JP2010138358A - Antifouling coating liquid, method of forming antifouling coating layer, and ceramic industry building material having antifouling coating layer - Google Patents
Antifouling coating liquid, method of forming antifouling coating layer, and ceramic industry building material having antifouling coating layer Download PDFInfo
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- JP2010138358A JP2010138358A JP2008318671A JP2008318671A JP2010138358A JP 2010138358 A JP2010138358 A JP 2010138358A JP 2008318671 A JP2008318671 A JP 2008318671A JP 2008318671 A JP2008318671 A JP 2008318671A JP 2010138358 A JP2010138358 A JP 2010138358A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 102
- 238000000576 coating method Methods 0.000 title claims abstract description 99
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000011247 coating layer Substances 0.000 title claims abstract description 19
- 239000004566 building material Substances 0.000 title claims description 6
- 239000000919 ceramic Substances 0.000 title claims description 6
- 239000007788 liquid Substances 0.000 title abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010419 fine particle Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 35
- 238000012360 testing method Methods 0.000 description 10
- 239000003973 paint Substances 0.000 description 7
- 238000011109 contamination Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 230000001846 repelling effect Effects 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002009 diols Chemical group 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- IUKSYUOJRHDWRR-UHFFFAOYSA-N 2-diazonio-4,6-dinitrophenolate Chemical compound [O-]C1=C([N+]#N)C=C([N+]([O-])=O)C=C1[N+]([O-])=O IUKSYUOJRHDWRR-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ZUQAPLKKNAQJAU-UHFFFAOYSA-N acetylenediol Chemical group OC#CO ZUQAPLKKNAQJAU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
Description
本発明は、防汚コーティング液、防汚コーティング層形成方法、および防汚コーティング層を有する窯業建材に関する。 The present invention relates to an antifouling coating liquid, an antifouling coating layer forming method, and a ceramic building material having an antifouling coating layer.
外壁材の建築板の表面上には、しばしば、防汚コーティング液の塗布により、セルフクリーニング機能を有する防汚膜を形成する処理が施される。セルフクリーニング機能とは、防汚コーティング液から形成された親水性塗膜表面に汚れ成分が付着した場合に、さらに雨水などが連続的に付着すると、前記汚れ成分と前記親水性塗膜の間に雨水が入り込むことにより、雨水と共に当該汚れ成分が除去される機能をいう。このような防汚コーティング液としては、シリカ微粒子の水性分散液などが使用されている。シリカ微粒子を含有する防汚コーティング剤を外壁剤の建築板の塗膜表面に塗布すると、当該塗膜表面上に、前記シリカ微粒子から形成される超親水性の防汚膜が形成され、前述のセルフクリーニング機能による防汚が可能になる。
しかし、通常、アルコールを含有しない防汚コーティング液を塗膜の表面に塗布しても、塗膜の表面でハジキ現象が発生してしまうので、均一な塗布を行うことはできない。このため、従来、塗膜との濡れ性を付与する目的で、防汚コーティング液にアルコールを添加することが必須であった。
例えば、特許文献１には、凹凸模様を有する板材の表面に塗装を施し、塗膜を形成し、その上にシリカ微粒子と、アルコールと、水と、界面活性剤とを含有する防汚処理剤を塗布することを特徴とする防汚層の形成方法、が記載されている。
However, even if an antifouling coating solution that does not contain alcohol is usually applied to the surface of the coating film, a repellency phenomenon occurs on the surface of the coating film, so that uniform application cannot be performed. For this reason, it has been essential to add alcohol to the antifouling coating solution for the purpose of imparting wettability with the coating film.
For example, Patent Document 1 discloses that an antifouling treatment agent is applied to a surface of a plate material having a concavo-convex pattern to form a coating film on which silica fine particles, alcohol, water, and a surfactant are contained. A method for forming an antifouling layer, characterized in that is applied.
しかし、近年の揮発性有機化合物の排出抑制意識の高まりから、アルコールのような有機溶剤を実質的に含有しない防汚コーティング液が求められている。
したがって、本発明では、アルコールを含有しない水性液をはじく性質を有する被塗物の表面にも均一に塗布することが可能であり、かつアルコールのような有機溶剤を実質的に含有しない防汚コーティング液を提供する事を目的とする。
However, with the recent increase in awareness of emission control of volatile organic compounds, an antifouling coating solution that does not substantially contain an organic solvent such as alcohol is required.
Therefore, in the present invention, the antifouling coating can be uniformly applied to the surface of an article to be coated that has the property of repelling an aqueous solution that does not contain alcohol, and substantially does not contain an organic solvent such as alcohol. The purpose is to provide liquid.
本発明は、必須成分としてシリカ微粒子と、水と、界面活性剤とを含有し、かつ、アルコールを実質的に含有しない防汚コーティング液に関する。
前記課題は、アルコールを実質的に含有しない防汚コーティング液の表面張力を３０ｄｙｎｅ／ｃｍ２以下にすることによって、達成される。
本発明は、後記の［１］〜［６］などを提供するものである。
［１］
必須成分としてシリカ微粒子と、界面活性剤と、水とを含有し、かつ、アルコールを実質的に含有しない防汚コーティング液。
［２］
表面張力が３０ｄｙｎｅ／ｃｍ２以下である前記［１］に記載の防汚コーティング液。
［３］
さらに酸化チタンを含有する前記［１］または［２］に記載の防汚コーティング液。
［４］
有機、無機、もしくは有機無機ハイブリッド塗膜の表面に、前記［１］〜［３］のいずれか１項に記載の防汚コーティング液を塗布することを特徴とする防汚コーティング層形成方法。
［５］
有機、無機、もしくは有機無機ハイブリッド塗膜の表面の水接触角が、６０度〜１２０度である前記［４］に記載の防汚コーティング層形成方法。
［６］
前記［４］または［５］に記載の防汚コーティング層形成方法によって形成された防汚コーティング層を有する窯業建材。
The present invention relates to an antifouling coating solution containing silica fine particles, water, and a surfactant as essential components, and substantially free of alcohol.
The object can be achieved by setting the surface tension of the antifouling coating liquid substantially free of alcohol to 30 dyne / cm 2 or less.
The present invention provides the following [1] to [6] and the like.
[1]
An antifouling coating solution containing silica fine particles, a surfactant, and water as essential components, and containing substantially no alcohol.
[2]
The antifouling coating solution according to [1], wherein the surface tension is 30 dyne / cm 2 or less.
[3]
Furthermore, the antifouling coating solution according to the above [1] or [2] containing titanium oxide.
[4]
A method for forming an antifouling coating layer, comprising applying the antifouling coating solution according to any one of [1] to [3] to a surface of an organic, inorganic, or organic-inorganic hybrid coating film.
[5]
The method for forming an antifouling coating layer according to [4] above, wherein the water contact angle on the surface of the organic, inorganic, or organic-inorganic hybrid coating film is 60 to 120 degrees.
[6]
A ceramic building material having an antifouling coating layer formed by the method for forming an antifouling coating layer according to [4] or [5].
本発明によれば、水性液をはじく性質を有する被塗物表面に塗装しても、均一な塗膜を形成することが可能であり、かつアルコールのような有機溶剤を実質的に含有しない防汚コーティング液が提供される。 According to the present invention, a uniform coating film can be formed even when coated on the surface of an object having the property of repelling an aqueous liquid, and an organic solvent such as alcohol is not substantially contained. A dirty coating solution is provided.
［防汚コーティング液］
本発明の防汚コーティング液は、必須成分としてシリカ微粒子を含有する。
本発明の防汚コーティング液に用いられるシリカ微粒子は、好ましくは、１次粒子径が３〜５０ｎｍである。１次粒子径が３ｎｍ未満では、汚染防止効果が不十分となる恐れがあり、５０ｎｍを超えると塗膜外観が低下する恐れがある。より好ましい１次粒子径は、１０〜２５ｎｍである。シリカ微粒子の１次粒子径の測定は、電子顕微鏡観察などのよく知られた測定方法により求めることができる。
[Anti-fouling coating solution]
The antifouling coating liquid of the present invention contains silica fine particles as an essential component.
The silica fine particles used in the antifouling coating solution of the present invention preferably have a primary particle diameter of 3 to 50 nm. If the primary particle diameter is less than 3 nm, the effect of preventing contamination may be insufficient, and if it exceeds 50 nm, the appearance of the coating film may be deteriorated. A more preferable primary particle diameter is 10 to 25 nm. The measurement of the primary particle diameter of the silica fine particles can be obtained by a well-known measurement method such as observation with an electron microscope.
本発明の防汚コーティング液におけるシリカ微粒子の含有率は、防汚コーティング液全体１００質量部に対して、０．１〜１０質量部が好ましく、０．５〜５質量部がより好ましい。０．１質量部未満では、十分な防汚効果を得られない恐れがあり、１０質量部を超えると塗膜外観の低下の恐れがある。 0.1-10 mass parts is preferable with respect to 100 mass parts of the whole antifouling coating liquid, and, as for the content rate of the silica fine particle in the antifouling coating liquid of this invention, 0.5-5 mass parts is more preferable. If the amount is less than 0.1 parts by mass, a sufficient antifouling effect may not be obtained. If the amount exceeds 10 parts by mass, the appearance of the coating film may be deteriorated.
本発明の防汚コーティング液は、必須成分として界面活性剤を含有する。
界面活性剤の添加により、本発明の防汚コーティング液の表面張力を３０ｄｙｎｅ／ｃｍ２以下にすることができる。その結果、アルコールのような有機溶剤を添加することなく、水性液をはじく性質を有する塗膜表面にも防汚コーティング液を均一に塗布することが可能になる。
したがって、本発明の防汚コーティング液の表面張力は、好ましくは、３０ｄｙｎｅ／ｃｍ２以下（例、２０〜３０ｄｙｎｅ／ｃｍ２）である。
なお、本発明の防汚コーティング液の表面張力は、「色材と高分子材料のための最新機器分析法−分析と物性評価−」（ソフトサイエンス社 社団法人色材協会編 編集代表 星埜由典、ｐ．２８９ 表面張力測定法、「Ｄｕ Ｎｏｕｙ円環法」）に記載の方法に従って測定される。
本発明の防汚コーティング液における界面活性剤の含有率は、防汚コーティング液全体１００質量部に対して、好ましくは、０．０２〜５質量部、より好ましくは、０．１〜１質量部である。０．０２質量部未満であると、防汚コーティング液の表面張力を３０ｄｙｎｅ／ｃｍ２以下にすることができず、塗膜表面に防汚コーティング液を均一に塗布することができない恐れがある。一方、５質量部を超えても効果の向上が認められない恐れがあり、塗膜性能が低くなる恐れがある。
The antifouling coating liquid of the present invention contains a surfactant as an essential component.
By adding the surfactant, the surface tension of the antifouling coating solution of the present invention can be reduced to 30 dyne / cm 2 or less. As a result, it becomes possible to uniformly apply the antifouling coating liquid to the coating film surface having the property of repelling the aqueous liquid without adding an organic solvent such as alcohol.
Therefore, the surface tension of the antifouling coating solution of the present invention is preferably 30 dyne / cm 2 or less (eg, 20 to 30 dyne / cm 2 ).
In addition, the surface tension of the antifouling coating solution of the present invention is “the latest instrumental analysis method for color materials and polymer materials—analysis and physical property evaluation” (edited by Yukinori Hoshizaki, Editor-in-Chief of Soft Science Corporation Color Material Association, p.289 Surface tension measurement method, “Du Nouy ring method”)).
The content of the surfactant in the antifouling coating solution of the present invention is preferably 0.02 to 5 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the entire antifouling coating solution. It is. If the amount is less than 0.02 parts by mass, the surface tension of the antifouling coating solution cannot be reduced to 30 dyne / cm 2 or less, and the antifouling coating solution may not be uniformly applied to the coating film surface. On the other hand, even if it exceeds 5 parts by mass, the improvement of the effect may not be recognized, and the coating film performance may be lowered.
本発明の防汚コーティング液に用いられる界面活性剤としては、防汚コーティング液の安定性の観点から、ノニオン系界面活性剤が好ましい。前記ノニオン系界面活性剤としては、例えば、アルキレンオキサイドユニットを有する界面活性剤、アセチレンジオールユニットを有する（すなわち、同一分子内にアセチレン結合と２つの水酸基を同時に有する）界面活性剤、アルキレンオキサイドユニットとアセチレンジオールユニットとを有する界面活性剤、アクリル系ポリマー、シリコン系界面活性剤、およびフッ素系界面活性剤などが挙げられる。これらの界面活性剤は、単独で用いてもよく、本発明の防汚コーティング液の塗布の均一性を改良するなどの目的で、２種以上を併用してもよい。
前記「アルキレンオキサイドユニットを有する界面活性剤」としては、例えば、
ニューコール２３０２、２３０３、２３０５、２３０７、２３０８、２３０８ＨＥ、２３１０、２３１２、１２０４、１２１０、１３０５、１３１０、２５０２−Ａ、３５０４−Ｃ、２３０３−Ｙ、２３０４−ＹＭ、２３０４−Ｙ、ＮＴ−３、ＮＴ−５、ＮＴ−７、ＮＴ−９（商品名、日本乳化剤株式会社）；
ナロアクティーＮ−４０、ＩＤ−４０、エマルミン４０、５０、６０、セドランＦＦ−１８０、２００、２１０、セドランＳＦ−５０６、イオネットＤＬ−２００、ＭＯ−２００、サンモリン１１（商品名、三洋化成株式会社）；および
ＳＮウェット３６６、９８０、９８４（商品名、サンノプコ株式会社）
が挙げられる。
前記「アセチレンジオールを有する界面活性剤」としては、例えば、
サーフィノール１０４、４２０、４４０、４６５、ＭＤ２０、ＰＳＡ−３３６、２５０２、ダイノール６０４、６０７（商品名、エアープロダクツジャパン株式会社）が挙げられる。
前記「アクリル系ポリマー界面活性剤」としては、例えば、
ポリフローＷＳ、ＷＳ−３０、ＷＳ−３１４（商品名、共栄社化学株式会社）；および
ＢＹＫ−３８０Ｎ、ＢＹＫ−３８１（商品名、ビッグケミージャパン株式会社）
が挙げられる。
前記「シリコン系界面活性剤」としては、例えば、
グラノール１００、４００、４４０、ポリフローＫＬ−２４５、ＫＬ−２７０、ＫＬ−２８０、ＫＬ−６００（商品名、共栄社化学株式会社）；
ＢＹＫ−３０７、３３３、３４５、３４６、３４８、３７５、３７８（商品名、ビッグケミージャパン株式会社）；および
ＳＮウェット１２５、１２６（商品名、サンノプコ株式会社）
が挙げられる。
前記「フッ素界面活性剤」としては、例えば、
フタージェント２５０、２５１、２２２Ｆ、２０８Ｇ（商品名、株式会社ネオス）；
メガファックＦ−４４３、Ｆ−４４４、Ｆ−４４５、Ｆ−４７０、Ｆ−４７１、Ｆ−４７５、Ｆ−４７７、Ｆ−４７９（商品名、ＤＩＣ株式会社）；
ＮＯＶＥＣ ＦＣ−４４３０、４４３２（商品名、３Ｍ）；
ユニダイン ＤＳ−４０１、４０３（商品名、日進化成、ダイキン）；および
エフトップ ＥＦ−１２１、ＥＦ−１２２Ａ、ＥＦ−１２８Ｂ、ＥＦ−１２２Ｃ（商品名、ジェムコ）が挙げられる。
As the surfactant used in the antifouling coating solution of the present invention, a nonionic surfactant is preferable from the viewpoint of the stability of the antifouling coating solution. Examples of the nonionic surfactant include a surfactant having an alkylene oxide unit, a surfactant having an acetylene diol unit (that is, having an acetylene bond and two hydroxyl groups simultaneously in the same molecule), an alkylene oxide unit, Examples thereof include surfactants having an acetylenic diol unit, acrylic polymers, silicon surfactants, and fluorine surfactants. These surfactants may be used alone or in combination of two or more for the purpose of improving the uniformity of application of the antifouling coating solution of the present invention.
As the “surfactant having an alkylene oxide unit”, for example,
New Call 2302, 2303, 2305, 2307, 2308, 2308HE, 2310, 2312, 1204, 1210, 1305, 1310, 2502-A, 3504-C, 2303-Y, 2304-YM, 2304-Y, NT-3, NT-5, NT-7, NT-9 (trade name, Nippon Emulsifier Co., Ltd.);
NAROACTY N-40, ID-40, EMALMIN 40, 50, 60, Cedran FF-180, 200, 210, Cedran SF-506, Ionette DL-200, MO-200, Sanmorin 11 (trade name, Sanyo Chemical Co., Ltd. ); And SN wet 366, 980, 984 (trade name, San Nopco)
Is mentioned.
As the “surfactant having acetylenic diol”, for example,
Surfynol 104, 420, 440, 465, MD20, PSA-336, 2502, Dinol 604, 607 (trade name, Air Products Japan Co., Ltd.) may be mentioned.
As the “acrylic polymer surfactant”, for example,
Polyflow WS, WS-30, WS-314 (trade name, Kyoeisha Chemical Co., Ltd.); and BYK-380N, BYK-381 (trade name, Big Chemie Japan Co., Ltd.)
Is mentioned.
As the “silicone surfactant”, for example,
Granol 100, 400, 440, Polyflow KL-245, KL-270, KL-280, KL-600 (trade name, Kyoeisha Chemical Co., Ltd.);
BYK-307, 333, 345, 346, 348, 375, 378 (trade name, Big Chemie Japan Co., Ltd.); and SN wet 125, 126 (trade name, San Nopco Corporation)
Is mentioned.
As the “fluorine surfactant”, for example,
Footage 250, 251, 222F, 208G (trade name, Neos Co., Ltd.);
Megafuck F-443, F-444, F-445, F-470, F-471, F-475, F-477, F-479 (trade name, DIC Corporation);
NOVEC FC-4430, 4432 (trade names, 3M);
Unidyne DS-401, 403 (trade name, Nisshinsei, Daikin); and F-top EF-121, EF-122A, EF-128B, EF-122C (trade name, Gemco).
本発明の防汚コーティング液は、必須成分として水を含有する。
本発明の防汚コーティング液における水の含有率は、他の成分との合計が１００質量部になるように調整すればよい。
The antifouling coating solution of the present invention contains water as an essential component.
What is necessary is just to adjust the content rate of the water in the antifouling coating liquid of this invention so that the sum total with another component may be 100 mass parts.
本発明の防汚コーティング液は、さらに、光触媒活性機能を有する酸化チタンを含有してもよい。
酸化チタンの光触媒作用により、本発明の防汚コーティング液から形成される防汚層に、汚れ分解機能を付加するとともに、より強い親水性を付与することができる。
本発明の防汚コーティング液に用いられる酸化チタンは、好ましくは、平均粒子径５０ｎｍ〜１２０ｎｍの粒子であり、より好ましくは７０ｎｍ〜１００ｎｍの粒子である。平均粒子径は、レーザーを利用した散乱法によって測定できる。平均粒子径が５０ｎｍ未満では、塗膜の透明性は高くなるが、防汚層の成膜時にひび割れやすくなるため、膜厚を増加させることが困難となる恐れがある。一方、平均粒子径が１２０ｎｍを超えると、元来酸化チタンは白色顔料であるため、隠蔽性が高く、塗膜を白濁化する恐れがある。また、酸化チタンは比重が大きいので、前記の好ましい平均粒径を上回る酸化チタンを添加した場合、防汚コーティング液の保管中に沈殿物が生じる恐れがある。
本発明の防汚コーティング液における光触媒活性機能を有する酸化チタンの含有率は、防汚コーティング液全体１００質量部に対して、０．００５〜２質量部が好ましく、０．０２５〜０．５質量部がより好ましい。
The antifouling coating solution of the present invention may further contain titanium oxide having a photocatalytic activity function.
Due to the photocatalytic action of titanium oxide, it is possible to add a soil decomposition function to the antifouling layer formed from the antifouling coating solution of the present invention and to impart stronger hydrophilicity.
The titanium oxide used in the antifouling coating solution of the present invention is preferably particles having an average particle size of 50 nm to 120 nm, and more preferably 70 nm to 100 nm. The average particle diameter can be measured by a scattering method using a laser. When the average particle diameter is less than 50 nm, the transparency of the coating film is increased, but cracking is likely to occur when the antifouling layer is formed, and thus it may be difficult to increase the film thickness. On the other hand, when the average particle diameter exceeds 120 nm, titanium oxide is originally a white pigment, so that the concealability is high and the coating film may become clouded. In addition, since titanium oxide has a large specific gravity, when titanium oxide exceeding the preferable average particle diameter is added, a precipitate may be generated during storage of the antifouling coating solution.
The content of titanium oxide having a photocatalytic activity function in the antifouling coating solution of the present invention is preferably 0.005 to 2 parts by mass, and 0.025 to 0.5 parts by mass with respect to 100 parts by mass of the entire antifouling coating solution. Part is more preferred.
本発明の防汚コーティング液は、アルコールを実質的に含有しないことを特徴とする。より好ましくは、本発明の防汚コーティング液は、アルコール等の有機溶媒を含有しない。
本明細書中、「アルコール（または、有機溶媒）を実質的に含有しない」とは、防汚コーティング液における含有率が０．１質量％未満であることを意味する。
これにより、本発明の防汚コーティング液は、環境への負荷が小さい。
The antifouling coating solution of the present invention is characterized in that it contains substantially no alcohol. More preferably, the antifouling coating liquid of the present invention does not contain an organic solvent such as alcohol.
In the present specification, “substantially free of alcohol (or organic solvent)” means that the content in the antifouling coating solution is less than 0.1% by mass.
As a result, the antifouling coating liquid of the present invention has a low environmental load.
本発明の屋外設置物用防汚コーティング剤は、公知の方法により、前記した各成分を混合することにより、製造することができる。 The antifouling coating agent for outdoor installations of the present invention can be produced by mixing the above-described components by a known method.
［防汚コーティング層形成方法］
本発明の防汚コーティング層形成方法は、有機、無機、もしくは有機無機ハイブリッド塗膜の表面に、前記で説明した本発明の防汚コーティング液を塗布することを含む。
当該塗膜は、好ましくは、水接触角が、６０度〜１２０度である。
本明細書中、塗膜の水接触角は、
４μＬの純水を塗膜表面に滴下させ、液滴の接線と固体表面とのなす角度として求められる。なお、接触角の測定は、θ／２法によって、行われる。
水接触角が６０度未満の塗膜に対しても、本発明の防汚コーティング層形成方法を好適に適用できるが、このような塗膜は元々撥水性が低いので、本発明の防汚コーティング層形成方法を適用しても、特段の利益は得られない。
本発明の防汚コーティング液を有機、無機、もしくは有機無機ハイブリッド塗膜の表面に塗布、および乾燥させることにより、防汚コーティング層が形成される。
本発明の防汚コーティング液を有機、無機、もしくは有機無機ハイブリッド塗膜の表面に塗布する方法としては、水性塗料に用いられる慣用の方法を用いればよく、その例としては、刷毛、ローラー、スプレー、またはエアレススプレーなどを用いて塗布する方法が挙げられる。
当該塗布後の乾燥は、常温で行ってもよく、乾燥時間を短縮するため、加熱して行ってもよい。
本発明の防汚コーティング層形成方法を適用する有機、無機、もしくは有機無機ハイブリッド塗膜は、好ましくは、屋外で長期間使用される物品（例、窯業建材）の表面上に形成された塗膜である。
このようにして形成された防汚コーティング層を有する窯業建材もまた、本発明の一態様である。
[Method for forming antifouling coating layer]
The antifouling coating layer forming method of the present invention includes applying the antifouling coating solution of the present invention described above to the surface of an organic, inorganic, or organic-inorganic hybrid coating film.
The coating film preferably has a water contact angle of 60 degrees to 120 degrees.
In this specification, the water contact angle of the coating film is
4 μL of pure water is dropped on the surface of the coating film, and the angle formed by the tangent of the droplet and the solid surface is obtained. The contact angle is measured by the θ / 2 method.
The method for forming an antifouling coating layer of the present invention can also be suitably applied to a coating film having a water contact angle of less than 60 degrees, but since such a coating film originally has low water repellency, the antifouling coating of the present invention Even if the layer forming method is applied, no particular advantage is obtained.
The antifouling coating layer is formed by applying and drying the antifouling coating solution of the present invention on the surface of an organic, inorganic, or organic-inorganic hybrid coating film.
As a method for applying the antifouling coating solution of the present invention to the surface of an organic, inorganic, or organic-inorganic hybrid coating film, a conventional method used for water-based paints may be used. Examples thereof include brushes, rollers, sprays. Or a method of coating using an airless spray or the like.
The drying after the application may be performed at room temperature, or may be performed by heating in order to shorten the drying time.
The organic, inorganic, or organic-inorganic hybrid coating film to which the antifouling coating layer forming method of the present invention is applied is preferably a coating film formed on the surface of an article (eg, ceramic building material) that is used outdoors for a long period of time. It is.
A ceramic building material having the antifouling coating layer thus formed is also an embodiment of the present invention.
以下に、本発明を実施例によって更に詳細に説明するが、本発明はこれに限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
実施例１〜２、比較例１〜３
シリカ微粒子 １質量部に対し、次表に従い、界面活性剤［ニューコール２３０３−Ｙ（日本乳化剤社製）、サーフィノール４２０、サーフィノール４８５（日信化学工業）、エマール１０Ｇ（花王）、陰イオン性界面活性剤；ＦＣ−４４３０（３Ｍ）］および水にて１００質量部になるよう調整した。
In accordance with the following table, 1 part by mass of silica fine particles, surfactant [Newcol 2303-Y (manufactured by Nippon Emulsifier Co., Ltd.), Surfinol 420, Surfinol 485 (Nisshin Chemical Industry), Emar 10G (Kao), anion Surfactant; FC-4430 (3M)] and water were adjusted to 100 parts by mass.
凹凸模様のある建築板に、アクリルシーラー用塗料（オーデタイト１２８シーラー、日本ペイント）を塗装し、その上にシリコンアクリル樹脂水性エマルションエナメル塗料（オーデタイト３９０、日本ペイント）、さらに、シリコンアクリル樹脂水性エマルションクリヤー塗料（オーデタイト２３５クリヤー、日本ペイント）を上塗りとして塗布した。塗膜の水接触角は、８５°だった。なお、水接触角は、後記の方法によって測定した。
各塗料塗布ごとに、ジェット乾燥機にて、１００℃×風速１０ｍ×３分の条件で加熱乾燥させ、防汚コーティング液はレシプロエアースプレーにて４０ｇ／ｍ２の割合でスプレー塗布し、防汚層を形成した。
この時の塗布状態（均一に塗装されているかどうか）、泡立ち性（スプレー吹きした際に塗面に残泡するかどうか）を目視にて観察した。
塗布後、１日間放置し、以下の試験を行った。
［試験１］汚染試験（カーボンブラック水懸濁液による吹き付け試験）
以下の組成で、カーボンブラックＦＷ−２００（デグサ社製）を純水に分散させた。
カーボンブラックＦＷ−２００ ５質量％
純水 ９５質量％
前記分散液を、霧吹きで塗膜に塗布し、
塗膜を６０℃で１時間乾燥させた後、室温まで冷却し、
流水下にて、塗膜面汚れ物質をガーゼで除去しながら洗浄し、
洗浄後、乾燥したガーゼで塗膜面を拭き取り、室温で３時間乾燥させ、その外観を評価した。
［試験２］接触角試験
４μＬの純水を塗膜表面に滴下させ、液滴の接線と固体表面とのなす角度として接触角を求めた。なお、接触角の測定は、θ／２法によって、行った。
［試験３］雨だれ曝露試験
自然環境下で、垂直架設した塗板表面を６ヶ月間、雨水に曝露させた後に、この塗板表面の外観を評価した。
結果を次表に示す。なお、表中、○は良を表し、×は不良を表す。
A paint for acrylic sealer (Auditeite 128 sealer, Nippon Paint) is applied to the concavo-convex building board, and a silicone acrylic resin aqueous emulsion enamel paint (Auditeite 390, Nippon Paint) is applied on top of it. An emulsion clear paint (Odetite 235 Clear, Nippon Paint) was applied as a top coat. The water contact angle of the coating film was 85 °. The water contact angle was measured by the method described later.
For each coating application, heat drying with a jet dryer under conditions of 100 ° C. × wind speed 10 m × 3 minutes, and the antifouling coating solution is spray applied at a rate of 40 g / m 2 with reciprocating air spray to prevent antifouling. A layer was formed.
The coating state at this time (whether it was uniformly coated) and foaming property (whether or not residual bubbles were formed on the coated surface when sprayed) were visually observed.
After the application, it was left for 1 day, and the following tests were conducted.
[Test 1] Contamination test (carbon black water suspension spray test)
Carbon black FW-200 (manufactured by Degussa) was dispersed in pure water with the following composition.
Carbon black FW-200 5% by mass
95% pure water
Apply the dispersion to the coating film by spraying,
After the coating film was dried at 60 ° C. for 1 hour, it was cooled to room temperature,
Under running water, clean the surface of the paint film while removing it with gauze.
After washing, the coated surface was wiped with dry gauze and dried at room temperature for 3 hours, and the appearance was evaluated.
[Test 2] Contact angle test 4 μL of pure water was dropped on the surface of the coating film, and the contact angle was determined as the angle formed between the tangent of the droplet and the solid surface. The contact angle was measured by the θ / 2 method.
[Test 3] Raindrop exposure test In a natural environment, the surface of a vertically installed coated plate was exposed to rainwater for 6 months, and then the appearance of the coated plate surface was evaluated.
The results are shown in the following table. In the table, ◯ represents good and x represents poor.
（汚染試験評価基準）
５点：ほとんど汚染しない ４点：少し汚染する ３点：汚染する
２点：汚染程度が大きい １点：ひどく汚染する
（雨だれ試験評価基準）
５点：ほとんど汚染せず、雨筋もない ４点：雨筋はないが、若干汚染する
３点：若干の雨筋が認められる ２点：はっきりと雨筋が入っている
１点：ひどい雨筋が確認される
(Contamination test evaluation criteria)
5 points: hardly contaminated 4 points: slightly contaminated 3 points: contaminated 2 points: high degree of contamination 1 point: severely contaminated (evaluation criteria for raindrop test)
5 points: almost no pollution, no rain streaks 4 points: no rain streaks, slightly contaminated 3 points: some rain streaks are observed 2 points: clear rain streaks 1 point: heavy rain Streaks are confirmed
表２に明らかなように、表面張力が３０ｄｙｎｅ／ｃｍ２以下である実施例１および２では、非常に良好な低汚染塗膜を得ることができた。また、実施例２に示すように、２種類の界面活性剤を併用することにより、表面張力を３０ｄｙｎｅ／ｃｍ２以下にすることができ、また、そのコート剤を塗布することにより、非常に良好な低汚染塗膜を得ることができた。比較例５、６のように、界面活性剤量が少なすぎると、十分な濡れ性が得られず、汚染状態も良好でないことが明らかになった。一方、界面活性剤量が多すぎると、泡立ち性が高すぎるだけでなく、塗膜性能が低下し、耐水白化などが発生した。 As is apparent from Table 2, in Examples 1 and 2 having a surface tension of 30 dyne / cm 2 or less, very good low-contamination coating films could be obtained. Further, as shown in Example 2, the surface tension can be reduced to 30 dyne / cm 2 or less by using two kinds of surfactants together, and it is very good by applying the coating agent. A low-pollution coating film could be obtained. As in Comparative Examples 5 and 6, it was revealed that when the amount of the surfactant was too small, sufficient wettability could not be obtained and the contamination state was not good. On the other hand, when the amount of the surfactant was too large, not only the foaming property was too high, but also the coating film performance was lowered, and water whitening occurred.
Claims (6)
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| JP2017165833A (en) * | 2016-03-15 | 2017-09-21 | 日本ペイント・インダストリアルコ−ティングス株式会社 | Antifouling coating composition, method for forming antifouling coating layer and method for manufacturing ceramic housing material |
| WO2017159205A1 (en) * | 2016-03-15 | 2017-09-21 | 日本ペイント・インダストリアルコーティングス株式会社 | Antifouling coating composition, method for forming antifouling coating layer, and method for producing ceramic building material |
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| AU2017233628B2 (en) * | 2016-03-15 | 2020-11-19 | Nippon Paint Industrial Coatings Co., Ltd. | Antifouling coating composition, method for forming antifouling coating layer, and method for producing ceramic building material |
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