簡単に拭き取ることができる。
本発明の親水防汚コーティング組成物は、車両の車体、車両又は建築物の窓ガラス、ミラー、タイル、水洗トイレ、衛生陶器（洗面台、トイレ便器など）、ステンレス部位（台所の流し台など）、メッキ部位（台所の流し台、水道栓など）の表面に塗布し、親水防汚被膜を形成することが出来る。
The hydrophilic antifouling coating composition of the present invention can improve the film strength by using an appropriate reactive crosslinking agent after film formation.
That is, the surface of the colloidal silica surface is coated by applying a reactive diluent containing a tetrafunctional alkylalkoxysilane in a state in which a little water immediately after the formation of the water-dispersible silica sol as the composition of the present invention remains. Silanol groups, silanol groups remaining on the glass surface, and the like and a tetrafunctional alkylalkoxysilane undergo a condensation reaction, and the bond between the colloidal silica particles becomes stronger and the film strength can be increased. Examples of such tetrafunctional alkylalkoxysilanes include tetramethoxysilane, tetraethoxysilane, and the like. These react with moisture to dilute an appropriate amount in an organic solvent such as alcohol and use as a reactive diluent. be able to.
Furthermore, in the hydrophilic antifouling coating composition of the present invention, a preservative for preventing liquid decay and a boiling point for speeding up drying of 100 ° C. or less as long as the performance is not affected as necessary. Alcohols, ammonia for pH adjustment for improving the storage stability of silica sol, volatile amines, fragrances, coloring agents, and the like can be blended.
The composition of the present invention is usually applied by a method such as spraying, brushing or dipping. After coating, the film is formed by natural drying, and no special drying equipment is required, but it may be forcibly heated and dried as necessary.
If the coating becomes dirty, damaged, or no longer necessary, it can be easily wiped off with a waste cloth or the like.
The hydrophilic antifouling coating composition of the present invention is a vehicle body, vehicle or building window glass, mirror, tile, flush toilet, sanitary ware (basin, toilet bowl, etc.), stainless steel part (kitchen sink, etc.), A hydrophilic antifouling film can be formed by applying to the surface of the plating site (kitchen sink, water tap, etc.).
本発明の実施の形態をまとめると以下の通りである。
（１）アンモニア又は揮発性アミンで中和した水分散性シリカゾルと、水溶性の陰イオン及び／又は非イオン界面活性剤と、水溶性溶剤とを含み、シリカゾル中の酸化ナトリウム含有量が０．２質量％より小さく、水溶性溶剤の沸点が１２０℃以上であり、かつ、水溶性溶剤が、２０℃の粘性率が１０ｍＰａ・ｓ以下であり、かつ、２５℃の表面張力が４０ｍＮ／ｍより小さいことを特徴とする親水防汚コーティング組成物。
（２）アンモニア又は揮発性アミンで中和した水分散性シリカゾルのシリカ平均粒子径が５〜５０ｎｍであることを特徴とする上記（１）に記載した親水防汚コーティング組成物。
（３）アンモニア又は揮発性アミンで中和した水分散性シリカゾルの固形分濃度が０．０１〜２．０質量％の範囲にあることを特徴とする上記（１）又は上記（２）に記載した親水防汚コーティング組成物。
（４）界面活性剤の濃度が、０．０１〜０．５質量％の範囲であり、かつ、水溶性の陰イオン及び／又は非イオン界面活性剤の０．１質量％水溶液の２５℃における表面張力が３５ｍＮ／ｍより小さいことを特徴とする上記（１）〜上記（３）のいずれかひとつに記載した親水防汚コーティング組成物。
（５）沸点が１２０℃以上の水溶性溶剤がグリコールエーテルから選ばれた１種又は２種以上を含むことを特徴とする上記（１）〜
上記（４）のいずれかひとつに記載した親水防汚コーティング組成物。
（６）アンモニア又は揮発性アミンで中和した水分散性シリカゾルと、水溶性の陰イオン及び／又は非イオン界面活性剤と、水溶性溶剤とを含み、シリカゾル中の酸化ナトリウム含有量が０．２質量％より小さく、水溶性溶剤の沸点が１２０℃以上であり、かつ、水溶性溶剤が、２０℃の粘性率が１０ｍＰａ・ｓ以下であり、かつ、２５℃の表面張力が４０ｍＮ／ｍより小さいことを特徴とする親水防汚コーティング組成物を、被塗布物上に塗布した後、乾燥させる被膜の形成方法。
（７）親水防汚コーティング組成物が、上記（２）〜上記（５）のいずれかひとつに記載した親水防汚コーティング組成物である上記（６）に記載した被膜の形成方法。
（８）アンモニア又は揮発性アミンで中和した水分散性シリカゾルと、水溶性の陰イオン及び／又は非イオン界面活性剤と、水溶性溶剤とを含み、シリカゾル中の酸化ナトリウム含有量が０．２質量％より小さく、水溶性溶剤の沸点が１２０℃以上であり、かつ、水溶性溶剤が、２０℃の粘性率が１０ｍＰａ・ｓ以下であり、かつ、２５℃の表面張力が４０ｍＮ／ｍより小さいことを特徴とする親水防汚コーティング組成物を、被塗布物上に塗布した後、４官能性アルキルアルコキシシランを含む反応性希釈液を塗布し反応させる親水防汚コーティング膜の耐久性を向上させる被膜の形成方法。
（９）親水防汚コーティング組成物が、請求項２〜請求項５のいずれかひとつに記載した親水防汚コーティング組成物である上記（８）に記載した親水防汚コーティング膜の耐久性を向上させる被膜の形成方法。
（１０）被塗布物が、車両の車体、車両又は建築物の窓ガラス、ミラー、タイル、衛生陶器、流台のステンレス部位、メッキ部位である上記（６）〜上記（９）のいずれかひとつに記載した被膜の形成方法。
次に実施例によって本発明をさらに具体的に詳細に亘って説明するが、本発明はこれらの例によって何ら限定されるものではない。
The embodiments of the present invention are summarized as follows.
(1) with ammonia or water-dispersible silica sol is neutralized with volatile amine, a water-soluble anionic and / or nonionic surfactants, and a water-soluble solvent, sodium oxide content in the silica sol is 0. Less than 2% by mass, the boiling point of the water-soluble solvent is 120 ° C. or higher, the water-soluble solvent has a viscosity at 20 ° C. of 10 mPa · s or less, and a surface tension at 25 ° C. of 40 mN / m A hydrophilic antifouling coating composition characterized by being small.
(2) The hydrophilic antifouling coating composition as described in (1) above, wherein the water-dispersible silica sol neutralized with ammonia or a volatile amine has a silica average particle size of 5 to 50 nm.
(3) The solid content concentration of the water-dispersible silica sol neutralized with ammonia or a volatile amine is in the range of 0.01 to 2.0% by mass, as described in (1) or (2) above Hydrophilic antifouling coating composition.
(4) The concentration of the surfactant is in the range of 0.01 to 0.5% by mass, and a 0.1% by mass aqueous solution of a water-soluble anionic and / or nonionic surfactant at 25 ° C. The hydrophilic antifouling coating composition as described in any one of (1) to (3) above, wherein the surface tension is less than 35 mN / m.
(5) The water-soluble solvent having a boiling point of 120 ° C. or higher contains one or two or more selected from glycol ethers.
The hydrophilic antifouling coating composition described in any one of the above (4).
(6) with ammonia or water-dispersible silica sol is neutralized with volatile amine, a water-soluble anionic and / or nonionic surfactants, and a water-soluble solvent, the sodium oxide content in the
(7) The method for forming a film according to (6), wherein the hydrophilic antifouling coating composition is the hydrophilic antifouling coating composition described in any one of (2) to (5) above.
(8) with ammonia or water-dispersible silica sol is neutralized with volatile amine comprises a water-soluble anionic and / or nonionic surfactant, a water-soluble solvent, sodium oxide content in the silica sol is 0. Less than 2% by mass, the boiling point of the water-soluble solvent is 120 ° C. or higher, the water-soluble solvent has a viscosity at 20 ° C. of 10 mPa · s or less, and a surface tension at 25 ° C. of 40 mN / m Improving the durability of a hydrophilic antifouling coating film in which a hydrophilic antifouling coating composition characterized by a small size is applied on an object to be coated and then reacted with a reactive diluent containing a tetrafunctional alkylalkoxysilane. A method of forming a film to be caused.
(9) The hydrophilic antifouling coating composition is a hydrophilic antifouling coating composition according to any one of claims 2 to 5, which improves the durability of the hydrophilic antifouling coating film according to (8). A method of forming a film to be caused.
(10) Any one of the above (6) to (9), wherein the object to be coated is a vehicle body, a window glass of a vehicle or a building, a mirror, a tile, a sanitary ware, a stainless steel part of a flow platform, or a plating part. The method for forming the coating described in 1.
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
イオン交換水９７．９ｇ中に、アンモニア又は揮発性アミンで中和した水分散性シリカゾルとして、スノーテックスＮ（シリカ含有量２０〜２１質量％／日産化学工業株式会社製）を１ｇ、陰イオン界面活性剤として、ジアルキルスルホコハク酸エステルナトリウム０．１ｇ、水溶性溶剤として、２−エトキシエタノール１ｇを配合し、均一に混合して実施例１の親水防汚コーティング組成物を得た。
1 g of Snowtex N (silica content 20 to 21% by mass / manufactured by Nissan Chemical Industries, Ltd.) as an aqueous dispersible silica sol neutralized with ammonia or volatile amine in 97.9 g of ion-exchanged water, anion interface 0.1 g of sodium dialkylsulfosuccinate as an activator and 1 g of 2-ethoxyethanol as a water-soluble solvent were blended and mixed uniformly to obtain a hydrophilic antifouling coating composition of Example 1.
イオン交換水９７．９ｇ中に、アンモニア又は揮発性アミンで中和した水分散性シリカゾルとして、スノーテックスＮ（シリカ含有量２０〜２１質量％／日産化学工業株式会社製）を１ｇ、陰イオン界面活性剤として、ジアルキルスルホコハク酸エステルナトリウム０．１ｇ、水溶性溶剤として、２−ブトキシエタノール１ｇを配合し、均一に混合して実施例２の親水防汚コーティング組成物を得た。
1 g of Snowtex N (silica content 20 to 21% by mass / manufactured by Nissan Chemical Industries, Ltd.) as an aqueous dispersible silica sol neutralized with ammonia or volatile amine in 97.9 g of ion-exchanged water, anion interface As an activator, 0.1 g of sodium dialkylsulfosuccinate ester and 1 g of 2-butoxyethanol as a water-soluble solvent were blended and mixed uniformly to obtain a hydrophilic antifouling coating composition of Example 2.
イオン交換水９７．９ｇ中に、アンモニア又は揮発性アミンで中和した水分散性シリカゾルとして、スノーテックスＮ（シリカ含有量２０〜２１質量％／日産化学工業株式会社製）を１ｇ、陰イオン界面活性剤として、ポリオキシエチレンアルキルフェニルエーテル硫酸エステルアンモニウム０．１ｇ、水溶性溶剤として、ジエチレングリコールモノエチルエーテル１ｇを配合し、均一に混合して実施例３の親水防汚コーティング組成物を得た。
1 g of Snowtex N (silica content 20 to 21% by mass / manufactured by Nissan Chemical Industries, Ltd.) as an aqueous dispersible silica sol neutralized with ammonia or volatile amine in 97.9 g of ion-exchanged water, anion interface As an activator, 0.1 g of ammonium polyoxyethylene alkylphenyl ether sulfate ester and 1 g of diethylene glycol monoethyl ether as a water-soluble solvent were blended and mixed uniformly to obtain a hydrophilic antifouling coating composition of Example 3.
イオン交換水９７．９ｇ中に、アンモニア又は揮発性アミンで中和した水分散性シリカゾルとして、スノーテックスＮ（シリカ含有量２０〜２１質量％／日産化学工業株式会社製）を１ｇ、非イオン界面活性剤として、ポリオキシエチレンラウリルエーテル０．１ｇ、水溶性溶剤として、ジプロピレングリコールモノメチルエーテル１ｇを配合し、均一に混合して実施例４の親水防汚コーティング組成物を得た。
1 g of Snowtex N (silica content 20 to 21% by mass / manufactured by Nissan Chemical Industries, Ltd.) as a water-dispersible silica sol neutralized with ammonia or volatile amine in 97.9 g of ion-exchanged water, non-ionic interface As an activator, 0.1 g of polyoxyethylene lauryl ether and 1 g of dipropylene glycol monomethyl ether as a water-soluble solvent were blended and mixed uniformly to obtain a hydrophilic antifouling coating composition of Example 4.
イオン交換水９８．４ｇ中に、アンモニア又は揮発性アミンで中和した水分散性シリカゾルとして、ルドックスＡＳ（シリカ含有量４０質量％／グレースジャパン株式会社製）を０．５ｇ、陰イオン界面活性剤として、ドデシルベンゼンスルホン酸ナトリウム０．１ｇ、水溶性溶剤として、１−エトキシ−２−プロパノール１ｇを配合し、均一に混合して実施例５の親水防汚コーティング組成物を得た。
In 98.4 g of ion-exchanged water, 0.5 g of Ludox AS (silica content 40% by mass / produced by Grace Japan KK) as an aqueous dispersible silica sol neutralized with ammonia or a volatile amine, an anionic surfactant As a water-soluble solvent, 0.1 g of sodium dodecylbenzenesulfonate and 1 g of 1-ethoxy-2-propanol were blended and mixed uniformly to obtain a hydrophilic antifouling coating composition of Example 5.
イオン交換水９６．９５ｇ中に、アンモニア又は揮発性アミンで中和した水分散性シリカゾルとして、ルドックスＡＳ（シリカ含有量４０質量％／グレースジャパン株式会社製）を１．０ｇ、非イオン界面活性剤として、ポリオキシプロピレンデシルエーテル０．０５ｇ、水溶性溶剤として、ジプロピレングリコールモノエチルエーテル２ｇを配合し、均一に混合して実施例６の親水防汚コーティング組成物を得た。 As a water-dispersible silica sol neutralized with ammonia or a volatile amine in 96.95 g of ion-exchanged water, 1.0 g of Ludox AS (silica content 40% by mass / Grace Japan Co., Ltd.), nonionic surfactant As a water-soluble solvent, 0.05 g of polyoxypropylene decyl ether and 2 g of dipropylene glycol monoethyl ether were blended and mixed uniformly to obtain a hydrophilic antifouling coating composition of Example 6.
イオン交換水９９．２５ｇ中に、アンモニア又は揮発性アミンで中和した水分散性シリカゾルとして、ルドックスＡＳ（シリカ含有量４０質量％／グレースジャパン株式会社製）を０．２ｇ、陰イオン界面活性剤として、ポリオキシエチレンアルキルエーテル硫酸エステルアンモニウム０．０５ｇ、水溶性溶剤として、ジプロピレングリコールモノメチルエーテル０．５ｇを配合し、均一に混合して実施例７の親水防汚コーティング組成物を得た。 In 99.25 g of ion-exchanged water, 0.2 g of Ludox AS (silica content 40% by mass / produced by Grace Japan KK) as an aqueous dispersible silica sol neutralized with ammonia or a volatile amine, an anionic surfactant As a water-soluble solvent, 0.05 g of polyoxyethylene alkyl ether sulfate ammonium and 0.5 g of dipropylene glycol monomethyl ether were blended and mixed uniformly to obtain a hydrophilic antifouling coating composition of Example 7.
実施例５の組成物に、揮発性アミンであるトリエチルアミンを０．１ｇ配合し、均一に混合して実施例８の親水防汚コーティング組成物を得た。
The composition of Example 5 was mixed with 0.1 g of triethylamine, which is a volatile amine, and mixed uniformly to obtain the hydrophilic antifouling coating composition of Example 8.
（比較例１）
イオン交換水９７．９ｇ中に、ナトリウムで中和した水分散性シリカゾルとして、スノーテックス２０（シリカ含有量２０〜２１質量％／日産化学工業株式会社製）を１ｇ、陰イオン界面活性剤として、ジアルキルスルホコハク酸エステルナトリウム０．１ｇ、水溶性溶剤として、２−エトキシエタノール１ｇを配合し、均一に混合して比較例１の親水防汚コーティング組成物を得た。
(Comparative Example 1)
As a water-dispersible silica sol neutralized with sodium in 97.9 g of ion-exchanged water, 1 g of Snowtex 20 (silica content 20 to 21% by mass / manufactured by Nissan Chemical Industries, Ltd.) as an anionic surfactant, 0.1 g of sodium dialkylsulfosuccinate ester and 1 g of 2-ethoxyethanol as a water-soluble solvent were blended and mixed uniformly to obtain a hydrophilic antifouling coating composition of Comparative Example 1.
（比較例２）
イオン交換水９８ｇ中に、アンモニア又は揮発性アミンで中和した水分散性シリカゾルとして、スノーテックスＮ（シリカ含有量２０〜２１質量％／日産化学工業株式会社製）を１ｇ、水溶性溶剤として、２−エトキシエタノール１ｇを配合し、界面活性剤を用いることなく、均一に混合して比較例２の親水防汚コーティング組成物を得た。
(Comparative Example 2)
As a water-dispersible silica sol neutralized with ammonia or volatile amine in 98 g of ion-exchanged water, 1 g of Snowtex N (silica content 20 to 21% by mass / manufactured by Nissan Chemical Industries, Ltd.) as a water-soluble solvent, 1 g of 2-ethoxyethanol was blended and mixed uniformly without using a surfactant to obtain a hydrophilic antifouling coating composition of Comparative Example 2.
（比較例３）
イオン交換水９８．９ｇ中に、アンモニア又は揮発性アミンで中和した水分散性シリカゾルとして、スノーテックスＮ（シリカ含有量２０〜２１質量％／日産化学工業株式会社製）を１ｇ、陰イオン界面活性剤として、ジアルキルスルホコハク酸エステルナトリウム０．１ｇを配合し、水溶性溶剤を用いることなく、均一に混合して比較例３の親水防汚コーティング組成物を得た。
(Comparative Example 3)
1 g of Snowtex N (silica content 20 to 21% by mass / manufactured by Nissan Chemical Industries, Ltd.) as an aqueous dispersible silica sol neutralized with ammonia or volatile amine in 98.9 g of ion-exchanged water, anion interface As an activator, 0.1 g of sodium dialkylsulfosuccinate was blended and mixed uniformly without using a water-soluble solvent to obtain a hydrophilic antifouling coating composition of Comparative Example 3.
（比較例４）
イオン交換水９７．９ｇ中に、アンモニア又は揮発性アミンで中和した水分散性シリカゾルとして、スノーテックスＮ（シリカ含有量２０〜２１質量％／日産化学工業株式会社製）を１ｇ、陰イオン界面活性剤として、ジアルキルスルホコハク酸エステルナトリウム０．１ｇ、水溶性溶剤として、２−プロパノール１ｇを配合し、均一に混合して比較例４の親水防汚コーティング組成物を得た。
(Comparative Example 4)
1 g of Snowtex N (silica content 20 to 21% by mass / manufactured by Nissan Chemical Industries, Ltd.) as an aqueous dispersible silica sol neutralized with ammonia or volatile amine in 97.9 g of ion-exchanged water, anion interface As an activator, 0.1 g of sodium dialkylsulfosuccinate ester and 1 g of 2-propanol as a water-soluble solvent were blended and mixed uniformly to obtain a hydrophilic antifouling coating composition of Comparative Example 4.
（比較例５）
イオン交換水９７．９ｇ中に、アンモニア又は揮発性アミンで中和した水分散性シリカゾルとして、スノーテックスＮ（シリカ含有量２０〜２１質量％／日産化学工業株式会社製）を１ｇ、陰イオン界面活性剤として、ジアルキルスルホコハク酸エステルナトリウム０．１ｇ、水溶性溶剤として、１,２−プロパンジオール１ｇを配合し、均一に混合して比較例５の親水防汚コーティング組成物を得た。
(Comparative Example 5)
1 g of Snowtex N (silica content 20 to 21% by mass / manufactured by Nissan Chemical Industries, Ltd.) as an aqueous dispersible silica sol neutralized with ammonia or volatile amine in 97.9 g of ion-exchanged water, anion interface As an activator, 0.1 g of sodium dialkylsulfosuccinate ester and 1 g of 1,2-propanediol as a water-soluble solvent were blended and mixed uniformly to obtain a hydrophilic antifouling coating composition of Comparative Example 5.
実施例１〜８及び比較例１〜３に用いたコロイダルシリカ平均粒子径、シリカ中の酸化ナトリウム含有量、界面活性剤の種類、水溶性溶剤の沸点、２０℃における粘性率（ｍＰａ・ｓ）、２５℃における表面張力（ｍＮ／ｍ）について表１に示す。
実施例７の組成物をソーダガラス試験板（７×１５ｍｍ）上にスプレー塗装して、表面の水分が乾燥した後、テトラメトキシシラン１ｇをイソプロピルアルコール９９ｇに混合した反応性希釈剤を、膜上に均一にスプレーし、自然乾燥させ、実施例９の試験板とした。 After spraying the composition of Example 7 onto a soda glass test plate (7 × 15 mm) and drying the surface moisture, a reactive diluent obtained by mixing 1 g of tetramethoxysilane with 99 g of isopropyl alcohol was applied on the film. The sample was sprayed uniformly and allowed to air dry to give a test plate of Example 9.
実施例１〜８及び比較例１〜３の組成物をソーダガラス試験板（７×１５ｍｍ）上にスプレー塗装して、自然乾燥させた後、膜の外観を目視で評価し、水滴の接触角を測定した。
また、試験板を１ヶ月間屋外に暴露して、汚れの付着状態を観察した。
さらに、１ヶ月間屋外に暴露した試験板の半面を、水を含ませた洗車用スポンジで表面を擦り、さらに１ヶ月間屋外に暴露して、汚れの付着状態を観察した。
実施例１の親水防汚コーティング組成物をソーダガラス試験板上にスプレー塗装して、自然乾燥させた後、１ヶ月間屋外に暴露した屋外暴露試験の写真を図４に示す。
なお、何も処理していないソーダガラス板を１ヶ月間屋外に暴露した屋外暴露試験の写真を比較のため図４に添付した。
After spray-coating the compositions of Examples 1 to 8 and Comparative Examples 1 to 3 on a soda glass test plate (7 × 15 mm) and air-drying, the appearance of the film was visually evaluated, and the contact angle of water droplets Was measured.
In addition, the test plate was exposed to the outdoors for one month, and the state of dirt adhesion was observed.
Further, half of the test plate exposed to the outdoors for 1 month was rubbed with a water-washing sponge for water and exposed to the outdoors for another month to observe the state of adhesion of dirt.
FIG. 4 shows a photograph of an outdoor exposure test in which the hydrophilic antifouling coating composition of Example 1 was spray-coated on a soda glass test plate, allowed to dry naturally, and then exposed to the outdoors for one month.
In addition, the photograph of the outdoor exposure test which exposed the soda glass board which has not processed anything outdoors for one month was attached to FIG. 4 for the comparison.
（比較例６）
何も塗装しないソーダガラス試験板を比較例比較例６とした。
(Comparative Example 6)
A soda glass test plate on which nothing was painted was designated as Comparative Example 6.
実施例１〜９及び比較例１〜４の試験板の評価結果を表２に示す。
外観・・・目視
水の接触角・・・自動接触角計（ＦＡＭＡＳ／協和界面科学製）による測定
汚れの付着状況・・・目視
Table 2 shows the evaluation results of the test plates of Examples 1 to 9 and Comparative Examples 1 to 4.
Appearance ... Visual Contact angle of water ... Measurement by automatic contact angle meter (FAMAS / Kyowa Interface Science)
本発明の親水防汚コーティング組成物は、塗布した表面を親水化でき、親水効果を一定期間持続させることができるとともに、被塗物表面の雨跡汚れなどの付着を防止できるばかりか、水を主溶剤として選択できるために、作業者や地球環境にやさしい。また、車両や建築物の表面に広く適用できるので、産業上きわめて利用可能性が高いものである。
The hydrophilic antifouling coating composition of the present invention can make the applied surface hydrophilic and can maintain the hydrophilic effect for a certain period of time, and can prevent adhesion of rain marks and the like on the surface of the object to be coated. Because it can be selected as the main solvent, it is friendly to workers and the global environment. Moreover, since it can be widely applied to the surface of a vehicle or a building, it is extremely highly applicable in industry.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008189884A (en) * | 2007-02-07 | 2008-08-21 | Mitsubishi Rayon Co Ltd | Water-based coating materials and painted products |
| JP2012506771A (en) * | 2008-10-31 | 2012-03-22 | ディーエスエム アイピー アセッツ ビー．ブイ． | Anti-adhesion coating composition comprising functionalized nanoparticles |
| JP2012239997A (en) * | 2011-05-20 | 2012-12-10 | Kaneka Corp | Method for manufacturing photoelectric conversion apparatus with anti-reflection film, and method for diagnosing coating characteristic of film forming composition |
| JP5968469B2 (en) * | 2012-02-27 | 2016-08-10 | スリーエム イノベイティブ プロパティズ カンパニー | Basic composition comprising inorganic oxide nanoparticles and organic base, coated substrate, article, and method |
| JP6127322B2 (en) * | 2012-09-28 | 2017-05-17 | 大日本塗料株式会社 | Composition for forming hydrophilic coating film and hydrophilic coating film |
| JP6161671B2 (en) * | 2015-10-08 | 2017-07-12 | 株式会社Ｙｏｏコーポレーション | Car body coating composition and coating method |
| JP7329909B2 (en) * | 2018-06-28 | 2023-08-21 | 小林製薬株式会社 | Coating agent for toilet bowl |
| CN109266058B (en) * | 2018-09-18 | 2021-07-16 | 湖南凯斯利新材料有限公司 | Catalysis method and use method of water-based inorganic nano-coating |
| DE112021007781T5 (en) | 2021-06-07 | 2024-03-28 | Mitsubishi Electric Corporation | Coating composition, coating film and article, optical device and lighting device |
| CN115725105A (en) * | 2022-11-29 | 2023-03-03 | 长春工业大学 | A kind of hydrophilic silicone rubber graphene antifouling composite material modified by polyvinylpyrrolidone and preparation method thereof |
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| JPS61235468A (en) * | 1985-04-10 | 1986-10-20 | Kashiyuu Kk | Hydrophilic film-forming aqueous composition |
| JPS6295361A (en) * | 1985-10-22 | 1987-05-01 | Yoshio Ichikawa | Coating composition |
| JPH0832854B2 (en) * | 1987-01-06 | 1996-03-29 | 日本合成ゴム株式会社 | Coating composition |
| JP2001164173A (en) * | 1999-12-13 | 2001-06-19 | Asahi Glass Co Ltd | Painted articles for building materials |
| JP2001181535A (en) * | 1999-12-27 | 2001-07-03 | Nippon Parkerizing Co Ltd | Photocatalytic paint for environmental purification |
| JP2003284959A (en) * | 2002-03-28 | 2003-10-07 | Toto Ltd | Photocatalytic member |
| WO2005075583A1 (en) * | 2004-02-04 | 2005-08-18 | Mitsubishi Rayon Co., Ltd. | Coating, process for producing the same and coated article furnished with the coating |
| JPWO2006049008A1 (en) * | 2004-11-08 | 2008-05-29 | 旭硝子株式会社 | Inorganic coating composition, hydrophilic coating film and method for forming hydrophilic coating film |
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