JP4352721B2 - Functional inorganic paint and its coating composition - Google Patents
Functional inorganic paint and its coating composition Download PDFInfo
- Publication number
- JP4352721B2 JP4352721B2 JP2003045991A JP2003045991A JP4352721B2 JP 4352721 B2 JP4352721 B2 JP 4352721B2 JP 2003045991 A JP2003045991 A JP 2003045991A JP 2003045991 A JP2003045991 A JP 2003045991A JP 4352721 B2 JP4352721 B2 JP 4352721B2
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- JP
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- Prior art keywords
- coating
- paint
- photocatalyst
- coating film
- silicon compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003973 paint Substances 0.000 title claims description 36
- 239000008199 coating composition Substances 0.000 title description 4
- 238000000576 coating method Methods 0.000 claims description 87
- 239000011248 coating agent Substances 0.000 claims description 86
- 239000011941 photocatalyst Substances 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 46
- 150000003377 silicon compounds Chemical class 0.000 claims description 23
- 230000005855 radiation Effects 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008119 colloidal silica Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
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- 239000003054 catalyst Substances 0.000 description 8
- 230000000844 anti-bacterial effect Effects 0.000 description 7
- 230000003373 anti-fouling effect Effects 0.000 description 7
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- 239000002184 metal Substances 0.000 description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
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- 241000894006 Bacteria Species 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- 239000011247 coating layer Substances 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
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- 229940121375 antifungal agent Drugs 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
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- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
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Images
Description
【０００１】
【発明の属する技術分野】
この出願の発明は、機能性無機質塗料とその塗装構成体に関するものである。さらに詳しくは、この出願の発明は、建築材等の製造において有用な、防汚性、抗菌性、消臭性に優れ、しかも塗膜密着性や耐久性等も良好な、光触媒を含有する新しい組成の機能性無機質塗料とこれを用いた塗装構成体に関するものである。
【０００２】
【従来の技術】
従来より、外装材やインテリア部材等の建築材の表面処理として、酸化チタン等の光触媒を含有した塗膜を形成させることが知られており、この光触媒含有の塗膜の形成についての様々な提案がなされてもいる。
【０００３】
光触媒は光照射によりラジカルを発生し、このラジカルが有機物の分解作用を有するため、光触媒を含む層を基材の表面に形成させた材料には、排気ガスやラバコ成分等の空気中の汚れ成分を分解する防汚性や、アルデヒド、ＶＯＣ、アンモニア、メルカプタン等の悪臭成分を分解する消臭性、大腸菌や黄色ブドウ球菌等の菌成分の発生を妨げる抗菌性等の機能が期待されている。そのような光触媒を応用した表面処理がすでに建築材に適用されており、たとえば、光触媒を分散させた塗料、塗り材、それらを塗布した鏡、ガラス、ボード、シート、タイル、などが商品化されている。
【０００４】
しかしながら、現状では、光触媒を配合、分散した塗膜では、光触媒の表面がバインダー、顔料等の他の塗料成分で被覆されたり、塗料内部で固定化され、光触媒が十分表面に露出していないために、配合した酸化チタン等の光触媒機能が十分に発現されていないのが実情である。
【０００５】
このため、表面に露出していない光触媒の機能を引き出すとともに、暗所でも光触媒機能を有するものとすることのできる塗膜組成物の実現が望まれていた。
【０００６】
このような課題に対して、微量の放射線を含む天然鉱石を光触媒とともに基材や塗料中に含有させることにより、光が照射されていない状態でも放射線による光触媒の励起を生じさせて、暗所でも光触媒効果を発揮させ、表面に露出していない光触媒の機能を引き出すことができるようにするとの提案（特許文献１）がなされている。
【０００７】
だが、この提案においても、暗所での光触媒効果の発揮や、表面に露出していない光触媒の機能の引き出しは充分でなく、また塗料としても、塗膜密着性、耐久性等の特性において実用的に満足できるものではないという問題があった。
【０００８】
【特許文献１】
特開２０００−１６７３９７号公報
【０００９】
【発明が解決しようとする課題】
そこでこの出願の発明は、上記の問題点を解消し、塗料としての組成特性に配慮することで、暗所での光触媒効果の発揮や、表面露出していない光触媒の機能の引き出しを充分なものとし、また塗料としても、塗膜密着性、耐久性等の特性において実用的に満足できる新しい塗料と、これを用いた新しい塗装構成体を提供することを課題としている。
【００１０】
【課題を解決するための手段】
この発明は、上記の課題を解決するものとして、第１には、塗膜形成成分として、（Ａ）放射線を放出する天然鉱石粉末および（Ｃ）ケイ素化合物を含有する下層用塗料と、塗膜形成成分として、（Ｂ）光触媒および（Ｃ）ケイ素化合物を含有する上層用塗料とよりなり、下層用塗料および上層用塗料を基材上に塗布して形成された塗膜が前記（Ａ）（Ｂ）（Ｃ）の成分のみによって形成されたものとすることを特徴とする機能性無機質塗料を提供する。
【００１１】
そして、第２には、塗膜を形成する前記（Ａ）（Ｂ）（Ｃ）の成分の重量比が、合計量１００部として（Ａ）放射線を放出する天然鉱石粉末が１〜１０部、（Ｂ）光触媒の固形分が１０〜８０部、（Ｃ）ケイ素化合物の固形分が２０〜８０部であることを特徴とする機能性無機質塗料を提供する。
【００１２】
また、第３には、（Ａ）放射線を放出する天然鉱石粉末は、５０ベクレル／ｇ以下の放射線を放出するものであることを特徴とする機能性無機質塗料を、第４には、（Ａ）放射線を放出する天然鉱石粉末は、（Ｂ）光触媒固形分に対して、両者の合計量の５重量％以上配合されていることを特徴とする機能性無機質塗料を、第５には（Ｃ）ケイ素化合物は、コロイダルシリカおよび次式
Ｒ２ ｎＳｉ（ＯＲ１）４−ｎ
（ｎは０〜３のうちの整数を示し、Ｒ１およびＲ２は、各々、同一または別異の炭化水素基を示す）
で表わされる１種以上の化合物が加水分解もしくは重縮合されて調製されたものであることを特徴とする機能性無機質塗料を提供する。
【００１３】
さらにこの出願の発明は、第６には、上記いずれかの塗料が塗布されて形成されていることを特徴とする塗装構成体を提供し、第７には、基材上に前記（Ａ）（Ｃ）成分を含有する下層用塗料の塗布により下層が形成された後に、前記（Ｂ）（Ｃ）成分を含有する上層用塗料の塗布により上層が形成されていることを特徴とする塗装構成体を、第８には、下地層として前記（Ａ）（Ｂ）成分を含有せずに（Ｃ）ケイ素化合物成分を含有する塗料による塗膜が形成されていることを特徴とする塗装構成体を提供する。
【００１４】
【発明の実施の形態】
この出願の発明は上記のとおりの特徴をもつものであるが、以下にその実施の形態について説明する。
【００１５】
この出願の発明の前記の機能性無機質塗料を構成する塗膜形成成分（Ａ）の放射線を放出する放射線放出天然鉱石としては、たとえば、デービド鉱、ブランネル石、センウラン鉱、ニンギョウ石、リンカイウラン石、カルノー石、ツヤムン石、マタチャムン石、フランセビル石、トール石、コフィン石、サマルスキー石、トリウム石、トロゴム石、モナズ石等が挙げられる。成分（Ａ）としての粉末は、これらの鉱石を粉砕して微粉末としたものであって、その一次粒径としては２００μｍ以下のものが一般的な目安とされるが、なかでも、一次粒径が５０μｍ以下のものが好ましい。また、放射線の放出レベルとしては、当然、人体に悪影響のないレベルであることが必要であり、５０ベクレル／ｇ以下の材料であることが望ましい。
【００１６】
これらの材料は、放射線の効果により、空気中の酸素、水分子等の会合物からなるマイナスイオンを発生させることができるという特徴を有している。
【００１７】
（Ｂ）成分の光触媒としては、酸化チタン、酸化亜鉛、酸化錫、酸化ジルコニウム、酸化タングステン、酸化鉄、酸化ニオブが挙げられ、１種のみ用いてもよいし、２種以上を併用してもよい。光触媒の一次粒径は一般的には１００μｍ以下が目安とされるが、５０μｍ以下のものが好ましい。
【００１８】
また、光触媒は金属を担持したものであってもよい。担持させる金属としては、特に限定されないが、金、銀、銅、テルル、亜鉛、ニッケル、コバルト、白金、ルテニウム、パラジウム、ロジウム、レニウム等が挙げられ、一種のみ、または、二種以上併用してもよい。金属を担持することにより、光触媒の電荷分離の促進や、ナノレベルでの担持で新たな励起準位が生じ、光触媒の活性を向上させることができる。金属を担持させる場合の担体としては、上記の酸化物粒子をはじめ、シリカ、アルミナ等の粒子であってもよい。これらの一次粒子の大きさは一般的には２００μｍ以下、さらには、上記と同程度とすることが好ましい。そして、金属の担持量としては、０．１〜５重量％であることが好ましい。金属の担持方法は、とくに限定されないが、浸漬法、スプレー法、光還元法が挙げられる。
【００１９】
光触媒は、粉体、ゾルの形で配合され、光触媒の塗料全体の固形分に対する割合は１０％以上８０％以下の重量割合であることが好ましい。比率は多いほど光触媒機能が発揮されるが、多すぎるとバインダー比率が下がり塗膜強度が低下することになる。
【００２０】
バインダー成分としては、光触媒によって分解しにくいバインダーを用いる必要があり、この出願の発明においては（Ｃ）成分としてのケイ素化合物を用いている。
【００２１】
このケイ素化合物としては、たとえば、コロイダルシリカと前記のとおりの一般式：
Ｒ2 nＳｉ（ＯＲ1）4-n
で表される化合物から調製されたものが好適に使用される（ｎは０から３の整数）。
【００２２】
ここで符号Ｒ１ は炭化水素基を示しており、なかでも、より好ましくは、炭素数１から４のアルキル基を主とし、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ターシャリーブチル基のいずれかであることが好ましい。
【００２３】
また、Ｒ ２ も炭化水素基を示しており、より好適には、炭素数１〜８の置換または非置換の炭化水素基である。たとえば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等のアルキル基、フェニル基等のアリール基、ビニル基等のアルケニル基、クロロメチル基、クロロプロピル基、トリフルオロプロピル基等のハロゲン置換炭化水素基、メタクリオキシプロピル基、グリシドキシプロピル基等の置換炭化水素基等が例示される。
【００２４】
以上のようなＲ1およびＲ2を有するケイ素化合物としては、たとえば、ｎ＝０の場合には、テトラメトキシシラン、テトラエトキシシラン等のテトラアルコキシシラン、ｎ＝１の場合には、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン等のオルガノトリアルコキシシラン、ｎ＝２の場合にはジメチルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン等のジオルガノジアルコキシシラン、ｎ＝３の場合には、トリメチルメトキシシラン、トリメチルエトキシシラン、トリメチルイソプロポキシシラン等が例として挙げられる。
【００２５】
成分（Ｃ）のケイ素化合物の好適なものは、コロイダルシリカとこれら化合物の１種以上のものを溶剤で希釈し、硬化剤として水または触媒を用いて、加水分解及び重縮合を行って調整したものとすることができる。たとえば、テトラアルコキシドおよびコロイダルシリカの少くともいずれか２０〜２００部、オルガノトリアルコキシシラン３０〜１００部、ジオルガノジアルコキシシラン０〜６０部の重量割合の組成物から調整し、ポリスチレン換算で重量平均分子量が９００以上に調整されたものである。
【００２６】
この出願の発明の機能性無機質塗料は、たとえば以上のように例示される
（Ａ）放射線を放出する天然鉱石粉末および（Ｃ）ケイ素化合物を含有する下層用塗料と、
（Ｂ）光触媒および（Ｃ）ケイ素化合物を含有する上層用塗料とよりなり、
下層用塗料および上層用塗料を基材上に塗布して形成された塗膜が前記（Ａ）（Ｂ）（Ｃ）の成分のみによって形成されたものとすることを特徴としている。このことから、塗膜が多層構成の場合には、たとえば（Ａ）（Ｃ）成分含有の塗料と（Ｂ）（Ｃ）成分含有の塗料の多層構成としてもよいし、あるいはこれらの塗料とともに、（Ａ）（Ｂ）（Ｃ）の成分を含有する塗料によって多層構成としてもよい。
【００２７】
塗料としての調製には、分散溶媒として、特に限定されることはないが、水、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類、エチレングリコール類等が用いられ、また、それらと併用して、トルエン、キシレン、酢酸エチル、酢酸ブチル等も用いることができる。また、加熱を行わず常温で硬化させる場合は、硬化触媒を添加することもできる。触媒としては、特に限定されないが、シロキサンの重縮合を進める場合には、硬化触媒を用いることができる。
【００２８】
また、必要に応じて、分散性、安定性向上や着色のため、顔料、染料、分散剤、増粘材等を添加してもよいし、耐電防止剤、防カビ材、抗菌剤、等を添加してもよい。
【００２９】
塗膜形成成分としての上記（Ａ）（Ｂ）（Ｃ）成分の配合割合については、これら成分が、重量比として、（Ａ）の放射線放出鉱石粉末１〜１０部、（Ｂ）の光触媒材料固形分１０〜８０部、（Ｃ）のケイ素化合物固形分２０〜８０部、ただし、（Ａ）＋（Ｂ）＋（Ｃ）＝１００部となるようにするのが好ましい。（Ａ）（Ｃ）成分の塗料と（Ｂ）（Ｃ）成分の塗料とを分けて使用する場合にも、全体として上記割合になるようにするのが好ましい。そして、いずれの場合も、（Ａ）の放射線放出鉱石粉末は（Ｂ）の光触媒の固形成分に対して、合計量の５重量％以上用いるのが好ましい。その理由として、放射線放出鉱石は光触媒を励起させるために配合するものであって、光触媒に対して、５％以上用いることにより、光触媒の機能向上が可能となるためである。
【００３０】
また、上記の配合においては、ケイ素化合物の割合が少なすぎると、塗膜としての密着性や耐久性が得られなくなり、他方で過剰であると、光触媒の機能向上を図ることが難しくなる。
【００３１】
そして、この出願の発明の塗料を用いての塗膜構成体の形成のための塗布方法については、特に限定されることはないが、スプレー、はけ塗り、バーコーター、スピンコーター、ディッピング、ロールコーター、フローコーター等の各種の方法が用いられる。また、必要に応じて、加熱処理を施すことにより塗膜硬化を進めることもできるし、硬化触媒を用いることにより、常温で硬化を進めてもよい。硬化を進める場合、２００℃以下の温度で硬化させることが好ましい。
【００３２】
塗膜の厚みは、とくに限定されないが、塗膜が長期的に安定、密着、保持され、かつ、クラックや剥離が発生しないためには、たとえば、５０μｍ以下、０．１〜２０μｍ程度が好ましい。
【００３３】
被塗布基材としては、とくに限定されないが、アルミニウム、鉄、ステンレス、ブリキ、それらの合金等の金属基材、木材、合板、ＭＤＦ、パーティクルボード等の木質建材等の木質基材、ＦＲＰ、人造大理石、樹脂成形品等のプラスチック基材、ガラス、ホーロー、セラミックス、石膏ボード、珪酸カルシウム板、ロックウール板、各種セメント板、粘土板、陶磁器質タイル、スレート、等の無機基材、その他、シート、紙、繊維、不織布、等の各種のものであってよく、その種類はとくに限定されることがない。さらに、それらの基材に有機塗装を施したものでもよい。また、木質基材、樹脂基材、シート等の有機材料の場合、一旦光触媒を含まない該塗料を塗布した後、光触媒を含む塗料を塗布することにより、光触媒による基材の劣化を防止することができる。たとえば、下地層の第一塗膜層として、上記の（Ｃ）のケイ素化合物のみを含有する塗料塗膜を形成させた後、第二塗膜層として（Ａ）（Ｂ）（Ｃ）成分による機能性塗膜を形成させることも有効である。
【００３４】
また、下層として、（Ａ）の微量の放射線を放出する天然鉱石と（Ｃ）のケイ素化合物を含有する下層用塗料により形成された塗膜を配設した後、上層として（Ｂ）の光触媒と（Ｃ）のケイ素化合物を含有する上層用塗料により形成された塗膜を配設する。その場合も、塗膜を形成する塗料の全体としては、（Ａ）の放射線放出鉱石と（Ｂ）の光触媒の比率は上記のとおりの５％以上となるようにするのが好ましい。（Ａ）と（Ｂ）をそれぞれの塗膜層に分けると、第一塗膜層は鉱石粉末添加により、未添加の場合よりも、凹凸性が増し、第二膜との密着性が向上し、さらには表面の第二塗膜層の平滑性、耐久性は向上する。
【００３５】
以上のとおりのこの出願の発明の機能性無機質塗膜を形成させた建築材及び物品は、屋外、室内用部材に用いることができる。たとえば、屋外部材としては、外装材、瓦、雨樋、門、フェンス、ドア、窓や、それらの周辺部材が挙げられ、室内部材としては、天井、壁、床、収納部材、造作材、キッチン、トイレ、洗面、浴室、窓や、それらの周辺部材への使用や、照明カバー、ランプ、障子、ふすま等の建具、便器、インテリア部材等が挙げられる。とくに光量の少ない室内用途での従来例の部材に比べて優れた機能を発現できるため、たとえば、建材として天井、壁、床、収納部材、窓への使用や、照明カバー、ランプ、障子、ふすま等の建具へ用いることが考慮される。
【００３６】
そこで以下に実施例を示し、さらに詳しく説明する。もちろん、以下の例によって発明が限定されることはない。
【００３７】
【実施例】
（比較例１）
メチルトリメトキシシラン１００重量部、テトラエトキシシラン１０重量部、オルガノシリカゾル（触媒化成社製：商品名ＯＳＣＡＬ１４３２）を９０重量部、ジメチルジメトキシシランを３０重量部、イソプロピルアルコールを１００重量部混合した後に、水を９０重量部添加し、攪拌後、６０℃で重量平均分子量約１５００に調整し、さらにメタノールを混合して固形分１０重量％の無機質塗料を得た。該塗料をガラス板に１００ｇ／ｍ2スプレー塗布し、風乾後、１５０℃で硬化処理を行い、機能性塗膜基材を作製した。
【００３８】
（比較例２）
メチルトリメトキシシラン１００重量部、テトラエトキシシラン１０重量部、オルガノシリカゾル（触媒化成社製：商品名ＯＳＣＡＬ１４３２）を９０重量部、ジメチルジメトキシシランを３０重量部、イソプロピルアルコールを１００重量部混合した後に、水を９０重量部添加し、攪拌後、６０℃で重量平均分子量約１５００に調整した。さらに、光触媒ゾル（石原産業製ＳＴＳ−０１）を上記のケイ素化合物固形分との重量比が、固形分／光触媒固形分＝５０／５０になるように添加した後、メタノールで固形分１０重量％になるように調整し、光触媒無機質塗料を得た。該塗料をガラス板に１００ｇ／ｍ2スプレー塗布し、風乾後、１５０℃で硬化処理を行い、機能性塗膜基材を作製した。
【００３９】
（参考例１）
メチルトリメトキシシラン１００重量部、テトラエトキシシラン１０重量部、オルガノシリカゾル（触媒化成社製：商品名ＯＳＣＡＬ１４３２）を９０重量部、ジメチルジメトキシシランを３０重量部、イソプロピルアルコールを１００重量部混合した後に、水を９０重量部添加し、攪拌後、６０℃で重量平均分子量約１５００に調整した。さらに、光触媒ゾル（石原産業製ＳＴＳ−０１）を上記のケイ素化合物固形分との重量比が、固形分／光触媒固形分＝５０／５０になるように添加した後、メタノールで固形分１０重量％になるように調整し、さらに、その１００重量部に対してモナザイト鉱物粉末（平均一次粒径２０μｍ）を０．５重量部添加することにより、機能性無機質塗料を得た。該塗料をガラス板に１００ｇ／ｍ ２ スプレー塗布し、風乾後、１５０℃で硬化処理を行い、機能性塗膜基材を作製した。
【００４０】
（参考例２）
モナザイト鉱石添加量を１重量部にする以外は、参考例１と同様にして、機能性塗膜基材を作製した。
【００４１】
（参考例３）
比較例１の無機塗料をガラス基板に塗布し、第一膜を作製後、参考例１の機能性無機質塗料を塗布し第二膜を形成し、機能性塗膜基材を得た。
【００４２】
（実施例１）
比較例１の無機質塗料１００部に、モナザイト鉱物粉末（平均一次粒径２０μｍ）を０．５部添加する以外は同様にして第一膜（下層）作成後、比較例２の光触媒無機質塗料を塗布し、第二膜（上層）を形成し、機能性塗膜基材を得た。
【００４３】
（評価）
上記、実施例、参考例及び比較例の塗布基材について、抗菌性、防汚性、マイナスイオン発生量、密着性の評価を行った。
【００４４】
＜抗菌性＞
抗菌性の評価法は、大腸菌の菌液を滴下し、その上に低密度ポリエチレンフィルムをかぶせ、密着させ、室温（２０〜２５℃）、暗条件（遮光）および明条件（蛍光灯１０００Ｌｘの光照射下）で保存し、２４時間後の生菌数を測定した。その結果、たとえば表１に示したように、比較例１では菌数はほとんど初期とかわらず、蛍光灯照射によって増大しているのが認められるのに対し、比較例２では光触媒の効果により、光を照射した場合、抗菌効果が得られたが、参考例１および２では、放射線放出鉱石配合が増加するほど、光照射下ではより顕著に菌数が減少し、また、暗所下でも、同様の、比較例２に比べてはるかに優れた抗菌効果を確認された。
【００４５】
【表１】
＜防汚性＞
防汚性の評価は、タバコのヤニの付着性と付着したヤニの光照射での分解性を色差変化を測定することでおこなった。タバコのヤニの付着方法は、タバコに火をつけ、その上に基板を設置し、３分間放置し、初期との色差を測定した。次に、それらの基材を蛍光灯照射５０００Ｌｘ下に設置し、色差変化を測定した。その結果、ヤニの付着度合いでは、比較例２に対して、参考例１および２において放射線放出材料が増えるほど、色差が低くなり、すなわち、ヤニ汚れがつきにくくなっていることが確認された。これは、放射線放出鉱石添加により、放射線での空気中の酸素、水分子をイオン化させ、とくにマイナスイオンを多く放出することで、プラスに帯電したタバコ中の粉塵、ヤニ成分を中和させ、基材表面へのヤニ成分の付着を低減させたためであると推定される。
【００４７】
次に、蛍光灯で光照射させた場合、比較例２に対し、参考例１から２へ放射線放出鉱石配合量が増えることにより、図１のように色差が低くなり、ヤニ汚れの分解が進むことがわかる。また色差の低減度合いが照射日数との相関で急になり、表２のとおりの分解係数に大きな変化が生じることがわかる。したがって、放射線放出鉱石の添加により、光触媒機能を向上させることができ、ヤニの分解性能が大きくなったことが確認された。
【００４８】
【表２】
（密着性）
次に、密着性の評価はＪＩＳ−Ｋ５４００の煮沸試験での評価点で行った。
【００５０】
その結果、表３のとおり、モナザイト鉱石を配合した塗膜は密着性が比較例２と同等もしくは少し低下するが、比較例３のように下地層による多層とする場合には密着性は良好となり、そして実施例１のように、第一膜（下層）にモナザイト鉱石を配合後、第二膜（上層）を形成することにより、第一膜表面の凹凸性が増し、第一膜との密着性が向上し、さらに、表面の第二膜の平滑性、耐久性が向上することが確認された。
【００５１】
【表３】
【発明の効果】
以上詳しく説明したとおり、この出願の発明によって、暗所での光触媒効果の発揮や、表面に露出していない光触媒の機能の引き出しを充分なものとし、放射線作用により光触媒機能を向上させ、長期間、優れた防汚性を保持し、暗所でも抗菌性を発現、保持することができる。さらに空気中の水分を励起し、マイナスイオンを放出し、防汚性を向上することができる。また塗料としても、塗膜密着性、耐久性等の特性において実用的に満足できるものが提供され、さらには、第一膜に放射線放出鉱石を形成し、第二膜に光触媒無機塗料を形成することで、優れた耐久性を示す塗膜が得られる。
【図面の簡単な説明】
【図１】ヤニ汚れの分解性能の試験結果を例示した図である。[0001]
BACKGROUND OF THE INVENTION
The invention of this application relates to a functional inorganic coating material and a coating structure thereof. More specifically, the invention of this application is useful in the manufacture of building materials and the like, and has a new anti-fouling property, antibacterial property, deodorizing property, and good coating film adhesion and durability. The present invention relates to a functional inorganic paint having a composition and a coating structure using the same.
[0002]
[Prior art]
Conventionally, it is known to form a coating film containing a photocatalyst such as titanium oxide as a surface treatment of building materials such as exterior materials and interior members, and various proposals for the formation of a coating film containing this photocatalyst. Is also made.
[0003]
Photocatalysts generate radicals when irradiated with light, and these radicals have the effect of decomposing organic matter. Therefore, materials that have a photocatalyst-containing layer formed on the surface of the substrate include dirt components in the air such as exhaust gas and lavaco components. Functions such as antifouling properties for decomposing odors, deodorizing properties for degrading malodorous components such as aldehydes, VOCs, ammonia, mercaptans, and antibacterial properties that prevent the generation of bacterial components such as Escherichia coli and Staphylococcus aureus are expected. Surface treatments using such photocatalysts have already been applied to building materials. For example, paints, coating materials with dispersed photocatalysts, mirrors coated with them, glass, boards, sheets, tiles, etc. have been commercialized. ing.
[0004]
However, at present, in the coating film in which the photocatalyst is blended and dispersed, the surface of the photocatalyst is coated with other paint components such as a binder and a pigment, or is fixed inside the paint, and the photocatalyst is not sufficiently exposed on the surface. Furthermore, the actual situation is that the photocatalytic function such as the blended titanium oxide is not sufficiently expressed.
[0005]
For this reason, the realization of the coating composition which can draw out the function of the photocatalyst which is not exposed on the surface and has a photocatalytic function even in a dark place has been desired.
[0006]
In response to such a problem, by incorporating a natural ore containing a small amount of radiation in a base material or paint together with a photocatalyst, the photocatalyst is excited by radiation even in a state where no light is irradiated, and even in a dark place. There has been proposed (Patent Document 1) that the photocatalytic effect can be exhibited and the function of the photocatalyst not exposed on the surface can be extracted.
[0007]
However, even in this proposal, the photocatalytic effect in the dark is not sufficiently exhibited, and the function of the photocatalyst not exposed on the surface is not sufficient, and the paint is also practical in terms of coating adhesion, durability, etc. There was a problem that it was not satisfactory.
[0008]
[Patent Document 1]
Japanese Patent Laid-Open No. 2000-167397
[Problems to be solved by the invention]
Therefore, the invention of this application solves the above-mentioned problems and considers the composition characteristics as a paint, thereby sufficiently exerting the photocatalytic effect in a dark place and drawing out the function of the photocatalyst not exposed on the surface. In addition, as a coating material, it is an object to provide a new coating material that can be practically satisfied in properties such as coating film adhesion and durability, and a new coating composition using the same.
[0010]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present invention firstly includes, as a coating film forming component, (A) a natural ore powder that emits radiation and (C) a coating for a lower layer containing a silicon compound, and a coating film. As a forming component, (B) a photocatalyst and (C) a coating material for an upper layer containing a silicon compound, and a coating film formed by applying a coating material for a lower layer and a coating material for an upper layer on a substrate is the above-mentioned (A) ( provides functionality inorganic coating, characterized in that the one formed only by Ingredients of B) (C).
[0011]
And secondly, the weight ratio of the components (A), (B), and (C) that form the coating film is 1 to 10 parts of natural ore powder that emits radiation (A) as a total amount of 100 parts, (B) The functional inorganic coating material is characterized in that the solid content of the photocatalyst is 10 to 80 parts and the solid content of the (C) silicon compound is 20 to 80 parts.
[0012]
Thirdly, (A) a natural ore powder that emits radiation is a functional inorganic coating material that emits radiation of 50 Bq / g or less, and fourth, (A ) The natural ore powder that emits radiation is a functional inorganic paint characterized in that (B) 5% by weight or more of the total amount of both is (B) photocatalyst solid content. ) Silicon compounds include colloidal silica and the following formula: R 2 n Si (OR 1 ) 4-n
(N represents an integer of 0 to 3, R 1 and R 2 each represent the same or different hydrocarbon group)
A functional inorganic coating material characterized in that it is prepared by hydrolysis or polycondensation of one or more compounds represented by the formula:
[0013]
Furthermore the invention of this application, the sixth, the provides a coated structure in which any of the paint is characterized in that it is formed by applying, to the seventh, the on the substrate (A) after the lower layer was formed by coating the lower layer coating material containing the component (C), characterized in that the upper layer is formed by coating a layer-coating material containing the (B) component (C) Eighth, the coating composition is characterized in that a coating film made of a paint containing (C) a silicon compound component is formed as an underlayer without containing the components (A) and (B). Provide a construct.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The invention of this application has the features as described above, and an embodiment thereof will be described below.
[0015]
Examples of the radiation-emitting natural ore that emits radiation of the film-forming component (A) constituting the functional inorganic paint of the invention of this application include, for example, Davide ore, blannelite, senurite ore, nymphite, and lincayurite , Carnotite, Tsuyamun stone, Matachamun stone, Franceville stone, Tall stone, Coffin stone, Samarsky stone, Thorium stone, Trogamite, Monazite and the like. The powder as the component (A) is obtained by pulverizing these ores into a fine powder, and the primary particle size is generally 200 μm or less. A thing with a diameter of 50 micrometers or less is preferable. In addition, the radiation emission level must naturally be a level that does not adversely affect the human body, and is desirably a material of 50 becquerels / g or less.
[0016]
These materials have a feature that negative ions composed of associated substances such as oxygen and water molecules in the air can be generated by the effect of radiation.
[0017]
Examples of the photocatalyst of component (B) include titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, iron oxide, and niobium oxide. One type may be used, or two or more types may be used in combination. Good. The primary particle size of the photocatalyst is generally 100 μm or less, but is preferably 50 μm or less.
[0018]
Moreover, the photocatalyst may carry a metal. Although it does not specifically limit as a metal to carry | support, Gold, silver, copper, tellurium, zinc, nickel, cobalt, platinum, ruthenium, palladium, rhodium, rhenium etc. are mentioned, Only 1 type or 2 or more types is used together. Also good. By supporting the metal, it is possible to promote charge separation of the photocatalyst and to generate a new excitation level by supporting at the nano level, thereby improving the activity of the photocatalyst. The carrier for supporting the metal may be particles such as the above oxide particles, silica, alumina and the like. The size of these primary particles is generally 200 μm or less, and preferably about the same as described above. And it is preferable that it is 0.1 to 5 weight% as a metal load. The metal loading method is not particularly limited, and examples thereof include an immersion method, a spray method, and a photoreduction method.
[0019]
The photocatalyst is blended in the form of powder or sol, and the ratio of the photocatalyst to the solid content of the entire paint is preferably 10% or more and 80% or less. The photocatalytic function is exhibited as the ratio increases, but if the ratio is too high, the binder ratio decreases and the coating film strength decreases.
[0020]
As the binder component, it is necessary to use a binder that is difficult to be decomposed by a photocatalyst. In the invention of this application, a silicon compound as the component (C) is used.
[0021]
Examples of the silicon compound include colloidal silica and the general formula as described above:
R 2 n Si (OR 1 ) 4-n
What was prepared from the compound represented by these is used suitably (n is an integer of 0 to 3).
[0022]
Wherein reference numeral R 1 denotes a coal hydrocarbon group, among them, more preferably, mainly an alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- It is preferably any of a butyl group, an isobutyl group, and a tertiary butyl group.
[0023]
Further, R 2 is also shown the coal hydrocarbon group, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms. For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, alkyl group such as octyl group, aryl group such as phenyl group, alkenyl group such as vinyl group, chloromethyl group, chloropropyl Groups, halogen-substituted hydrocarbon groups such as trifluoropropyl group, substituted hydrocarbon groups such as methacryloxypropyl group and glycidoxypropyl group.
[0024]
Examples of the silicon compound having R 1 and R 2 as described above include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane when n = 0, and methyltrimethoxy when n = 1. Organotrialkoxysilanes such as silane, methyltriethoxysilane, methyltripropoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane, and dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldi when n = 2 Examples include diorganodialkoxysilanes such as ethoxysilane, and in the case of n = 3, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, and the like.
[0025]
A suitable silicon compound of component (C) was prepared by diluting colloidal silica and one or more of these compounds with a solvent, and performing hydrolysis and polycondensation using water or a catalyst as a curing agent. Can be. For example, it is prepared from a composition having a weight ratio of at least 20 to 200 parts of tetraalkoxide and colloidal silica, 30 to 100 parts of organotrialkoxysilane, and 0 to 60 parts of diorganodialkoxysilane, and is weight average in terms of polystyrene. The molecular weight is adjusted to 900 or more.
[0026]
The functional inorganic coating of the invention of this application includes, for example, (A) a natural ore powder that emits radiation and (C) a coating for a lower layer containing a silicon compound, as exemplified above .
(B) a coating for an upper layer containing a photocatalyst and (C) a silicon compound ,
For lower layer paint and upper layer paint coating film formed by coating on a substrate is characterized to Rukoto and those formed only by Ingredient of the (A) (B) (C ). From this, when the coating film has a multilayer structure, for example, it may have a multilayer structure of (A) (C) component-containing paint and (B) (C) component-containing paint, or with these paints. to be a multilayer configuration by paint containing Ingredients of (a) (B) (C ).
[0027]
The preparation as a paint is not particularly limited as a dispersion solvent, but water, alcohols such as methanol, ethanol and isopropyl alcohol, ethylene glycols and the like are used. Xylene, ethyl acetate, butyl acetate and the like can also be used. Moreover, when making it harden | cure at normal temperature without heating, a curing catalyst can also be added. Although it does not specifically limit as a catalyst, When a polycondensation of siloxane is advanced, a curing catalyst can be used.
[0028]
If necessary, pigments, dyes, dispersants, thickeners, etc. may be added to improve dispersibility, stability and color, antistatic agents, antifungal materials, antibacterial agents, etc. It may be added.
[0029]
Regarding the blending ratio of the above components (A), (B) and (C) as coating film forming components, these components are, as a weight ratio, 1 to 10 parts of the radiation emitting ore powder of (A), and the photocatalytic material of (B). Solid content 10-80 parts, (C) silicon compound solid content 20-80 parts, provided that (A) + (B) + (C) = 100 parts. Even when the (A) and (C) component paints and the (B) and (C) component paints are used separately, it is preferable to achieve the above ratio as a whole. In any case, the radiation-emitting ore powder (A) is preferably used in an amount of 5% by weight or more based on the total amount of the solid component of the photocatalyst (B). The reason is that the radiation-emitting ore is blended to excite the photocatalyst, and the function of the photocatalyst can be improved by using 5% or more of the photocatalyst.
[0030]
Further, in the above blending, if the ratio of the silicon compound is too small, adhesion and durability as a coating film cannot be obtained, and if it is excessive, it is difficult to improve the function of the photocatalyst.
[0031]
The coating method for forming the coating film structure using the paint of the invention of this application is not particularly limited, but spraying, brushing, bar coater, spin coater, dipping, roll Various methods such as a coater and a flow coater are used. Further, if necessary, the coating film can be cured by heat treatment, or curing can be performed at room temperature by using a curing catalyst. When proceeding with curing, it is preferable to cure at a temperature of 200 ° C. or lower.
[0032]
The thickness of the coating film is not particularly limited, but is preferably about 50 μm or less and about 0.1 to 20 μm, for example, so that the coating film can be stably, closely adhered and held for a long time and cracks and peeling do not occur.
[0033]
The base material to be coated is not particularly limited, but is a metal base material such as aluminum, iron, stainless steel, tinplate, and alloys thereof, wood base material such as wood, plywood, MDF, particle board, etc., FRP, artificial Plastic base materials such as marble and resin molded products, glass, enamel, ceramics, gypsum board, calcium silicate board, rock wool board, various cement boards, clay boards, ceramic tiles, slate, inorganic base materials, and other sheets , Paper, fiber, non-woven fabric, and the like, and the type is not particularly limited. Furthermore, those obtained by applying organic coating to those substrates may be used. In addition, in the case of organic materials such as wood substrates, resin substrates, sheets, etc., once the coating material not containing a photocatalyst is applied, the coating material containing the photocatalyst is applied to prevent deterioration of the substrate due to the photocatalyst. Can do. For example, after forming a coating film containing only the silicon compound (C) as the first coating layer of the base layer, the second coating layer depends on the components (A), (B) and (C). It is also effective to form a functional coating film.
[0034]
Further, as the lower layer, after arranging the coating film formed by the lower layer coating material containing a silicon compound of the natural ore that emits radiation traces (C) of (A), as the upper layer (B) disposing a coating film formed by layer-coating material containing a silicon compound of a photocatalyst (C). Even in such a case, it is preferable that the ratio of the radiation-emitting ore (A) to the photocatalyst (B) is 5% or more as described above for the entire paint forming the coating film. When (A) and (B) are divided into the respective coating film layers, the first coating film layer becomes more uneven by adding ore powder than when it is not added, and the adhesion with the second film is improved. Further, the smoothness and durability of the second coating layer on the surface are improved.
[0035]
The building materials and articles formed with the functional inorganic coating film of the invention of this application as described above can be used for outdoor and indoor members. For example, outdoor materials include exterior materials, tiles, rain gutters, gates, fences, doors, windows, and peripheral members thereof, and indoor materials include ceilings, walls, floors, storage members, construction materials, kitchens , Toilets, washbasins, bathrooms, windows, and their use for peripheral members, lighting covers, lamps, shoji, bran and other fittings, toilets, interior members, and the like. In particular, it can exhibit superior functions compared to conventional materials used in indoor applications where the amount of light is low. For example, it can be used as a building material for ceilings, walls, floors, storage materials, windows, lighting covers, lamps, shoji, bran It is considered to be used for joinery such as.
[0036]
Therefore, an example will be shown below and will be described in more detail. Of course, the invention is not limited by the following examples.
[0037]
【Example】
(Comparative Example 1)
After mixing 100 parts by weight of methyltrimethoxysilane, 10 parts by weight of tetraethoxysilane, 90 parts by weight of organosilica sol (manufactured by Catalyst Kasei Co., Ltd .: trade name OSCAL1432), 30 parts by weight of dimethyldimethoxysilane, and 100 parts by weight of isopropyl alcohol, 90 parts by weight of water was added, and after stirring, the weight average molecular weight was adjusted to about 1500 at 60 ° C., and methanol was further mixed to obtain an inorganic paint having a solid content of 10% by weight. The coating was applied to a glass plate by spraying 100 g / m 2 , air-dried, and cured at 150 ° C. to prepare a functional coating film substrate.
[0038]
(Comparative Example 2)
After mixing 100 parts by weight of methyltrimethoxysilane, 10 parts by weight of tetraethoxysilane, 90 parts by weight of organosilica sol (manufactured by Catalyst Kasei Co., Ltd .: trade name OSCAL1432), 30 parts by weight of dimethyldimethoxysilane, and 100 parts by weight of isopropyl alcohol, 90 parts by weight of water was added, and after stirring, the weight average molecular weight was adjusted to about 1500 at 60 ° C. Furthermore, after adding a photocatalyst sol (STS-01 manufactured by Ishihara Sangyo Co., Ltd.) such that the weight ratio of the above-mentioned silicon compound solids is solids / photocatalyst solids = 50/50, the solids content is 10% by weight with methanol. The photocatalyst inorganic coating material was obtained. The coating was applied to a glass plate by spraying 100 g / m 2 , air-dried, and cured at 150 ° C. to prepare a functional coating film substrate.
[0039]
( Reference Example 1)
After mixing 100 parts by weight of methyltrimethoxysilane, 10 parts by weight of tetraethoxysilane, 90 parts by weight of organosilica sol (manufactured by Catalyst Kasei Co., Ltd .: trade name OSCAL1432), 30 parts by weight of dimethyldimethoxysilane, and 100 parts by weight of isopropyl alcohol, 90 parts by weight of water was added, and after stirring, the weight average molecular weight was adjusted to about 1500 at 60 ° C. Furthermore, after adding a photocatalyst sol (STS-01 manufactured by Ishihara Sangyo Co., Ltd.) such that the weight ratio of the above-mentioned silicon compound solids is solids / photocatalyst solids = 50/50, the solids content is 10% by weight with methanol. Further, by adding 0.5 part by weight of monazite mineral powder (average primary particle size 20 μm) to 100 parts by weight of the mixture, a functional inorganic paint was obtained. The paint was applied to a glass plate by 100 g / m 2 spray, air-dried, and then cured at 150 ° C. to prepare a functional coating film substrate.
[0040]
( Reference Example 2)
A functional coating substrate was prepared in the same manner as in Reference Example 1 except that the amount of monazite ore added was 1 part by weight.
[0041]
( Reference Example 3)
The inorganic coating material of Comparative Example 1 was applied to a glass substrate to produce a first film, and then the functional inorganic coating material of Reference Example 1 was applied to form a second film to obtain a functional coating film substrate.
[0042]
(Example 1 )
The first film (lower layer) was prepared in the same manner except that 0.5 part of monazite mineral powder (average primary particle size 20 μm) was added to 100 parts of the inorganic paint of Comparative Example 1, and then the photocatalytic inorganic paint of Comparative Example 2 was applied. And the 2nd film | membrane (upper layer) was formed and the functional coating-film base material was obtained.
[0043]
(Evaluation)
About the application base material of the said Example , a reference example, and a comparative example, antibacterial property, antifouling property, negative ion generation amount, and adhesiveness were evaluated.
[0044]
<Antimicrobial properties>
The antibacterial evaluation method involves dropping a bacterial solution of Escherichia coli, covering it with a low-density polyethylene film, bringing it into close contact, room temperature (20 to 25 ° C.), dark conditions (light-shielding), and bright conditions (fluorescent light of 1000 Lx). The number of viable bacteria was measured after 24 hours. As a result, for example, as shown in Table 1, in Comparative Example 1, the number of bacteria is almost the same as the initial stage, but it is recognized that the number of bacteria is increased by irradiation with a fluorescent lamp, whereas in Comparative Example 2, due to the effect of the photocatalyst, When irradiated with light, an antibacterial effect was obtained, but in Reference Examples 1 and 2, as the radiation-emitting ore composition increased, the number of bacteria decreased more significantly under light irradiation, and even in the dark, The same antibacterial effect far superior to that of Comparative Example 2 was confirmed.
[0045]
[Table 1]
<Anti-fouling>
The antifouling property was evaluated by measuring the change in color difference of the adhesion of cigarettes and the degradation of the adhered spears by light irradiation. As a method for attaching the cigarette to the cigarette, the cigarette was lit, a substrate was placed on the cigarette, allowed to stand for 3 minutes, and the color difference from the initial stage was measured. Next, those base materials were placed under fluorescent lamp irradiation 5000 Lx, and the color difference change was measured. As a result, it was confirmed that the degree of adhesion of the stain became lower as the radiation emitting material increased in Reference Examples 1 and 2 than in Comparative Example 2, so that the color difference was lower, that is, the stain was less likely to be attached. This is due to the addition of radiation-emitting ore, which ionizes oxygen and water molecules in the air with radiation, and in particular releases many negative ions to neutralize dust and dust components in positively charged tobacco. This is presumably because the adhesion of the spider component to the surface of the material was reduced.
[0047]
Next, when light is irradiated with a fluorescent lamp, the amount of radiation-emitting ore is increased from Reference Example 1 to Reference Example 1 with respect to Comparative Example 2, so that the color difference is reduced as shown in FIG. I understand that. In addition, it can be seen that the degree of color difference reduction becomes steep due to the correlation with the number of irradiation days, and a large change occurs in the decomposition coefficient as shown in Table 2. Therefore, it was confirmed that the addition of the radiation-emitting ore can improve the photocatalytic function and increase the decomposition performance of the spear.
[0048]
[Table 2]
(Adhesion)
Next, evaluation of adhesiveness was performed by the evaluation point in the boiling test of JIS-K5400.
[0050]
As a result, as shown in Table 3, the adhesion of the monazite ore blended is similar to or slightly lower than that of Comparative Example 2, but the adhesion is good when it is a multi-layered base layer as in Comparative Example 3. And, as in Example 1 , by forming the second film (upper layer) after blending the monazite ore in the first film (lower layer) , the unevenness of the surface of the first film is increased, and the first film (close layer) is in close contact with the first film. As a result, it was confirmed that the smoothness and durability of the second film on the surface were improved.
[0051]
[Table 3]
【The invention's effect】
As described above in detail, the invention of this application makes it possible to sufficiently exhibit the photocatalytic effect in the dark and to draw out the function of the photocatalyst not exposed on the surface, improve the photocatalytic function by radiation action, It retains excellent antifouling properties and can exhibit and retain antibacterial properties even in the dark. Furthermore, it can excite moisture in the air, release negative ions, and improve antifouling properties. In addition, a coating material that is practically satisfactory in properties such as coating film adhesion and durability is provided. Further, a radiation-emitting ore is formed on the first film, and a photocatalytic inorganic coating is formed on the second film. Thereby, the coating film which shows the outstanding durability is obtained.
[Brief description of the drawings]
FIG. 1 is a diagram exemplifying a test result of disassembly performance of spear dirt.
Claims (8)
塗膜形成成分として、（Ｂ）光触媒および（Ｃ）ケイ素化合物を含有する上層用塗料とよりなり、
下層用塗料および上層用塗料を基材上に塗布して形成された塗膜が前記（Ａ）（Ｂ）（Ｃ）の成分のみによって形成されたものとすることを特徴とする機能性無機質塗料。As a coating film forming component, (A) a natural ore powder that emits radiation and (C) a coating for a lower layer containing a silicon compound;
The coating film forming component comprises (B) a photocatalyst and (C) a coating for an upper layer containing a silicon compound ,
Functional inorganic, characterized in that it is assumed that the coating film formed of the lower layer paint and upper layer paint is applied onto the substrate is formed by only Ingredient of the (A) (B) (C ) paint.
Ｒ２ ｎＳｉ（ＯＲ１）４−ｎ
（ｎは０〜３のうちの整数を示し、Ｒ１およびＲ２は、各々、同一または別異の炭化水素基を示す）
で表わされる１種以上の化合物が加水分解もしくは重縮合されて調製されたものであることを特徴とする請求項１ないし４のいずれかの機能性無機質塗料。(C) The silicon compound is colloidal silica and the following formula: R 2 n Si (OR 1 ) 4-n
(N represents an integer of 0 to 3, R 1 and R 2 each represent the same or different hydrocarbon group)
The functional inorganic coating material according to claim 1, wherein the functional inorganic coating material is prepared by hydrolysis or polycondensation of one or more compounds represented by the formula:
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| KR100765382B1 (en) * | 2006-07-18 | 2007-10-12 | (주)신우상역 | Structure of coating layer for heat-cooker |
| JP4730400B2 (en) | 2007-10-09 | 2011-07-20 | 住友化学株式会社 | Photocatalyst dispersion |
| JP5082950B2 (en) | 2008-03-13 | 2012-11-28 | 住友化学株式会社 | Method for decomposing volatile aromatic compounds |
| JP2010115635A (en) | 2008-06-05 | 2010-05-27 | Sumitomo Chemical Co Ltd | Photocatalyst dispersion, its method of manufacturing the same and application thereof |
| JP2011005475A (en) | 2009-05-29 | 2011-01-13 | Sumitomo Chemical Co Ltd | Photocatalyst dispersion liquid and photocatalyst functional product using the same |
| JP2011224534A (en) | 2009-09-16 | 2011-11-10 | Sumitomo Chemical Co Ltd | Photocatalyst composite and photocatalyst functional product using the same |
| EP2508257A4 (en) | 2009-12-01 | 2013-11-06 | Sumitomo Chemical Co | Antiviral agent, and antiviral agent functional product using same |
| JP2011136325A (en) | 2009-12-01 | 2011-07-14 | Sumitomo Chemical Co Ltd | Method for producing liquid dispersion of noble metal-supporting photocatalyst particles, liquid dispersion of noble metal-supporting photocatalyst particles, hydrophilizing agent, and photocatalytic functional product |
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