JP2002348525A - Emulsion coating containing titanium oxide having photocatalytic activity, coating method using the same and its coated film - Google Patents
Emulsion coating containing titanium oxide having photocatalytic activity, coating method using the same and its coated filmInfo
- Publication number
- JP2002348525A JP2002348525A JP2001157988A JP2001157988A JP2002348525A JP 2002348525 A JP2002348525 A JP 2002348525A JP 2001157988 A JP2001157988 A JP 2001157988A JP 2001157988 A JP2001157988 A JP 2001157988A JP 2002348525 A JP2002348525 A JP 2002348525A
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- acrylic resin
- titanium oxide
- colloidal silica
- coating
- 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.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 124
- 238000000576 coating method Methods 0.000 title claims abstract description 100
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000011248 coating agent Substances 0.000 title claims abstract description 85
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 41
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 94
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 94
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000003973 paint Substances 0.000 claims description 93
- 239000008119 colloidal silica Substances 0.000 claims description 89
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 79
- 229920001577 copolymer Polymers 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 25
- 238000007334 copolymerization reaction Methods 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 6
- 230000001747 exhibiting effect Effects 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 55
- 239000000126 substance Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 230000003373 anti-fouling effect Effects 0.000 description 14
- 239000011941 photocatalyst Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 239000010454 slate Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 7
- 238000010422 painting Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- -1 for example Chemical compound 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 102100028175 Abasic site processing protein HMCES Human genes 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 101001006387 Homo sapiens Abasic site processing protein HMCES Proteins 0.000 description 1
- 101000879758 Homo sapiens Sjoegren syndrome nuclear autoantigen 1 Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 102000003729 Neprilysin Human genes 0.000 description 1
- 108090000028 Neprilysin Proteins 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 102100037330 Sjoegren syndrome nuclear autoantigen 1 Human genes 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、機能性塗料に関す
るものであり、特に光触媒を含有して汚れを分解する防
汚性のある塗膜となる塗料、その塗装方法および塗膜に
関するものである。具体的には、本発明は、光触媒能を
有する酸化チタンを含有するエマルション塗料、その塗
装方法およびその塗膜に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a functional paint, and more particularly to a paint which contains a photocatalyst and becomes an antifouling coating which decomposes dirt, a coating method and a coating. . More specifically, the present invention relates to an emulsion paint containing titanium oxide having photocatalytic ability, a method for applying the same, and a coating film thereof.
【０００２】[0002]
【従来の技術】酸化チタンを代表とする紫外線に感応し
て例えば有機物を分解する光触媒は、ようやく実用化さ
れはじめ、それを使った応用製品、例えば脱臭抗菌装
置、エアクリーナー、消臭繊維および塗料などが、様々
な分野で提案されている。その中でも塗料は、汎用性が
あるだけに開発が盛んである。光触媒となる酸化チタン
自体は、通常固体の粉末であるから、基本的には支持体
への付着力に乏しい。酸化チタンと被分解物との接触面
積を上げるためにも、また感応する紫外線の照射面積を
上げるためにも、酸化チタンを支持体へ広くかつ強固に
付着せしめる接着技術の開発が、応用のためには最も重
要である。2. Description of the Related Art Photocatalysts such as titanium oxide, which decompose organic substances in response to ultraviolet rays, are finally being put into practical use, and applied products using them, such as deodorizing antibacterial devices, air cleaners, deodorizing fibers and paints. Have been proposed in various fields. Among them, paint has been actively developed because of its versatility. Since titanium oxide itself as a photocatalyst is usually a solid powder, it has basically poor adhesion to a support. In order to increase the contact area between titanium oxide and decomposed substances, and to increase the sensitive UV irradiation area, the development of an adhesive technology that allows titanium oxide to be widely and firmly adhered to the support has been developed. Is the most important.
【０００３】光触媒はC−C結合を分解することができる
から、有機系の接着剤は、光触媒の作用で容易に分解し
て薄膜が壊れ、付着能力を失って支持体から剥がれ落
ち、早期に光触媒の機能が失われるのが常であった。そ
こで、接着剤として結合エネルギーの高い無機系接着剤
を使用した塗料が検討されている。しかし無機系接着剤
は、薄膜化が困難でかつ接着力が弱く、分解耐久性には
優れるものの塗膜や塗装体としての初期物性が貧弱であ
る欠点がある。これらの問題点があるために光触媒を含
有する塗料は、機能は認められながら応用展開が遅れて
いるのが実状である。Since a photocatalyst can decompose a C—C bond, an organic adhesive is easily decomposed by the action of a photocatalyst to break a thin film, lose its adhering ability, and peel off from a support. Photocatalytic function was usually lost. Therefore, paints using an inorganic adhesive having a high binding energy as an adhesive have been studied. However, inorganic adhesives have difficulty in forming a thin film, have low adhesive strength, and have excellent decomposition durability, but have a drawback that initial physical properties as a coating film or a coated body are poor. Due to these problems, paints containing a photocatalyst have been recognized for their function but their application has been delayed.
【０００４】[0004]
【発明が解決しようとする課題】したがって、本発明の
第１の課題は、上記の問題点を克服した防汚性のある塗
膜となる塗料を提供することである。次に、本発明の第
２の課題は、上記の問題点を有しない防汚性のある塗膜
となる塗料の塗装方法を提供することである。さらに、
本発明の第３の課題は、上記の問題点を有しない防汚性
のある塗膜を提供することである。SUMMARY OF THE INVENTION Accordingly, it is a first object of the present invention to provide a paint which becomes an antifouling coating film overcoming the above-mentioned problems. Next, a second object of the present invention is to provide a method of applying a coating material that becomes a stain-resistant coating film that does not have the above-mentioned problems. further,
A third object of the present invention is to provide an antifouling coating film which does not have the above problems.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、光触媒能
を有する酸化チタンをよく分散し、よく薄膜化し、支持
体への付着力が高く、同時にその耐久性が高い接着剤を
見出し、本発明に至った。同時にまた、実塗装作業にお
いて重要な要件を解決した。すなわち、本発明者等は、
酸化チタンをコロイダルシリカ共重合アクリル樹脂エマ
ルションへ配合することにより、塗装作業において無用
の危険物や有害物を環境に放出しない水系塗料となし、
塗膜の硬化にあっては特別の加熱を必要としない常温硬
化型塗料となし、作業前に他の薬剤を添加しない一液型
塗料となし、厚膜塗装に当たり重ね塗り不要の固形分の
高い作業性に優れる塗料となし得た。かくして、上で述
べた課題は、本発明に従って解決することができる。以
下、これについて説明する。Means for Solving the Problems The present inventors have found an adhesive which disperses titanium oxide having a photocatalytic property well, forms a thin film, has high adhesion to a support, and at the same time has high durability. The present invention has been reached. At the same time, it solved important requirements in actual painting work. That is, the present inventors,
By blending titanium oxide with colloidal silica copolymer acrylic resin emulsion, there is no water-based paint that does not release unnecessary hazardous or harmful substances to the environment during painting work.
There is no room-temperature-curing paint that does not require special heating when curing the coating film, and there is no one-component paint that does not add other chemicals before work. A paint with excellent workability was obtained. Thus, the above-mentioned problem can be solved according to the present invention. Hereinafter, this will be described.
【０００６】まず、上で述べた第１の課題は、本発明に
係るエマルション塗料によって解決することができる。
すなわち、上で述べた第１の課題は、本発明に従って、 １．光触媒能を有する酸化チタンを、コロイダルシリカ
共重合アクリル樹脂エマルションへ配合してなる、エマ
ルション塗料。 ２．コロイダルシリカ共重合アクリル樹脂エマルション
と、それに分散した光触媒能を有する酸化チタンとを含
有する、エマルション塗料。 ３．該コロイダルシリカ共重合アクリル樹脂エマルショ
ンが、無水ケイ酸とアクリル系モノマーとのエマルショ
ン共重合によって得られるエマルションである、上記１
または２に記載のエマルション塗料。 ４．該光触媒能を有する酸化チタン１００重量部あた
り、５０〜４０００重量部、好ましくは２００〜２００
０重量部のコロイダルシリカ共重合アクリル樹脂固形分
を含有する、上記１〜３のいずれか１つに記載のエマル
ション塗料。 ５．該光触媒能を有する酸化チタンが、１〜１８０ｎ
ｍ、好ましくは３〜５０ｎｍの平均粒径を有する、上記
１〜４のいずれか１つに記載のエマルション塗料。 ６．該コロイダルシリカ共重合アクリル樹脂エマルショ
ンが、アクリル系モノマー１００重量部を、２０〜５０
０重量部、好ましくは３０〜４００重量部の無水ケイ酸
とエマルション共重合することによって得られるエマル
ションである、上記１〜５のいずれか１つに記載のエマ
ルション塗料。 ７．該無水ケイ酸が５〜８０ｎｍ、好ましくは２０〜６
０ｎｍの平均粒径を有する粒子である、上記３または６
に記載のエマルション塗料。 ８．該コロイダルシリカ共重合アクリル樹脂固形分が、
該コロイダルシリカ共重合アクリル樹脂エマルションの
５〜７０重量％、好ましくは２０〜５０重量％である、
上記１〜７のいずれか１つに記載のエマルション塗料。
によって、解決することができる。First, the first problem described above can be solved by the emulsion paint according to the present invention.
That is, the first problem described above is achieved according to the present invention by: An emulsion paint comprising titanium oxide having photocatalytic ability mixed with a colloidal silica copolymer acrylic resin emulsion. 2. An emulsion paint containing a colloidal silica copolymerized acrylic resin emulsion and titanium oxide having photocatalytic activity dispersed therein. 3. The colloidal silica copolymer acrylic resin emulsion is an emulsion obtained by emulsion copolymerization of silicic anhydride and an acrylic monomer.
Or the emulsion paint according to 2. 4. 50 to 4000 parts by weight, preferably 200 to 200 parts by weight, per 100 parts by weight of the titanium oxide having photocatalytic ability.
The emulsion paint according to any one of the above items 1 to 3, which contains 0 parts by weight of a colloidal silica copolymerized acrylic resin solid content. 5. The titanium oxide having the photocatalytic ability is 1 to 180 n
m, preferably 3 to 50 nm, the emulsion paint according to any one of the above 1 to 4. 6. The colloidal silica copolymerized acrylic resin emulsion was used in an amount of 20 to 50 parts by weight of an acrylic monomer.
The emulsion paint according to any one of the above 1 to 5, which is an emulsion obtained by emulsion copolymerization with 0 parts by weight, preferably 30 to 400 parts by weight of silicic anhydride. 7. The silicic acid anhydride is 5 to 80 nm, preferably 20 to 6 nm.
3 or 6 above, which is a particle having an average particle size of 0 nm.
3. The emulsion paint according to item 1. 8. The colloidal silica copolymer acrylic resin solid content,
5 to 70% by weight, preferably 20 to 50% by weight of the colloidal silica copolymerized acrylic resin emulsion,
The emulsion paint according to any one of the above 1 to 7.
Can solve it.
【０００７】次に、上で述べた第２の課題は、本発明に
係る塗装方法によって解決することができる。すなわ
ち、上で述べた第２の課題は、本発明に従って、 ９．上記１〜８のいずれか１つに記載のエマルション塗
料を塗布しそして乾燥または焼き付けすることによっ
て、塗膜を形成することを特徴とする塗装方法。 １０．コロイダルシリカ共重合アクリル樹脂エマルショ
ンを含有し、かつ光触媒能を有する酸化チタンを含有し
ないエマルション塗料を塗布しそして乾燥または焼き付
けすることによって、下地を形成し、次いで、上記１〜
８のいずれか１つに記載のエマルション塗料を、下地の
上に塗布しそして乾燥または焼き付けすることによっ
て、下地の上に、塗膜を形成することを特徴とする塗装
方法。によって解決することができる。Next, the above-mentioned second problem can be solved by the coating method according to the present invention. That is, the above-mentioned second problem is solved according to the present invention. A coating method, wherein a coating film is formed by applying the emulsion paint described in any one of the above items 1 to 8, followed by drying or baking. 10. A base is formed by applying an emulsion paint containing a colloidal silica copolymerized acrylic resin emulsion and not containing titanium oxide having photocatalytic ability and drying or baking,
A coating method, wherein a coating film is formed on a base by applying the emulsion paint according to any one of the above items 8 on the base and drying or baking. Can be solved by
【０００８】さらに、上で述べた第３の課題は、本発明
に係る塗膜によって解決することができる。すなわち、
上で述べた第３の課題は、本発明に従って、 １１．上記９または１０に記載の塗装方法によって形成
した塗膜。 １２．コロイダルシリカ共重合アクリル樹脂と、それに
分散した光触媒能を有する酸化チタンを含有する塗膜。 １３．光触媒能を有する酸化チタンを含有しないコロイ
ダルシリカ共重合アクリル樹脂からなる下地の上に形成
した、コロイダルシリカ共重合アクリル樹脂と、それに
分散した光触媒能を有する酸化チタンを含有する塗膜。 １４．光触媒能を有する酸化チタン１００重量部あた
り、５０〜４０００重量部、好ましくは２００〜２００
０重量部のコロイダルシリカ共重合アクリル樹脂を含有
する上記１２または１３に記載の塗膜。 によって解決することができる。Further, the third problem described above can be solved by the coating film according to the present invention. That is,
The third problem mentioned above is according to the present invention. A coating film formed by the coating method described in 9 or 10 above. 12. A coating film containing colloidal silica copolymerized acrylic resin and titanium oxide having photocatalytic activity dispersed therein. 13. A coating containing a colloidal silica copolymerized acrylic resin and a photocatalytically dispersed titanium oxide dispersed thereon formed on a base made of a colloidal silica copolymerized acrylic resin not containing titanium oxide having photocatalytic ability. 14． 50 to 4000 parts by weight, preferably 200 to 200 parts by weight, per 100 parts by weight of titanium oxide having photocatalytic ability
14. The coating according to the above item 12 or 13, which contains 0 parts by weight of a colloidal silica copolymerized acrylic resin. Can be solved by
【０００９】[0009]
【発明の実施の態様】以下、これらの発明について、詳
しく説明する。まず最初に、本発明に係る光触媒能を有
する酸化チタンについて説明する。本明細書において、
光触媒能を有する酸化チタンとは、光線、例えば紫外線
に感応して、他の物質に触媒作用を及ぼすことができる
酸化チタンをいう。酸化チタンが他の物質に触媒作用を
及ぼすことができる例の1つは、酸化チタンが塗膜に付
着した有機質の汚れを分解することである。本発明に係
る光触媒能を有する酸化チタンの例として、アナタース
型酸化チタン（アナターゼ型酸化チタン）を含有する酸
化チタンを挙げることができる。ルチル型酸化チタンも
光触媒能を有するが、一般にアナタース型酸化チタンの
方が、ルチル型酸化チタンよりも光触媒能において優れ
ている。本発明に係る光触媒能を有する酸化チタンは、
アナタース型酸化チタンを５０重量％以上、好ましくは
７５重量％以上、より好ましくは９５重量％以上含有す
るものであることができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, these inventions will be described in detail. First, the titanium oxide having photocatalytic ability according to the present invention will be described. In this specification,
Titanium oxide having photocatalytic ability refers to titanium oxide that can catalyze other substances in response to light, for example, ultraviolet light. One example in which titanium oxide can catalyze other substances is that titanium oxide decomposes organic soil attached to the coating. Examples of the titanium oxide having photocatalytic ability according to the present invention include titanium oxide containing anatase-type titanium oxide (anatase-type titanium oxide). Rutile-type titanium oxide also has photocatalytic ability, but in general anatase-type titanium oxide is superior in photocatalytic ability to rutile-type titanium oxide. Titanium oxide having photocatalytic ability according to the present invention,
It may contain at least 50% by weight, preferably at least 75% by weight, more preferably at least 95% by weight of anatase type titanium oxide.
【００１０】ところで、光触媒能を有する酸化チタン
は、その表面において、光線、例えば紫外線に感応し
て、他の物質に触媒作用を及ぼす。従って、光触媒能を
有する酸化チタンは、比表面積の大きいことが望まし
い。この点からすると、光触媒能を有する酸化チタン
は、小さな粒子であることが望ましい。本発明に係る光
触媒能を有する酸化チタンは、粒子の直径の平均（平均
粒径）が１〜１８０ナノメートル（ｎｍ）であることが
好ましく、平均粒径が３〜５０ｎｍであることがより好
ましい。光触媒能を有する酸化チタンは、平均粒径が１
ｎｍ以下であると、一般には、製造が困難となって製造
コストが増大し、平均粒径が１８０ｎｍ以上であると、
比表面積が小さすぎて、一般には、触媒作用が不十分で
ある。[0010] By the way, titanium oxide having photocatalytic activity exerts a catalytic action on other substances on its surface in response to light, for example, ultraviolet rays. Therefore, it is desirable that titanium oxide having photocatalytic ability has a large specific surface area. From this point, it is desirable that the titanium oxide having photocatalytic ability be small particles. The titanium oxide having photocatalytic ability according to the present invention preferably has an average particle diameter (average particle diameter) of 1 to 180 nanometers (nm), and more preferably has an average particle diameter of 3 to 50 nm. . Titanium oxide having photocatalytic ability has an average particle size of 1
If the average particle diameter is 180 nm or more, the production becomes difficult and the production cost increases.
The specific surface area is too small and, in general, the catalysis is insufficient.
【００１１】本発明に係る光触媒能を有する酸化チタン
は、他の物質との配合、例えばコロイダルシリカ共重合
アクリル樹脂エマルションとの配合を容易にするため、
ゾル形状またはスラリー形状さらにはコート剤形状に加
工されていることができる。本発明に係る光触媒能を有
する酸化チタンは、一般に、安定なエマルション塗料を
製造するために、種々の前処理を施してもよい。The photocatalytic titanium oxide according to the present invention can be easily blended with other substances, for example, with a colloidal silica copolymerized acrylic resin emulsion.
It can be processed into a sol shape or a slurry shape, or even a coating agent shape. In general, the titanium oxide having photocatalytic ability according to the present invention may be subjected to various pretreatments in order to produce a stable emulsion paint.
【００１２】本発明に係る光触媒能を有する酸化チタン
は、少量成分として、例えば５０重量％以下の他の物質
を含んでいてもよい。少量成分としての他の物質は、例
えば光触媒能を有する酸化チタンが感応しうる光線の波
長を長くすることができる物質であることができる。本
発明において使用する光触媒能を有する酸化チタンは、
市販の酸化チタン、例えばテイカ株式会社、から入手す
ることができる酸化チタンであることができる。The photocatalytic titanium oxide according to the present invention may contain, as a minor component, for example, 50% by weight or less of another substance. Other substances as minor components can be, for example, substances that can increase the wavelength of light to which titanium oxide having photocatalytic properties can be sensitive. Titanium oxide having photocatalytic ability used in the present invention,
It can be a commercially available titanium oxide, for example, titanium oxide available from Teika Corporation.
【００１３】次に、本発明に係るコロイダルシリカ共重
合アクリル樹脂エマルションについて説明する。本明細
書において、コロイダルシリカ共重合アクリル樹脂エマ
ルションとは、水を主成分とする溶媒を用いて、ケイ酸
含有物質、例えば無水ケイ酸の存在下で、アクリル系モ
ノマーを乳化共重合（エマルション共重合）することに
よって得られるエマルション（乳濁液）をいう。無水ケ
イ酸と、アクリル酸を主体とするアクリル系モノマーを
乳化共重合（エマルション共重合）することによって得
られるエマルション（乳濁液）は、その1つの例であ
る。Next, the colloidal silica copolymer acrylic resin emulsion according to the present invention will be described. In the present specification, a colloidal silica copolymerized acrylic resin emulsion is an emulsion copolymerization (emulsion copolymerization) of an acrylic monomer in the presence of a silicic acid-containing substance such as silicic anhydride using a solvent containing water as a main component. (Emulsion) obtained by polymerization. An emulsion (emulsion) obtained by emulsion copolymerization (emulsion copolymerization) of silicic anhydride and an acrylic monomer mainly containing acrylic acid is one example.
【００１４】本発明に係る無水ケイ酸は、粒子の直径の
平均（平均粒径）が５〜８０ナノメートル（ｎｍ）であ
ることが好ましく、平均粒径が２０〜６０ｎｍであるこ
とがより好ましい。本発明に係る無水ケイ酸は、例えば
表面処理により安定化したシリカゾルであることができ
る。The silica anhydride according to the present invention preferably has an average particle diameter (average particle diameter) of 5 to 80 nanometers (nm), and more preferably has an average particle diameter of 20 to 60 nm. . The silicic anhydride according to the present invention can be, for example, a silica sol stabilized by a surface treatment.
【００１５】また、本明細書において、アクリル系モノ
マーとは、炭素炭素二重結合ならびに炭素炭素二重結合
の炭素原子に結合したカルボキシル基および／またはエ
ステル基を有する共重合可能な化合物をいう。本発明に
係るアクリル系モノマーの例として、アクリル酸、アク
リル酸メチルエステル、アクリル酸エチルエステル、メ
タアクリル酸、メタアクリル酸メチルエステル、メタア
クリル酸エチルエステル等を挙げることができる。本発
明に係るコロイダルシリカ共重合アクリル樹脂エマルシ
ョンは、１種または２種またはそれ以上のアクリル系モ
ノマーを共重合して得たコロイダルシリカ共重合アクリ
ル樹脂エマルションであることができる。本発明に係る
コロイダルシリカ共重合アクリル樹脂エマルションを調
製する際に、得られるコロイダルシリカ共重合アクリル
樹脂エマルションの物性に不利な影響を及ぼさない限
り、アクリル系モノマーに加えて、少量の他の共重合性
モノマー、例えば酢酸ビニル、スチレン、アクリロニト
リルなどを加えてもよい。In the present specification, the acrylic monomer means a copolymerizable compound having a carbon-carbon double bond and a carboxyl group and / or an ester group bonded to a carbon atom of the carbon-carbon double bond. Examples of the acrylic monomer according to the present invention include acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, and ethyl methacrylate. The colloidal silica copolymer acrylic resin emulsion according to the present invention can be a colloidal silica copolymer acrylic resin emulsion obtained by copolymerizing one or two or more acrylic monomers. When preparing the colloidal silica copolymerized acrylic resin emulsion according to the present invention, in addition to the acrylic monomer, a small amount of other copolymerization, as long as it does not adversely affect the physical properties of the obtained colloidal silica copolymerized acrylic resin emulsion. Anionic monomers such as vinyl acetate, styrene, acrylonitrile and the like may be added.
【００１６】本発明に係るコロイダルシリカ共重合アク
リル樹脂エマルションは、ポリマー中に酸化ケイ素のユ
ニットを取り込んだ変性アクリル樹脂エマルションであ
ることができる。本発明に係る共重合は、コロイダルシ
リカ表面でのアクリル系モノマーのグラフト共重合と考
えることができる。グラフト共重合であると考えること
ができる理由は、本発明に係るコロイダルシリカ共重合
アクリル樹脂エマルションから得られるコロイダルシリ
カ共重合アクリル樹脂のフィルムが、アクリル樹脂とコ
ロイダルシリカの単なるブレンドによって得られるフィ
ルムよりも柔軟性が大きく、耐水性および透明性におい
て優れているという事実である。本発明に係るコロイダ
ルシリカ共重合アクリル樹脂エマルションは、水または
水を主成分とする溶媒を用いて、例えば１００重量部の
アクリル系モノマーを、２０〜５００重量部、好ましく
は３０〜４００重量部の無水ケイ酸の存在下で、乳化共
重合（エマルション共重合）することによって得られ
る。コロイダルシリカの共重合率を上げるために、例え
ば、表面が処理されたタイプの無水ケイ酸を使用しても
差し支えない。The colloidal silica copolymerized acrylic resin emulsion according to the present invention can be a modified acrylic resin emulsion in which a unit of silicon oxide is incorporated in a polymer. The copolymerization according to the present invention can be considered as graft copolymerization of an acrylic monomer on the surface of colloidal silica. The reason that it can be considered as a graft copolymer is that the film of the colloidal silica copolymerized acrylic resin obtained from the colloidal silica copolymerized acrylic resin emulsion according to the present invention is better than the film obtained by merely blending the acrylic resin and colloidal silica. Is also flexible and excellent in water resistance and transparency. The colloidal silica copolymer acrylic resin emulsion according to the present invention, using water or a solvent containing water as a main component, for example, 100 parts by weight of an acrylic monomer, 20 to 500 parts by weight, preferably 30 to 400 parts by weight It is obtained by emulsion copolymerization (emulsion copolymerization) in the presence of silicic anhydride. In order to increase the copolymerization rate of colloidal silica, for example, silicic anhydride of a surface-treated type may be used.
【００１７】本明細書において、コロイダルシリカ共重
合アクリル樹脂エマルションの固形分とは、コロイダル
シリカ共重合アクリル樹脂エマルションから揮発成分を
蒸発した残りの固形分である。コロイダルシリカ共重合
アクリル樹脂エマルションは、１０〜７０重量％、好ま
しくは２０〜５０重量％の固形分を含有していることが
できる。固形分の主たる成分は、コロイダルシリカ共重
合アクリル樹脂であることができる。コロイダルシリカ
共重合アクリル樹脂エマルションから揮発成分を蒸発し
て固形分を得る操作は、例えば、０〜１５０℃、好まし
くは２０〜１２０℃の温度で、例えば、１分〜１０時
間、好ましくは１０分〜１時間、大気圧下、減圧下また
は加圧下で、実施することができる。In the present specification, the solid content of the colloidal silica copolymerized acrylic resin emulsion is a solid content obtained by evaporating volatile components from the colloidal silica copolymerized acrylic resin emulsion. The colloidal silica copolymerized acrylic resin emulsion may contain 10 to 70% by weight, preferably 20 to 50% by weight of solids. The main component of the solid content can be a colloidal silica copolymerized acrylic resin. The operation of evaporating volatile components from the colloidal silica copolymer acrylic resin emulsion to obtain a solid content is performed, for example, at a temperature of 0 to 150 ° C, preferably 20 to 120 ° C, for example, 1 minute to 10 hours, preferably 10 minutes. It can be carried out at atmospheric pressure, reduced pressure or increased pressure for up to 1 hour.
【００１８】一般に、本発明に係る共重合ポリマーの製
造は、乳化共重合（エマルション共重合）により行い、
共重合ポリマーは安定な乳化共重合体として得られるよ
うに工夫する。本発明に係る塗料は、溶剤が無公害の水
でなる利点があるので、コロイダルシリカ共重合アクリ
ル樹脂がエマルション状態で得られることは好都合であ
る。なお、有機溶剤系塗料は、下地や下地塗料を侵して
色むらを生じさせるとか、硬化を遅らせるとかの欠点が
ある。In general, the production of the copolymer according to the present invention is carried out by emulsion copolymerization (emulsion copolymerization).
The copolymer is devised so as to be obtained as a stable emulsion copolymer. Since the coating material according to the present invention has an advantage that the solvent is harmless water, it is advantageous that the colloidal silica copolymerized acrylic resin can be obtained in an emulsion state. In addition, the organic solvent-based paint has a drawback that it causes color unevenness by attacking the undercoat or the undercoat, or delays curing.
【００１９】また、コロイダルシリカ共重合アクリル樹
脂を、固体とか有機溶剤溶液など他の状態で得て、後工
程により、例えばホモジナイザーとかコロイドミル等の
機械的分散方法により、エマルション状態のポリマー分
散液にすることもあり得て、本発明の一部をなし得る。Further, the colloidal silica copolymerized acrylic resin is obtained in another state such as a solid or an organic solvent solution, and is converted into an emulsion state polymer dispersion by a post-process, for example, by a mechanical dispersion method such as a homogenizer or a colloid mill. And may form part of the present invention.
【００２０】本発明に係るコロイダルシリカ共重合アク
リル樹脂エマルションは、用途に従って共重合モノマー
の種類と量を変え、無水ケイ酸とアクリル系モノマーと
の量比を変えることにより、広範囲のものが得られる。
本発明において使用されるコロイダルシリカ共重合アク
リル樹脂に係る無水ケイ酸の量は、アクリル系モノマー
１００重量部に対して、２０〜５００重量部、好ましく
は３０〜４００重量部である。２０重量部以下ではコロ
イダルシリカを共重合した効果が出難いし、５００重量
部以上では塗膜が脆くなって最初から塗膜物性が貧弱で
ある。乳化共重合（エマルション共重合）に供される乳
化剤は、一般にはノニオンを主体としたアニオンである
が、希望する物性に依存して、その量と種類を変えても
差し支えない。The colloidal silica copolymerized acrylic resin emulsion according to the present invention can be obtained in a wide range by changing the type and amount of the copolymerized monomer according to the application and by changing the ratio of the amount of silicic anhydride to the acrylic monomer. .
The amount of silicic anhydride in the colloidal silica copolymerized acrylic resin used in the present invention is 20 to 500 parts by weight, preferably 30 to 400 parts by weight based on 100 parts by weight of the acrylic monomer. If the amount is less than 20 parts by weight, the effect of copolymerizing colloidal silica is difficult to obtain, and if it is more than 500 parts by weight, the coating film becomes brittle and the physical properties of the coating film are poor from the beginning. The emulsifier provided for the emulsion copolymerization (emulsion copolymerization) is generally an anion mainly composed of nonions, but the amount and type thereof may be changed depending on the desired physical properties.
【００２１】かくして得られる本発明に係るコロイダル
シリカ共重合アクリル樹脂エマルションの一般的物性
は、例えば、PHが７．０〜９．０であり、固形分が１１
０℃で３０分間乾燥後２０〜５０重量％であり、粘度が
０．００２〜０．１パスカル・秒（Pa・s）、すなわち
２〜１００センチポアズ（cP）であり、最低造膜温度が
ー１０〜５０℃である。また、塗膜のガラス転移点（ガ
ラス転移温度）は、例えば−２０〜４０℃である。もち
ろん必要に応じて、コロイダルシリカ共重合アクリル樹
脂エマルションである限りは、その物性をいかように変
えても一般には差し支えない。本発明において使用する
コロイダルシリカ共重合アクリル樹脂エマルションは、
市販のコロイダルシリカ共重合アクリル樹脂エマルショ
ン、例えば大日本インキ化学工業株式会社から入手する
ことができるコロイダルシリカ共重合アクリル樹脂エマ
ルションであることができる。The general physical properties of the thus obtained colloidal silica copolymerized acrylic resin emulsion according to the present invention are, for example, a pH of 7.0 to 9.0 and a solid content of 11
It is 20 to 50% by weight after drying at 0 ° C for 30 minutes, has a viscosity of 0.002 to 0.1 Pascal second (Pa · s), that is, 2 to 100 centipoise (cP), and has a minimum film forming temperature of- 10 to 50 ° C. The glass transition point (glass transition temperature) of the coating film is, for example, -20 to 40 ° C. Of course, if necessary, as long as the emulsion is a colloidal silica copolymer acrylic resin emulsion, the physical properties thereof can be changed in any way. Colloidal silica copolymer acrylic resin emulsion used in the present invention,
A commercially available colloidal silica copolymer acrylic resin emulsion, for example, a colloidal silica copolymer acrylic resin emulsion available from Dainippon Ink and Chemicals, Inc. can be used.
【００２２】本発明に係るエマルション塗料は、かかる
酸化チタンとかかるコロイダルシリカ共重合アクリル樹
脂エマルションを配合してなるものである。その配合
は、酸化チタン１００重量部に対して、コロイダルシリ
カ共重合アクリル樹脂エマルションを、コロイダルシリ
カ共重合アクリル樹脂固形分が５０〜４０００重量部、
好ましくは２００〜２０００重量部となるように実施す
る。コロイダルシリカ共重合アクリル樹脂固形分が５０
重量部以下では酸化チタンの付着が不充分であり、コロ
イダルシリカ共重合アクリル樹脂固形分が４０００重量
部以上では酸化チタンがコロイダルシリカ共重合アクリ
ル樹脂に埋没して、光触媒としての効果を発揮できない
ことが多い。本発明に係る安定なエマルション塗料を製
造するためには、酸化チタンの前処理を含む種々の工夫
が取られ得るが、本発明の効果を発揮し得る方法であれ
ば、いずれの方法でも構わない。例えば、コロイダルシ
リカ共重合アクリル樹脂エマルションを撹拌しつつ、酸
化チタンを水に配合して予め調製したスラリーを徐々に
添加する方法もある。The emulsion paint according to the present invention comprises the titanium oxide and the colloidal silica copolymer acrylic resin emulsion. The blend is based on 100 parts by weight of titanium oxide, the colloidal silica copolymerized acrylic resin emulsion, the solid content of the colloidal silica copolymerized acrylic resin is 50 to 4000 parts by weight,
It is preferably carried out so as to be 200 to 2000 parts by weight. Colloidal silica copolymerized acrylic resin solid content of 50
If the amount is less than 4 parts by weight, the adhesion of titanium oxide is insufficient, and if the solid content of the colloidal silica copolymer acrylic resin is 4000 parts by weight or more, the titanium oxide is buried in the colloidal silica copolymer acrylic resin and cannot exhibit the effect as a photocatalyst. There are many. In order to produce the stable emulsion paint according to the present invention, various measures including pretreatment of titanium oxide can be taken, but any method may be used as long as the method can exert the effects of the present invention. . For example, there is a method in which a slurry prepared in advance by mixing titanium oxide with water while stirring the colloidal silica copolymerized acrylic resin emulsion is gradually added.
【００２３】エマルション塗料の塗料物性を改良するた
めに、塗料中に種々の改良剤を添加するのは構わない。
一例を挙げれば、塗料の作業性や安定性を改良する増粘
剤、消泡剤、分散助剤、流動調整剤、沈降防止剤等があ
る。一方、本発明に係る塗膜の諸物性を改良するために
又は他の目的のために、造膜助剤または他の樹脂エマル
ション、水溶性無機ポリマー、コロイダルシリカなどの
微粒子または顔料などを、本発明の効果を損なわない限
り配合しても構わない。例えば、白色顔料として重量で
１〜１０倍の酸化チタン、例えばルチル型酸化チタン
を、触媒能を有する酸化チタンに本発明の効果を損なわ
ない限り配合しても構わない。In order to improve the paint properties of the emulsion paint, various additives may be added to the paint.
Examples include thickeners, defoamers, dispersing aids, flow regulators, antisettling agents, etc., which improve the workability and stability of paints. On the other hand, in order to improve the physical properties of the coating film according to the present invention or for other purposes, a film forming aid or other resin emulsion, a water-soluble inorganic polymer, fine particles or pigments such as colloidal silica, etc. They may be blended as long as the effects of the invention are not impaired. For example, 1 to 10 times by weight of titanium oxide, for example, rutile type titanium oxide may be added to the titanium oxide having catalytic activity as a white pigment as long as the effects of the present invention are not impaired.
【００２４】本発明に係るエマルション塗料は、本発明
に係る塗装方法によって、本発明に係る塗膜とすること
ができる。本発明に係る塗膜は、本発明に係るエマルシ
ョン塗料の乾燥または焼き付けにより現出する。乾燥
は、外壁など大型構造物の場合は常温乾燥であるが、乾
燥機に入るほどの小型形状物は、例えば２００℃で１時
間以内に乾燥するのが、支持体への接着力が高まって好
ましい。支持体への塗布方法は、本発明に係るエマルシ
ョン塗料をよく細部まで塗布し得て、目的に合致した状
態へ乾燥または焼き付けることができる方法であれば、
いずれの方法でもよい。例えば、塗布方法には、塗料中
へ支持体を浸漬する浸漬法、刷毛塗り法およびスプレー
コート法などがある。エマルションという分散体を安定
に塗布するためには、例えば、低圧スプレーコート法が
望ましい。The emulsion paint according to the present invention can be made into the coating film according to the present invention by the coating method according to the present invention. The coating film according to the present invention appears by drying or baking the emulsion paint according to the present invention. Drying is performed at room temperature in the case of a large structure such as an outer wall, but a small-sized object that can enter the dryer is dried at, for example, 200 ° C. within one hour. preferable. The method of applying to the support is such that the emulsion paint according to the present invention can be applied to the details in detail and can be dried or baked in a state that meets the purpose.
Either method may be used. For example, the coating method includes a dipping method in which a support is dipped in a paint, a brush coating method, a spray coating method, and the like. In order to stably apply a dispersion called an emulsion, for example, a low pressure spray coating method is desirable.
【００２５】本発明に係るエマルション塗料の塗布量
は、被塗体または支持体の用途または期待する効果の程
度により変わり得るが、一般には乾燥塗膜重量として、
４〜５００ｇ／ｍ２、好ましくは１０〜３００ｇ／ｍ２
である。本発明に係るエマルション塗料の塗布量が、４
ｇ／ｍ２以下では効果を発現しづらいし、５００ｇ／ｍ
２以上では経済性を損なう。The amount of the emulsion paint according to the present invention applied
Depends on the intended use of the substrate or substrate
Although it can vary depending on the degree, generally, as a dry coating weight,
4 to 500 g / m2, Preferably 10 to 300 g / m2
It is. When the coating amount of the emulsion paint according to the present invention is 4
g / m2In the following, it is difficult to exhibit the effect, and 500 g / m
2The above impairs economic efficiency.
【００２６】本発明に係るエマルション塗料の塗布に当
たって支持体や被塗体への下地処理は、塗布物の付着力
を上げるためにも美感を保つためにも重要である。特に
基材が有機物を含む場合には、耐久力のある防汚性を期
待すれば、光触媒との間の接触を防ぐバリアー（保護
層）ともなり得る有機質が無いかまたは少ない塗料の下
地塗布が好ましい。本発明者らは、本発明に係るエマル
ション塗料に配合するコロイダルシリカ共重合アクリル
樹脂エマルションそれ自体が、非常に優れた下地塗料と
なり得ることを見出した。下地塗料の塗布量は、例えば
本発明に係るエマルション塗料の０．２〜１０倍の量が
好ましい。強固な塗装をするためには下地塗料が充分乾
燥した後に、本発明に係るエマルション塗料を塗布する
ことが必要である。In the application of the emulsion paint according to the present invention, the undercoating of the support or the object to be coated is important for increasing the adhesion of the coated object and for maintaining the aesthetic appearance. In particular, when the base material contains an organic substance, if a durable antifouling property is expected, a base coating of a coating material having no or little organic material which can also be a barrier (protective layer) for preventing contact with the photocatalyst is required. preferable. The present inventors have found that the colloidal silica copolymer acrylic resin emulsion blended in the emulsion paint according to the present invention itself can be a very excellent base paint. The application amount of the base paint is preferably, for example, 0.2 to 10 times the amount of the emulsion paint according to the present invention. In order to apply a strong coating, it is necessary to apply the emulsion coating according to the present invention after the base coating is sufficiently dried.
【００２７】本発明に係る塗膜の防汚効果や窒素酸化物
（ＮＯｘ）分解効果などは、配合した紫外線に感応した
酸化チタン、特にアナタース型酸化チタンの触媒作用に
よるものである。一方、光触媒能を有する酸化チタン、
特にアナタース型酸化チタンを支持体あるいは被塗体へ
強固に固着させ、光触媒の効果をよく上げ得ている機能
は、配合した一方のコロイダルシリカ共重合アクリル樹
脂のバインダーとしての耐久力のある付着力によるもの
である。しかしながら、光触媒は、付着した有機物を分
解して防汚機能を発現するという公知の知見の中にあっ
て、有機物の接着剤であるアクリル樹脂自体が、コロイ
ダルシリカで修飾されているとはいえ、よく分解に耐
え、耐久性のある防汚効果をもたらせているという事実
は、全く予期せぬ発見であった。The antifouling effect and the nitrogen oxide (NOx) decomposing effect of the coating film according to the present invention are due to the catalytic action of titanium oxide, particularly anatase type titanium oxide, which is sensitive to the compounded ultraviolet rays. On the other hand, titanium oxide having photocatalytic ability,
In particular, the function of firmly fixing the anatase type titanium oxide to the support or the coated object and improving the effect of the photocatalyst is a durable adhesive force as a binder of one of the blended colloidal silica copolymer acrylic resin It is due to. However, the photocatalyst is known in the art that it expresses an antifouling function by decomposing an attached organic substance, and although the acrylic resin itself, which is an organic substance adhesive, is modified with colloidal silica, The fact that it resists degradation and provides a durable antifouling effect was a completely unexpected finding.
【００２８】[0028]
【実施例】塗料の調製EXAMPLES Preparation of paint
【実施例１】コロイダルシリカ共重合アクリル樹脂エマ
ルション（大日本インキ化学工業株式会社製 ＶＯＮＣ
ＯＡＴ ＤＶ−９４０；ポリマーのガラス転移温度：−
２℃、コロイダルシリカ共重合量：アクリル酸モノマー
１００重量部に対し１００重量部、固形分：３１．０重
量％、PH：８．１、粘度：２３℃で０．００６Pa・s
（６cP）、最低造膜温度：０℃）１２０００ｇに対し、
酸化チタン粉末(テイカ株式会社製 ＡＭＴ―６００、
結晶型：アナタース型、純度：９８重量％、比表面積５
０ｍ２／ｇ、平均粒径：３０ｎｍ)５００ｇと２０００
ｇの水のペーストを、モルタルミキサーでエマルション
を撹拌しながら徐々に混合していった。次に造膜助剤、
消泡剤、分散剤および流動調整剤を適宜少量添加し、最
後に水で粘度を調節して乳白色エマルションを得た。粘
度：０．２２Pa・s（２２００cP）、固形分：２６．０
重量％、ＰＨ：７．２、比重１．１３。Example 1 Colloidal silica copolymer acrylic resin emulsion (VONC manufactured by Dainippon Ink and Chemicals, Inc.)
OAT DV-940; glass transition temperature of polymer:-
2 ° C., colloidal silica copolymerization amount: 100 parts by weight based on 100 parts by weight of acrylic acid monomer, solid content: 31.0% by weight, PH: 8.1, viscosity: 0.006 Pa · s at 23 ° C.
(6 cP), minimum film forming temperature: 0 ° C.)
Titanium oxide powder (AMT-600, manufactured by Teika Co., Ltd.)
Crystal type: Anatase type, purity: 98% by weight, specific surface area 5
0 m 2 / g, average particle size: 30 nm) 500 g and 2000
g of water paste was gradually mixed while stirring the emulsion with a mortar mixer. Next, a film-forming aid,
An antifoaming agent, a dispersant and a flow regulator were added in small amounts as appropriate, and finally the viscosity was adjusted with water to obtain a milky white emulsion. Viscosity: 0.22 Pa · s (2200 cP), solid content: 26.0
% By weight, PH: 7.2, specific gravity 1.13.
【００２９】[0029]
【実施例２】コロイダルシリカ共重合アクリル樹脂エマ
ルション(大日本インキ化学工業株式会社製 ＶＯＮＣ
ＯＡＴ ＤＶ−８７６；ポリマーのガラス転移温度：−
２℃、コロイダルシリカ共重合量：アクリル酸モノマー
１００重量部に対し５０重量部、固形分：３８．２重量
％、ＰＨ：８．７、粘度：２３℃で０．００９Pa・s
（９cP）、最低造膜温度：０℃)１２０００ｇに対し、
酸化チタン粉末(テイカ株式会社製 ＡＭＴ−６００、
結晶型：アナタース型、純度９８重量％、比表面積５０
ｍ２／ｇ、平均粒径：３０ｎｍ)８１８ｇと３２７０ｇ
の水のペーストを、モルタルミキサーでエマルションを
撹拌しながら徐々に混合していった。次にコロイダルシ
リカ(日産化学工業株式会社製；コロイダルシリカ水分
散液ＳＴ−４０、無水シリカ４０重量％、粒径：１０〜
２０ｎｍ)を３８２０ｇ添加し、トータルシリカ量とし
てはＤＶ−９４０と同様アクリル樹脂と等量となした。
さらに造膜助剤、消泡剤、分散剤および流動調整剤を適
宜少量添加して、最後に水で粘度を調節して乳白色エマ
ルションを得た。粘度：１．９Pa・s（１９００cP）、
固形分：２５．０重量％、ＰＨ：７．８、比重１．１
８。Example 2 Colloidal silica copolymerized acrylic resin emulsion (VONC manufactured by Dainippon Ink and Chemicals, Inc.)
OAT DV-876; glass transition temperature of polymer:-
2 ° C, colloidal silica copolymerization amount: 50 parts by weight based on 100 parts by weight of acrylic acid monomer, solid content: 38.2% by weight, PH: 8.7, viscosity: 0.009 Pa · s at 23 ° C
(9 cP), minimum film forming temperature: 0 ° C.)
Titanium oxide powder (AMT-600, manufactured by Teika Co., Ltd.)
Crystal type: Anatase type, purity 98% by weight, specific surface area 50
m 2 / g, average particle size: 30 nm) 818 g and 3270 g
Of water was gradually mixed while stirring the emulsion with a mortar mixer. Next, colloidal silica (manufactured by Nissan Chemical Industries, Ltd .; colloidal silica aqueous dispersion ST-40, anhydrous silica 40% by weight, particle size: 10 to 10%)
3820 g was added, and the total silica amount was equivalent to that of the acrylic resin as in the case of DV-940.
Further, a film-forming auxiliary, an antifoaming agent, a dispersant and a flow regulator were added in small amounts as appropriate, and finally the viscosity was adjusted with water to obtain a milky white emulsion. Viscosity: 1.9 Pa · s (1900 cP),
Solid content: 25.0% by weight, PH: 7.8, specific gravity 1.1
8.
【００３０】[0030]
【比較例１】通常の塗料用アクリル樹脂エマルション
(大日本インキ化学工業株式会社製ＶＯＮＣＯＡＴ Ｅ
Ｃ−８１７；固形分５０重量％、ＰＨ８．７、粘度２３
℃で０．５Pa・s（５００cP）以上、最低造膜温度：１
８℃)７２００ｇに対し、酸化チタン粉末(テイカ株式会
社製 ＡＭＴ−６００、結晶型：アナタース型、純度９
８重量％、比表面積５０ｍ２／ｇ、平均粒径３０ｎｍ)
５００ｇと２０００ｇの水のペーストを、モルタルミキ
サーでエマルションを撹拌しながら徐々に混合していっ
た。つぎに造膜助剤、消泡剤、分散剤および流動調整剤
を適宜少量添加して、最後に水で粘度を調節して乳白色
エマルションを得た。粘度：０．０９Pa・s（９０c
P）、固形分：３５．０重量％、ＰＨ７．８、比重１．
０８。[Comparative Example 1] Acrylic resin emulsion for ordinary paint
(VONCOATE manufactured by Dainippon Ink and Chemicals, Inc.
C-817; solid content 50% by weight, PH 8.7, viscosity 23
0.5Pa · s (500cP) or more at ℃, minimum film formation temperature: 1
Titanium oxide powder (AMT-600 manufactured by Teica Co., Ltd., crystal type: anatase type, purity 9)
(8% by weight, specific surface area 50 m 2 / g, average particle size 30 nm)
500 g and 2000 g of the water paste were gradually mixed while stirring the emulsion with a mortar mixer. Next, a film-forming aid, an antifoaming agent, a dispersant and a flow regulator were added in small amounts as appropriate, and finally the viscosity was adjusted with water to obtain a milky white emulsion. Viscosity: 0.09 Pa · s (90 c
P), solid content: 35.0% by weight, PH 7.8, specific gravity 1.
08.
【００３１】[0031]
【比較例２】比較例１と同様なアクリル樹脂エマルショ
ン３６００ｇと酸化チタン５００ｇの混合液中に、実施
例２で使ったコロイダルシリカ水分散液４５００ｇを添
加しコロイダルシリカとアクリル樹脂を等量になした。
次に造膜助剤、消泡剤、分散剤および流動調整剤を適宜
少量添加して、最後に水で粘度を調節して乳白色エマル
ションを得た。粘度：１．２Pa・s（１２００cP）、固
形分３８．０重量％、ＰＨ７．８、比重１．１６。Comparative Example 2 To a mixed solution of 3600 g of an acrylic resin emulsion and 500 g of titanium oxide as in Comparative Example 1, 4500 g of the aqueous dispersion of colloidal silica used in Example 2 was added to make the same amount of colloidal silica and acrylic resin. did.
Next, an appropriate amount of a film forming aid, an antifoaming agent, a dispersant, and a flow regulator was added, and finally, the viscosity was adjusted with water to obtain a milky white emulsion. Viscosity: 1.2 Pa · s (1200 cP), solid content 38.0% by weight, PH 7.8, specific gravity 1.16.
【００３２】[0032]
【比較例３】実施例１に使用したコロイダルシリカ共重
合アクリル樹脂エマルションのみに造膜助剤、消泡剤、
分散剤および流動調整剤を適宜少量添加して、最後に水
で粘度を調節して乳白色エマルションを得た。粘度：
０．００５Pa・s（５cP）、固形分：２９．０重量％、
ＰＨ：８．１、比重１．１０。Comparative Example 3 Only the colloidal silica copolymerized acrylic resin emulsion used in Example 1 was used as a film-forming aid, an antifoaming agent,
A small amount of a dispersant and a flow control agent were appropriately added, and finally, the viscosity was adjusted with water to obtain a milky white emulsion. viscosity:
0.005 Pa · s (5 cP), solid content: 29.0% by weight,
PH: 8.1, specific gravity 1.10.
【００３３】塗膜フィルムおよび塗装板の作成 塗膜物性測定用塗膜フィルムの作成 ガラス板上に各塗料を固形分の濃度に従って計り取り、
バーコーダーで塗り広げ室温で１〜２時間乾燥後、丁寧
に剥がして収縮を防ぎながら１１０℃で３０分乾燥して
塗膜フィルムを得た。塗膜フィルムの厚さはいずれも３
０〜４０μｍであった。これらの塗膜フィルムから１０
０ｍｍ×１０ｍｍの試験片を切り出し、引っ張り試験に
供した。Preparation of Coating Film and Coated Plate Preparation of Coating Film for Measurement of Coating Physical Properties Each coating was measured on a glass plate according to the solid content concentration,
After spreading with a bar coder and drying at room temperature for 1 to 2 hours, the film was dried at 110 ° C. for 30 minutes while carefully peeling off to prevent shrinkage to obtain a coated film. The thickness of each coating film is 3
It was 0 to 40 μm. From these coated films, 10
A test piece of 0 mm × 10 mm was cut out and subjected to a tensile test.
【００３４】強制耐候試験用塗装板の作成 ３０ｃｍ×３０ｃｍのスレート板に光触媒を含む各エマ
ルション塗料を低圧スプレーで(下地塗料なしで)直接コ
ートした。塗装板への塗布量はいずれも２７〜３３ｇ／
ｍ２になるよう調節した。塗装板はいずれも常温で乾燥
し、ウエザオメーターでの強制耐候試験用に１８０ｍｍ
×５０ｍｍに切り出した。Preparation of Coated Plate for Forced Weathering Test A 30 cm × 30 cm slate plate was directly coated with each emulsion paint containing a photocatalyst by a low pressure spray (without a base paint). The amount applied to the painted plate is 27 to 33 g /
It was adjusted to be in m 2. All painted boards are dried at room temperature and 180mm for forced weathering test with weatherometer
It cut out to × 50 mm.
【００３５】屋外暴露試験用塗装板の作成 トップ層（トップコート）の光触媒が下地の有機層に及
ぼす影響を観察するために、まず黄色のアクリル樹脂エ
マルション塗料を、６０ｃｍ×１２０ｃｍのスレート板
に低圧スプレーでコートした。塗布量はいずれも膜厚が
１０〜２０μｍになるよう調節した。塗装板はいずれも
常温で一日乾燥し、その後黄色下地塗料の上に実施例１
および２ならびに比較例１および３で得た各塗料を、低
圧スプレーで重ね塗りした。これらの塗装板の外に、実
施例１および２の塗料については、黄色の下地塗装の上
に、コロイダルシリカ共重合アクリル樹脂エマルション
ＶＯＮＣＯＡＴ ＤＶ―９４０を中間層としてコート
し(塗膜厚はほぼ３０μｍ)、さらにその上に光触媒を含
む実施例１および２ならびに比較例１および３で得た各
塗料を、低圧スプレー(塗布量はいずれも２７〜３３ｇ
／ｍ２)でコートして３層の塗膜を調製し、中間層とし
てコートしたコロイダルシリカ共重合アクリル樹脂のバ
リアー効果を観察した。塗装板はいずれも屋上にて屋外
暴露試験に供した。Preparation of Coating Plate for Outdoor Exposure Test In order to observe the effect of the photocatalyst of the top layer (top coat) on the underlying organic layer, first, a yellow acrylic resin emulsion paint was applied to a 60 cm × 120 cm slate plate at a low pressure. Coated with spray. The coating amount was adjusted so that the film thickness was 10 to 20 μm. Each coated plate was dried at room temperature for one day, and then dried on a yellow base paint.
And 2 and Comparative Examples 1 and 3 were overcoated with a low pressure spray. In addition to these coated plates, the coatings of Examples 1 and 2 were coated with a colloidal silica copolymer acrylic resin emulsion VONCOAT DV-940 as an intermediate layer on a yellow base coat (coating thickness was approximately 30 μm). ) And the paints obtained in Examples 1 and 2 and Comparative Examples 1 and 3 each containing a photocatalyst thereon were sprayed with a low-pressure spray (the amount of coating was 27 to 33 g).
/ M 2 ) to prepare a three-layer coating film, and observe the barrier effect of the colloidal silica copolymerized acrylic resin coated as an intermediate layer. All of the coated boards were subjected to an outdoor exposure test on the roof.
【００３６】試験結果 塗膜物性の測定結果 塗膜物性測定用塗膜フィルムの作成で得た短冊型試験
片の引っ張り試験を室温で行い、以下の結果を得た。Test Results Results of Measurement of Physical Properties of Coating Film A strip type test piece obtained by preparing a coating film for measuring physical properties of coating films was subjected to a tensile test at room temperature, and the following results were obtained.
【表１】 各塗膜の組成； 実施例１：酸化チタン＋コロイダルシリカ共重合アクリ
ル樹脂 ＤＶ−９４０ 実施例２：酸化チタン＋コロイダルシリカ共重合アクリ
ル樹脂 ＤＶ−８７６＋コロイダルシリカ 比較例１：酸化チタン＋アクリル樹脂 ＥＣ−８１７ 比較例２：酸化チタン＋アクリル樹脂 ＥＣ−８１７＋
コロイダルシリカ 比較例３：コロイダルシリカ共重合アクリル樹脂 ＤＶ
−９４０ 実施例１および２と比較例１は、酸化チタンとアクリル
樹脂およびコロイダルシリカの割合は等しいが、表１か
らわかるように、コロイダルシリカが一部でもアクリル
樹脂と共重合して初めて酸化チタンと相容した柔軟な塗
膜になる。また実施例１および２の塗膜フィルムの水蒸
気透過性は極めて高く、塗膜にふくれを作る分解ガスの
放出に好都合である。[Table 1] Composition of each coating film; Example 1: titanium oxide + colloidal silica copolymer acrylic resin DV-940 Example 2: titanium oxide + colloidal silica copolymer acrylic resin DV-876 + colloidal silica Comparative Example 1: titanium oxide + acrylic resin EC -817 Comparative Example 2: Titanium oxide + acrylic resin EC-817 +
Colloidal silica Comparative example 3: Colloidal silica copolymer acrylic resin DV
-940 In Examples 1 and 2 and Comparative Example 1, the proportions of titanium oxide, acrylic resin and colloidal silica were the same. It becomes a flexible coating film compatible with. Further, the water vapor permeability of the coated films of Examples 1 and 2 is extremely high, which is convenient for releasing a decomposition gas which causes blisters in the coated film.
【００３７】塗装板の強制耐候試験 強制耐候試験用塗装板の作成で得たスレート塗装板
を、サンシャインウエザオメーターにかけ１５００時間
後の汚れの程度を目視観察で測定し、そして塗膜の付着
性を基盤目剥離試験で測定した。Forced weathering test of the coated plate The slate coated plate obtained in the preparation of the coated plate for the forced weathering test was subjected to a sunshine weatherometer, and the degree of dirt after 1500 hours was measured by visual observation. Was measured by a base line peeling test.
【表２】 各塗膜の組成； 実施例１：酸化チタン＋コロイダルシリカ共重合アクリ
ル樹脂 ＤＶ−９４０ 実施例２：酸化チタン＋コロイダルシリカ共重合アクリ
ル樹脂 ＤＶ−８７６＋コロイダルシリカ 比較例１：酸化チタン＋アクリル樹脂 ＥＣ−８１７ 比較例２：酸化チタン＋アクリル樹脂 ＥＣ―８１７＋
コロイダルシリカ 比較例３：コロイダルシリカ共重合アクリル樹脂 ＤＶ
−９４０ 比較例１はバインダーがほぼ分解していた。比較例３は
バインダーこそ安定だったが酸化チタンが存在せず防汚
性効果がなかった。それに比較して実施例１および２は
期待通りの効果を示した。[Table 2] Composition of each coating film; Example 1: titanium oxide + colloidal silica copolymer acrylic resin DV-940 Example 2: titanium oxide + colloidal silica copolymer acrylic resin DV-876 + colloidal silica Comparative Example 1: titanium oxide + acrylic resin EC -817 Comparative Example 2: Titanium oxide + acrylic resin EC-817 +
Colloidal silica Comparative example 3: Colloidal silica copolymer acrylic resin DV
-940 In Comparative Example 1, the binder was almost decomposed. In Comparative Example 3, the binder was stable, but no titanium oxide was present and no antifouling effect was obtained. In comparison, Examples 1 and 2 showed the expected effect.
【００３８】屋外暴露試験 屋外暴露試験用塗装板の作成で得た黄色のスレート塗
装板を、１年間ビルの屋上にて屋外暴露し、汚れの程度
を目視した。Outdoor exposure test The yellow slate coated plate obtained by preparing the coated plate for the outdoor exposure test was exposed outdoors on the roof of a building for one year, and the degree of dirt was visually observed.
【表３】 各塗装板の構成 塗装例Ａ；スレート板／黄色アクリル樹脂塗料／実施例
１の塗料 塗装例Ｂ；スレート板／黄色アクリル樹脂塗料／下地塗
料／実施例１の塗料 塗装例Ｃ；スレート板／黄色アクリル樹脂塗料／実施例
２の塗料 塗装例Ｄ；スレート板／黄色アクリル樹脂塗料／下地塗
料／実施例２の塗料 塗装例Ｅ；スレート板／黄色アクリル樹脂塗料／比較例
１の塗料 塗装例Ｆ；スレート板／黄色アクリル樹脂塗料／比較例
３の塗料 塗装例Ｅはバインダーがかなり分解していた。塗装例Ｆ
は塗装として安定だが、防汚性機能はなかった。塗装例
Ａおよび塗装例Ｃではわずかなチョーキングが見られる
ものの、防汚機能は残っていた。特に下地塗料を塗った
塗装例Ｂおよび塗装例Ｄの場合、下地塗料が黄色の有機
塗料（黄色アクリル樹脂塗料）との間のバリアーになっ
ていると考えられ、塗装板は安定しており、下地塗料と
してのコロイダルシリカ共重合アクリル樹脂エマルショ
ンの効果が高いことがわかった。[Table 3] Composition of each coated plate Coating example A; Slate plate / yellow acrylic resin paint / paint of Example 1 Coating example B; Slate plate / yellow acrylic resin paint / base paint / paint of Example 1 Coating example C; Slate plate / yellow Acrylic resin paint / paint of Example 2 Painting example D; Slate plate / yellow acrylic resin paint / base paint / paint of Example 2 Painting example E; Slate plate / yellow acrylic resin paint / paint of comparative example 1 Painting example F; Slate plate / Yellow acrylic resin coating / Paint of Comparative Example 3 In coating example E, the binder was considerably decomposed. Painting example F
Is stable as a paint, but has no antifouling function. In coating examples A and C, slight choking was observed, but the antifouling function remained. Especially in the case of the coating example B and the coating example D in which the undercoat is applied, the undercoat is considered to be a barrier between the yellow organic paint (yellow acrylic resin paint) and the coated plate is stable, It was found that the effect of the colloidal silica copolymer acrylic resin emulsion as a base coating material was high.
【００３９】[0039]
【実施例３】本発明の塗膜のＮＯｘ分解力を測定するた
めに、実施例１の塗膜フィルムを１００ｍｍ×５０ｍｍ
に切り取り、１Ｌのガラス容器に入れ、ＮＯガスを１５
ｐｐｍ入れた後、高圧水銀灯(４００Ｗ、照明強度８．
５ｍＷ／ｃｍ２)を１０分間照射した後、ＮＯガスの残
量を測定した。ＮＯガスは１５ｐｐｍから０．８ｐｐｍ
へと減少していた。比較のため比較例３のフィルムを全
く同じ条件で実験したが、ＮＯの減少は見られなかっ
た。Example 3 In order to measure the NOx decomposing ability of the coating film of the present invention, the coating film of Example 1 was measured to be 100 mm × 50 mm.
Into a 1 L glass container,
ppm, a high-pressure mercury lamp (400 W, illumination intensity 8.
5 mW / cm 2 ) for 10 minutes, and the remaining amount of NO gas was measured. NO gas is 15ppm to 0.8ppm
Had decreased to For comparison, the film of Comparative Example 3 was tested under exactly the same conditions, but no decrease in NO was observed.
【００４０】[0040]
【実施例４】本発明の塗膜の抗菌性を測定するために、
実施例１の塗料２０ｇを直径８０ｍｍのガラスシャーレ
に入れ、１１０℃×２時間乾燥後、試験体となした。次
に試験体表面に大腸菌の菌液を０．６ｍｌ接種した。菌
液が乾燥しないように湿潤な環境を設定し、光が射し込
む部屋に室温で保存し、８時間の菌数変動を寒天培地の
混釈培養法により測定した。その結果大腸菌は３１００
０個／ｍｌから４１０個／ｍｌへと減じていた。比較の
ため比較例３の塗料で、全く同じ条件で実験したが、大
腸菌の減少は見られなかった。Example 4 In order to measure the antibacterial property of the coating film of the present invention,
20 g of the coating material of Example 1 was placed in a glass petri dish having a diameter of 80 mm, dried at 110 ° C. for 2 hours, and formed into a test body. Next, 0.6 ml of Escherichia coli bacterial solution was inoculated on the surface of the test body. A humid environment was set so that the bacterial solution was not dried, the cells were stored at room temperature in a room where light was irradiated, and the change in the number of bacteria for 8 hours was measured by a pour culture method on an agar medium. As a result, E. coli 3100
It was reduced from 0 / ml to 410 / ml. For comparison, an experiment was performed with the paint of Comparative Example 3 under exactly the same conditions, but no decrease in E. coli was observed.
【００４１】[0041]
【実施例５】実施例１の１０分の１の量で、コロイダル
シリカ共重合アクリル樹脂エマルション(大日本インキ
化学工業株式会社製 ＶＯＮＣＯＡＴ ＤＶ−９４０；
ポリマーのガラス転移温度：−２℃、コロイダルシリカ
共重合量：アクリル酸モノマー１００重量部に対し１０
０重量部、固形分：３１．０重量％、ＰＨ：８．１、粘
度：２３℃で０．００６Pa・s（６cP）、最低造膜温
度：０℃)１２００ｇに対し、酸化チタン粉末(テイカ株
式会社製 ＡＭＴ−６００、結晶型：アナタース型、純
度：９８重量％、比表面積５０ｍ２／ｇ、平均粒径：３
０ｎｍ)５０ｇと２００ｇの水のペーストを、モルタル
ミキサーでエマルションを攪拌しながら徐々に混合して
いった。次に造膜助剤、消泡剤、分散剤および流動調整
剤を一切用いず、水のみで粘度を調整した。実施例１と
同様に塗膜物性測定用塗膜フィルムを作成して、このフ
ィルムから１００ｍｍ×１０ｍｍの試験片を切り出し、
引っ張り試験に供した。測定結果は、下記のとおりであ
った。 引張強度 ６４ｋｇ／ｍｍ２ 引張伸度 １１０％ これらの値は実施例１と全く同様であり、造膜助剤、消
泡剤、分散剤および流動調整剤は塗料の特に作業性を改
良するものではあっても、塗膜物性を左右するものでは
ないことがわかった。Example 5 Colloidal with 1/10 the amount of Example 1
Silica copolymer acrylic resin emulsion (Dainippon Ink
VONCOAT DV-940 manufactured by Chemical Industry Co., Ltd .;
Glass transition temperature of polymer: -2 ° C, colloidal silica
Copolymerization amount: 10 per 100 parts by weight of acrylic acid monomer
0 parts by weight, solid content: 31.0% by weight, PH: 8.1, viscosity
Degree: 0.006 Pa · s (6 cP) at 23 ° C, minimum film forming temperature
Titanium oxide powder (Teica Corporation)
AMT-600, manufactured by Shikisha, crystal type: anatase type, pure
Degree: 98% by weight, specific surface area 50m2/ G, average particle size: 3
0nm) 50g and 200g of water paste
Mix the emulsion gradually with stirring with a mixer
said. Next, film forming aid, defoamer, dispersant and flow control
The viscosity was adjusted only with water without using any agent. Example 1 and
Similarly, a coating film for measuring coating film properties was prepared and
Cut out a 100mm x 10mm test piece from the film,
It was subjected to a tensile test. The measurement results are as follows
Was. Tensile strength 64kg / mm2 Tensile elongation 110% These values are exactly the same as those in Example 1, and
Foams, dispersants and flow modifiers can improve the workability of paints, especially.
Even if it is good, it does not affect the physical properties of the coating
I knew it wasn't.
【００４２】[0042]
【発明の効果】以上の説明からわかるように本発明に係
る塗膜は防汚性があり、ＮＯｘ分解能力の他に抗菌性を
有する。またその機能が長期間に亘って維持される。さ
らに本発明に係る塗膜は単なるアクリル樹脂との配合物
よりも耐熱性と耐薬品性があり、温度による影響を受け
にくい。本発明に係る塗料は必要に応じ水で希釈できる
水系塗料であり、乾燥に際して有害な有機溶剤を放出し
ない。さらに本発明に係る塗料は、本質的に１液型であ
り、常温乾燥するなど、作業性のよいものである。As can be seen from the above description, the coating film according to the present invention has antifouling properties and has antibacterial properties in addition to NOx decomposing ability. Also, its function is maintained for a long time. Further, the coating film according to the present invention has higher heat resistance and chemical resistance than a simple blend with an acrylic resin, and is less affected by temperature. The paint according to the present invention is a water-based paint which can be diluted with water as required, and does not emit harmful organic solvents upon drying. Furthermore, the paint according to the present invention is of a one-pack type in nature and has good workability such as drying at room temperature.
【００４３】本発明に係る塗料は、防汚、ＮＯｘ分解塗
料として構造物の外装、特に出窓や換気口の下の雨垂れ
汚れを起こす壁部分、屋根材、看板、車両、自動車、自
動販売機または道路周辺のコンクリート、トンネルの出
入り口などの塗装に使用することができる。とくに本発
明に係る塗料で塗装された外壁材などは、汚れが雨で流
し落とせる程に分解されるので、セルフクリーニング効
果とも言い得て、長期に亘りクリーンな表面を保つこと
ができる。本発明に係る塗料はまた抗菌性を利用して、
病院、養老院または食品を扱う部屋の内装塗料としても
使用できる。さらに本発明に係る塗料は機能性のある接
着剤としてフィルターなどに利用できる。また本発明に
係る塗料は広範な意味では劣化防止剤であり、劣化し易
い例えば外装の目地等にコートして利用できる。本発明
によれば、上で述べた防汚性などを有する塗膜を生成し
得る塗料、その塗料の塗装方法および防汚性などを有す
る塗膜が提供される。The paint according to the present invention is used as an antifouling, NOx decomposing paint for the exterior of a structure, especially for a wall portion, a roof material, a signboard, a vehicle, an automobile, a vending machine or the like, which causes raindrops under bay windows and ventilation openings. It can be used for painting concrete around roads and entrances and exits of tunnels. In particular, the outer wall material or the like coated with the paint according to the present invention is decomposed to such an extent that dirt can be washed away by rain, so that it can be said to be a self-cleaning effect, and a clean surface can be maintained for a long period of time. The paint according to the present invention also utilizes antibacterial properties,
It can also be used as interior paint for hospitals, nursing homes or food handling rooms. Further, the paint according to the present invention can be used as a functional adhesive for filters and the like. Further, the paint according to the present invention is a deterioration inhibitor in a broad sense, and can be used by coating it on the joints of the exterior which are liable to deteriorate, for example. According to the present invention, there are provided a paint capable of forming the above-mentioned paint film having antifouling properties, a coating method of the paint, and a paint film having antifouling properties.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０５Ｄ 7/24 ３０３ Ｃ０９Ｄ 5/00 Ｄ Ｃ０９Ｄ 5/00 Ｚ 5/02 5/02 151/10 151/10 Ｂ０１Ｄ 53/36 Ｊ Ｆターム(参考） 4D048 AA06 AB03 BA06X BA07X BA41X EA01 4D075 BB24Y CA34 DB02 DB12 DC03 DC05 DC12 EA13 EB22 EC03 4G069 AA03 AA08 BA02A BA02B BA04A BA04B BA48A CD10 DA05 EA08 EB18X EB18Y EB19 EC22Y FA03 FB23 FB29 4J038 CG031 CG141 CH031 CJ031 CJ081 CJ131 GA10 HA216 HA446 KA04 KA20 MA02 MA10 MA14 NA02 NA03 NA04 NA05 NA14 NA23 PA12 PB02 PB05 PB07 PC01 PC02 PC04──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B05D 7/24 303 C09D 5/00 D C09D 5/00 Z 5/02 5/02 151/10 151/10 B01D 53/36 J F term (reference) 4D048 AA06 AB03 BA06X BA07X BA41X EA01 4D075 BB24Y CA34 DB02 DB12 DC03 DC05 DC12 EA13 EB22 EC03 4G069 AA03 AA08 BA02A BA02B BA04A BA04B BA48A CD10 DA05 EB08 EB18 EB18 EB18 EB18 EB08 CJ031 CJ081 CJ131 GA10 HA216 HA446 KA04 KA20 MA02 MA10 MA14 NA02 NA03 NA04 NA05 NA14 NA23 PA12 PB02 PB05 PB07 PC01 PC02 PC04
Claims (14)
ダルシリカ共重合アクリル樹脂エマルションへ配合して
なる、エマルション塗料。1. An emulsion paint comprising titanium oxide having photocatalytic activity mixed with a colloidal silica copolymer acrylic resin emulsion.
マルションと、それに分散した光触媒能を有する酸化チ
タンとを含有する、エマルション塗料。2. An emulsion paint comprising a colloidal silica copolymerized acrylic resin emulsion and titanium oxide having photocatalytic activity dispersed therein.
エマルションが、無水ケイ酸とアクリル系モノマーとの
エマルション共重合によって得られるエマルションであ
る、請求項１または２に記載のエマルション塗料。3. The emulsion paint according to claim 1, wherein the colloidal silica copolymerized acrylic resin emulsion is an emulsion obtained by emulsion copolymerization of silicic anhydride and an acrylic monomer.
量部あたり、５０〜４０００重量部のコロイダルシリカ
共重合アクリル樹脂固形分を含有する、請求項１〜３の
いずれか１項に記載のエマルション塗料。4. The emulsion paint according to claim 1, wherein the emulsion paint contains 50 to 4000 parts by weight of a colloidal silica copolymerized acrylic resin solid content per 100 parts by weight of the titanium oxide having photocatalytic ability. .
１８０ｎｍの平均粒径を有する酸化チタン粉末である、
請求項１〜４のいずれか１項に記載のエマルション塗
料。5. The titanium oxide having a photocatalytic ability is 1 to 5.
A titanium oxide powder having an average particle size of 180 nm,
The emulsion paint according to any one of claims 1 to 4.
エマルションが、アクリル系モノマー１００重量部を、
２０〜５００重量部の無水ケイ酸とエマルション共重合
することによって得られるエマルションである、請求項
１〜５のいずれか１項に記載のエマルション塗料。6. The colloidal silica copolymerized acrylic resin emulsion contains 100 parts by weight of an acrylic monomer,
The emulsion paint according to any one of claims 1 to 5, which is an emulsion obtained by emulsion copolymerization with 20 to 500 parts by weight of silicic anhydride.
を有する粒子である、請求項３または６に記載のエマル
ション塗料。7. The emulsion paint according to claim 3, wherein the silicic anhydride is particles having an average particle size of 5 to 80 nm.
固形分が、該コロイダルシリカ共重合アクリル樹脂エマ
ルションの５〜７０重量％である、請求項１〜７のいず
れか１項に記載のエマルション塗料。8. The emulsion paint according to claim 1, wherein the solid content of the colloidal silica copolymerized acrylic resin is 5 to 70% by weight of the colloidal silica copolymerized acrylic resin emulsion.
マルション塗料を塗布しそして乾燥または焼き付けする
ことによって、塗膜を形成することを特徴とする、塗装
方法。9. A coating method, characterized in that a coating film is formed by applying the emulsion coating material according to claim 1 and drying or baking it.
エマルションを含有し、かつ光触媒能を有する酸化チタ
ンを含有しないエマルション塗料を塗布しそして乾燥ま
たは焼き付けすることによって、下地を形成し、次い
で、請求項１〜８のいずれか１項に記載のエマルション
塗料を、下地の上に塗布しそして乾燥または焼き付けす
ることによって、下地の上に、塗膜を形成することを特
徴とする、塗装方法。10. A base material is formed by applying an emulsion paint containing a colloidal silica copolymerized acrylic resin emulsion and not containing titanium oxide having photocatalytic activity, followed by drying or baking. A coating method, characterized in that a coating film is formed on a base by applying the emulsion paint according to any one of the above items 8 on the base and drying or baking.
によって形成した塗膜。11. A coating film formed by the coating method according to claim 9.
と、それに分散した光触媒能を有する酸化チタンを含有
する塗膜。12. A coating film containing colloidal silica copolymerized acrylic resin and titanium oxide having photocatalytic activity dispersed therein.
ないコロイダルシリカ共重合アクリル樹脂からなる下地
の上に形成した、コロイダルシリカ共重合アクリル樹脂
と、それに分散した光触媒能を有する酸化チタンを含有
する塗膜。13. A coating comprising a colloidal silica copolymerized acrylic resin formed on a base made of a colloidal silica copolymerized acrylic resin not containing titanium oxide having a photocatalytic function and titanium oxide having a photocatalytic function dispersed therein. film.
量部あたり、５０〜４０００重量部のコロイダルシリカ
共重合アクリル樹脂を含有する請求項１２または１３に
記載の塗膜。14. The coating film according to claim 12, comprising 50 to 4000 parts by weight of a colloidal silica copolymer acrylic resin per 100 parts by weight of titanium oxide having photocatalytic ability.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001157988A JP2002348525A (en) | 2001-05-25 | 2001-05-25 | Emulsion coating containing titanium oxide having photocatalytic activity, coating method using the same and its coated film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001157988A JP2002348525A (en) | 2001-05-25 | 2001-05-25 | Emulsion coating containing titanium oxide having photocatalytic activity, coating method using the same and its coated film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002348525A true JP2002348525A (en) | 2002-12-04 |
Family
ID=19001768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001157988A Pending JP2002348525A (en) | 2001-05-25 | 2001-05-25 | Emulsion coating containing titanium oxide having photocatalytic activity, coating method using the same and its coated film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002348525A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007177605A (en) * | 2005-12-01 | 2007-07-12 | Kubota Matsushitadenko Exterior Works Ltd | Roof structure |
| JP2008120055A (en) * | 2006-11-16 | 2008-05-29 | Toyoda Insatsu Kk | Printed matter with photocatalyst and its continuous manufacturing method |
| JP2008519116A (en) * | 2004-11-05 | 2008-06-05 | ビーエーエスエフ ソシエタス・ヨーロピア | Coating material |
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| JP2008519116A (en) * | 2004-11-05 | 2008-06-05 | ビーエーエスエフ ソシエタス・ヨーロピア | Coating material |
| KR101278128B1 (en) * | 2005-08-31 | 2013-06-24 | 미쓰이 가가쿠 토세로 가부시키가이샤 | Gas barrier film, gas barrier laminate and method for production of the film or laminate |
| JP2007177605A (en) * | 2005-12-01 | 2007-07-12 | Kubota Matsushitadenko Exterior Works Ltd | Roof structure |
| JP2008120055A (en) * | 2006-11-16 | 2008-05-29 | Toyoda Insatsu Kk | Printed matter with photocatalyst and its continuous manufacturing method |
| JP2008169400A (en) * | 2008-02-25 | 2008-07-24 | Mitsubishi Materials Corp | Method for manufacturing photocatalytic paint |
| JP4710919B2 (en) * | 2008-02-25 | 2011-06-29 | 三菱マテリアル株式会社 | Method for producing photocatalyst paint |
| EP2153897A1 (en) * | 2008-07-25 | 2010-02-17 | Neoformula Consulting & Développement | Transparent photocatalytic composition for internal and external building construction elements |
| JP2015520784A (en) * | 2012-05-05 | 2015-07-23 | ベーカー ギウリニ ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＫ Ｇｉｕｌｉｎｉ ＧｍｂＨ | Use of lithium polyacrylate as a dispersant |
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| US10301477B2 (en) * | 2013-03-15 | 2019-05-28 | Behr Process Corporation | Superhydrophilic coating composition |
| CN109749548A (en) * | 2017-08-22 | 2019-05-14 | 上海三银涂料科技股份有限公司 | Environmental protection coating material and preparation method thereof |
| CN109651908A (en) * | 2017-10-12 | 2019-04-19 | 上海三银涂料科技股份有限公司 | Environment-friendly type noise-proofing indoor coating and preparation method thereof |
| CN109694630A (en) * | 2017-10-24 | 2019-04-30 | 上海三银涂料科技股份有限公司 | Aqueous, environmental protective heat-insulating flame-retardant coating and preparation method thereof |
| CN110684411A (en) * | 2018-12-10 | 2020-01-14 | 哈尔滨雨阳佳泰环保新材料有限公司 | Nano TiO with catalytic property2Reflective heat-insulating finish paint and preparation and application thereof |
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