JP4348679B2 - Photocatalyst carrying paint and photocatalyst using the same - Google Patents
Photocatalyst carrying paint and photocatalyst using the same Download PDFInfo
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- JP4348679B2 JP4348679B2 JP2003288791A JP2003288791A JP4348679B2 JP 4348679 B2 JP4348679 B2 JP 4348679B2 JP 2003288791 A JP2003288791 A JP 2003288791A JP 2003288791 A JP2003288791 A JP 2003288791A JP 4348679 B2 JP4348679 B2 JP 4348679B2
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- photocatalyst
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- ammonium phosphate
- silicon compound
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- 239000011941 photocatalyst Substances 0.000 title claims description 44
- 239000003973 paint Substances 0.000 title claims description 29
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 32
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 24
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 24
- 239000004254 Ammonium phosphate Substances 0.000 claims description 23
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 23
- 150000003377 silicon compounds Chemical class 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- 239000002612 dispersion medium Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008119 colloidal silica Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 description 17
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000004332 deodorization Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- -1 alkyl silicate Chemical compound 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 2
- 229960002261 magnesium phosphate Drugs 0.000 description 2
- 235000010994 magnesium phosphates Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- ORVGYTXFUWTWDM-UHFFFAOYSA-N silicic acid;sodium Chemical compound [Na].O[Si](O)(O)O ORVGYTXFUWTWDM-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 101100258086 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-01 gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DIFFLMNDXWOKQJ-UHFFFAOYSA-N [K].O[Si](O)(O)O Chemical compound [K].O[Si](O)(O)O DIFFLMNDXWOKQJ-UHFFFAOYSA-N 0.000 description 1
- AWSZRNUJNSWBRK-UHFFFAOYSA-N [Li].[Si](O)(O)(O)O Chemical compound [Li].[Si](O)(O)(O)O AWSZRNUJNSWBRK-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229940009868 aluminum magnesium silicate Drugs 0.000 description 1
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940032158 sodium silicate Drugs 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
本発明は、塗料安定性が高く、耐久性に優れた光触媒体を得るための光触媒担持用塗料に関する。 The present invention relates to a photocatalyst-supporting paint for obtaining a photocatalyst having high paint stability and excellent durability.
光触媒はそのバンドギャップ以上のエネルギーを持つ波長の光を照射すると励起し、強い触媒活性が発現するものである。特に有機物やＮＯｘ等の一部無機物の酸化・分解力が大きく、エネルギー源として低コストで、環境負荷の非常に小さい光を利用できることから、近年環境浄化や脱臭、防汚、殺菌等へ応用されている。また、光触媒が励起するとその表面が親水性になり水との接触角が低下することが見出され、この作用を利用して防曇、防汚等への応用も進められている。光触媒には酸化物や硫化物等の金属化合物が用いられており、通常、前記用途にはこれらの光触媒を基体表面上に担持させた形態、所謂光触媒体として適用されている。 A photocatalyst is excited when irradiated with light having a wavelength equal to or greater than its band gap, and exhibits strong catalytic activity. In particular, some inorganic substances such as organic substances and NOx have large oxidizing and decomposing power, low cost as an energy source, and use of light with very little environmental impact, so it has recently been applied to environmental purification, deodorization, antifouling, sterilization, etc. ing. Further, it has been found that when the photocatalyst is excited, its surface becomes hydrophilic and the contact angle with water is lowered, and application to antifogging, antifouling, etc. is being promoted by utilizing this action. Metal compounds such as oxides and sulfides are used for the photocatalyst. Usually, the photocatalyst is applied as a so-called photocatalyst in a form in which these photocatalysts are supported on the substrate surface.
光触媒体を得る方法としては、金属のアルコキシド、アセチルアセトネート等の金属有機化合物を加水分解することにより得られた金属酸化物ゾルをバインダーに用い、基体表面上に光触媒を含む光触媒性塗膜を形成する技術が知られている（特許文献１参照）。金属酸化物ゾルのような無機系バインダーは光触媒作用により分解され難く、しかもスパッタ、真空蒸着等と比較して特別な設備を要しないので、工業的、経済的に有利に光触媒体が得られる。また、バインダーとしてアルカリケイ酸塩を用いる際に、リン酸、リン酸マグネシウム、リン酸アルミニウム、リン酸アンモニウムなどのバインダーの硬化を促進する硬化触媒を配合することが知られている（例えば、特許文献２参照）。また、バインダーとしてアルキルシリケートとアルカリケイ酸塩を用い、更にセルロース、ポリビニルアルコール等の高分子増粘剤を用いた光触媒性コート剤が提案されている（特許文献３参照）。 As a method for obtaining a photocatalyst, a metal oxide sol obtained by hydrolyzing a metal organic compound such as a metal alkoxide or acetylacetonate is used as a binder, and a photocatalytic coating film containing a photocatalyst is formed on the substrate surface. A forming technique is known (see Patent Document 1). Inorganic binders such as metal oxide sols are not easily decomposed by the photocatalytic action, and no special equipment is required as compared with sputtering, vacuum deposition, etc., so that a photocatalyst can be obtained advantageously industrially and economically. In addition, when using an alkali silicate as a binder, it is known to incorporate a curing catalyst that accelerates the curing of the binder such as phosphoric acid, magnesium phosphate, aluminum phosphate, and ammonium phosphate (for example, patents) Reference 2). Further, a photocatalytic coating agent using an alkyl silicate and an alkali silicate as a binder and further using a polymer thickener such as cellulose and polyvinyl alcohol has been proposed (see Patent Document 3).
前記特許文献１の金属酸化物ゾルは粘度が低く塗装性が悪い上に、保管中に光触媒が凝集、沈降してしまう。光触媒に用いる金属化合物は、一般的に微粒子で表面エネルギーが大きいので、強固な凝集物を形成し易く、このため、撹拌しても凝集物が十分に再分散せず、光触媒の有する光触媒活性が発現され難い。前記特許文献２などに記載の硬化触媒は、塗料のポットライフとの関係から、塗装直前に配合する必要があり、予め配合すると硬化が進み塗料安定性が悪くなる。また、前記特許文献３記載のコート剤は高分子増粘剤を用いているので、粘性が高く塗装性には優れているが、高分子増粘剤が有機系であるため、塗膜形成後、光触媒の作用により高分子増粘剤が分解され、塗膜中に欠陥が生じて塗膜強度が低下する。従来より塗料分野では、酸化アルミニウム、酸化マグネシウム、ケイ酸アルミニウムマグネシウム、粘土鉱物等の無機系増粘剤も知られているが、所望の塗料粘度を得るのに多くの量を要するので、塗膜中の光触媒の濃度を高くできない。本発明は、以上に述べた従来技術の問題点を克服し、塗料安定性に優れ、光触媒活性と塗膜強度が高い光触媒性塗膜を形成することができる光触媒担持用塗料を提供する。 The metal oxide sol of Patent Document 1 has a low viscosity and poor paintability, and the photocatalyst aggregates and settles during storage. Since the metal compound used for the photocatalyst is generally fine particles and has a large surface energy, it is easy to form strong aggregates. Therefore, even when stirred, the aggregates are not sufficiently redispersed, and the photocatalytic activity of the photocatalyst is high. It is hard to be expressed. The curing catalyst described in Patent Document 2 and the like needs to be blended immediately before coating because of the relationship with the pot life of the coating. If blended in advance, curing progresses and coating stability deteriorates. The coating agent described in Patent Document 3 uses a polymer thickener, so it has high viscosity and excellent paintability. However, since the polymer thickener is organic, The polymer thickener is decomposed by the action of the photocatalyst, and defects are generated in the coating film, resulting in a decrease in coating film strength. Conventionally, in the paint field, inorganic thickeners such as aluminum oxide, magnesium oxide, aluminum magnesium silicate, and clay minerals are also known, but a large amount is required to obtain a desired paint viscosity. The concentration of the photocatalyst cannot be increased. The present invention provides a photocatalyst-supporting coating material that can overcome the above-described problems of the prior art, and that can form a photocatalytic coating film that has excellent coating stability, high photocatalytic activity, and high coating strength.
本発明者は鋭意研究を重ねた結果、無機系バインダーに重合性ケイ素化合物を用い、一定量のリン酸アンモニウムを配合すると、塗料粘度が大きくなり塗装性が改善されるとともに、意外にも塗料安定性が図れることを見出し、本発明を完成した。 As a result of intensive research, the inventor has used a polymerizable silicon compound in an inorganic binder, and when a certain amount of ammonium phosphate is blended, the paint viscosity is increased and the paintability is improved. As a result, the present invention was completed.
即ち、本発明は、光触媒、重合性ケイ素化合物、リン酸アンモニウム及び分散媒を含み、リン酸アンモニウムの含有量が重量比でリン酸アンモニウム／重合性ケイ素化合物＝１／３０〜１／８の範囲にあることを特徴とする光触媒担持用塗料、及び、この塗料を用いて基体表面に光触媒を担持させてなることを特徴とする光触媒体である。 That is, the present invention includes a photocatalyst, a polymerizable silicon compound, ammonium phosphate and a dispersion medium, and the ammonium phosphate content is in the range of ammonium phosphate / polymerizable silicon compound = 1/30 to 1/8 in weight ratio. A photocatalyst-supporting coating material, and a photocatalyst body characterized in that a photocatalyst is supported on the surface of a substrate using the coating material.
本発明の塗料は、光触媒作用ではほとんど分解されない重合性ケイ素化合物をバインダーとして用いており、リン酸アンモニウムを配合することで、塗料安定性が高く、これを用いると耐久性が優れた光触媒体を得ることができる。 The coating material of the present invention uses a polymerizable silicon compound that is hardly decomposed by photocatalytic action as a binder. By adding ammonium phosphate, the coating material stability is high, and when this is used, a photocatalyst having excellent durability can be obtained. Obtainable.
本発明は光触媒、無機系バインダーとしての重合性ケイ素化合物、リン酸アンモニウム及び分散媒とを含む光触媒担持用塗料であって、リン酸アンモニウムの含有量が重量比で、リン酸アンモニウム／重合性ケイ素化合物＝１／３０〜１／８の範囲にある。リン酸アンモニウムの配合量が前記範囲内であれば、重合性ケイ素化合物の反応が部分的に生じるので、適度な粘性を塗料に付与できるものと推測される。このため、本発明の塗料は安定性に優れており、しかもリン酸アンモニウムや重合性ケイ素化合物は光触媒作用では分解され難いので、耐久性の優れた塗膜を基体表面に形成することができると考えられる。前記範囲よりリン酸アンモニウムの配合量が少ないと、所望の塗料粘度が得られず、多いと重合性ケイ素化合物との反応が進み過ぎ、塗料のポットライフが低下して塗料の保管中にゲル化または硬化してしまう。この重量比が１／２０〜１／１０の範囲であれば、更に好ましい。更に、塗装性にも優れ、厚塗りが可能となるので、厚膜の、即ち光触媒活性の優れた光触媒性塗膜を形成できる。一方、リン酸アンモニウム以外のリン酸、リン酸マグネシウム、リン酸アルミニウムなどの硬化触媒を用いると重合性ケイ素化合物の硬化を著しく促進し、塗料のポットライフが低下して塗料の保管中にゲル化または硬化してしまい、それらの硬化触媒の配合量を制御しても所望の塗料安定性を得ることはできない。本発明の塗料の粘度は、リン酸アンモニウムの配合量、固形分濃度により調整でき、基体の種類や塗装方法等に応じて適宜設定するが、通常は５０〜１０００ｍＰａ・ｓの範囲が好ましい。この範囲より低いと本発明に所望される塗装性が得られ難く、この範囲より高くなるとレベリング性が低下して平滑な塗膜が形成でき難く、場合によっては塗装が困難になる。より好ましい範囲は、５０〜５００ｍＰａ・ｓである。固形分濃度は、１〜５０重量％の範囲が好ましく、１０〜４０重量％の範囲が更に好ましい。 The present invention is a photocatalyst-supporting coating material comprising a photocatalyst, a polymerizable silicon compound as an inorganic binder, ammonium phosphate and a dispersion medium, wherein the ammonium phosphate content is in a weight ratio, and ammonium phosphate / polymerizable silicon. Compound = 1/30 to 1/8. If the blending amount of ammonium phosphate is within the above range, the reaction of the polymerizable silicon compound partially occurs, and it is estimated that an appropriate viscosity can be imparted to the paint. For this reason, the coating material of the present invention is excellent in stability, and ammonium phosphate and polymerizable silicon compounds are difficult to be decomposed by photocatalytic action, so that a highly durable coating film can be formed on the substrate surface. Conceivable. If the amount of ammonium phosphate is less than the above range, the desired paint viscosity cannot be obtained, and if it is too large, the reaction with the polymerizable silicon compound proceeds excessively, and the pot life of the paint is reduced, causing gelation during storage of the paint. Or it hardens. The weight ratio is more preferably in the range of 1/20 to 1/10. Furthermore, since it is excellent in paintability and can be thickly coated, a thick film, that is, a photocatalytic coating film excellent in photocatalytic activity can be formed. On the other hand, if a curing catalyst such as phosphoric acid other than ammonium phosphate, magnesium phosphate, or aluminum phosphate is used, the curing of the polymerizable silicon compound is remarkably accelerated, and the pot life of the paint is reduced, resulting in gelation during storage of the paint. Or it will harden | cure and even if it controls the compounding quantity of those curing catalysts, desired paint stability cannot be obtained. The viscosity of the paint of the present invention can be adjusted by the blending amount of ammonium phosphate and the solid content concentration, and is appropriately set according to the type of substrate, the coating method, and the like, but is usually preferably in the range of 50 to 1000 mPa · s. If it is lower than this range, it is difficult to obtain the coating properties desired in the present invention, and if it is higher than this range, the leveling properties are lowered and it is difficult to form a smooth coating film, and in some cases, coating becomes difficult. A more preferable range is 50 to 500 mPa · s. The solid content concentration is preferably in the range of 1 to 50% by weight, more preferably in the range of 10 to 40% by weight.
本発明におけるリン酸アンモニウムとは、リン酸２水素アンモニウム（ＮＨ４Ｈ２ＰＯ４）、リン酸水素２アンモニウム（（ＮＨ４）２ＨＰＯ４）、リン酸３アンモニウム（（ＮＨ４）３ＰＯ４）またはそれらの水和物を包含する化合物であり、これらは１種で用いても、２種以上を用いても良い。 In the present invention, ammonium phosphate refers to ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), di-ammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ), and tri-ammonium phosphate ((NH 4 ) 3 PO 4. Or a hydrate thereof, and these may be used alone or in combination of two or more.
本発明で用いることのできる重合性ケイ素化合物としては、例えば、加水分解性シランまたはその加水分解生成物またはその部分縮合物、水ガラス、コロイダルシリカ、オルガノポリシロキサン等が挙げられ、これらの中の１種を用いても、２種以上を混合して用いても良い。加水分解性シランはアルコキシ基、ハロゲン基等の加水分解性基を少なくとも１個含むもので、中でもアルコキシシランが安定性、経済性の点で望ましく、特に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が反応性が高く好ましい。水ガラスとしてはナトリウム−ケイ酸系、カリウム−ケイ酸系、リチウム−ケイ酸系等を用いることができ、中でもナトリウム−ケイ酸系が安定性が高いので好ましい。ナトリウム−ケイ酸系の水ガラスはＮａ２ＯとＳｉＯ２のモル比が２〜４の範囲にあると硬化性が高く、安定性と硬化性とのバランスから前記モル比が３の３号水ガラスが特に好ましい。コロイダルシリカやオルガノポリシロキサンとしては、シラノール基を有するものを用いることができる。 Examples of the polymerizable silicon compound that can be used in the present invention include hydrolyzable silane or its hydrolysis product or its partial condensate, water glass, colloidal silica, organopolysiloxane, and the like. One type may be used, or two or more types may be mixed and used. Hydrolyzable silanes contain at least one hydrolyzable group such as an alkoxy group or a halogen group. Among these, alkoxysilanes are desirable in terms of stability and economy, and in particular, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane. Silane is preferred because of its high reactivity. As the water glass, sodium-silicic acid system, potassium-silicic acid system, lithium-silicic acid system and the like can be used. Among them, sodium-silicic acid system is preferable because of high stability. A sodium-silicate-based water glass has high curability when the molar ratio of Na 2 O and SiO 2 is in the range of 2 to 4, and No. 3 water has a molar ratio of 3 from the balance between stability and curability. Glass is particularly preferred. As colloidal silica or organopolysiloxane, those having a silanol group can be used.
光触媒としては、バンドギャップ以上のエネルギーを有する波長の光を照射することにより、触媒活性を示すものであれば特に制限はなく、例えば酸化チタン、酸化亜鉛、酸化タングステン、酸化鉄、あるいはそれらの２種以上の混合物、複合物等の公知のものを用いることができる。また光触媒にはその触媒活性を高めるなどのためにバナジウム、鉄、コバルト、ニッケル、銅、亜鉛等の元素が、１種または２種以上含有しても良い。光触媒の中でも酸化チタン、特に平均一次粒子径が０．００５〜０．１μｍの範囲の微粒子のものが光触媒活性が高いので好ましい。用いることのできる酸化チタンの種類には特に制限はなく、無水酸化チタン、含水酸化チタン、水酸化チタン、チタン酸等いずれでも良く、またルチル型やアナターゼ型等の結晶性のものや不定形であっても良く、これらが混合したものであっても良い。光触媒の含有量は塗料の固形分に対し５０〜９５重量％の範囲が好ましく、７０〜９５重量％の範囲がより好ましい。 The photocatalyst is not particularly limited as long as it exhibits catalytic activity by irradiating light having a wavelength greater than the band gap. For example, titanium oxide, zinc oxide, tungsten oxide, iron oxide, or their two A known material such as a mixture or composite of two or more species can be used. The photocatalyst may contain one or more elements such as vanadium, iron, cobalt, nickel, copper and zinc in order to increase the catalytic activity. Among photocatalysts, titanium oxide, particularly those having an average primary particle diameter in the range of 0.005 to 0.1 μm, are preferable because of high photocatalytic activity. The type of titanium oxide that can be used is not particularly limited, and may be any of anhydrous titanium oxide, hydrous titanium oxide, titanium hydroxide, titanic acid, etc., and may be crystalline or amorphous such as a rutile type or anatase type. It may be present or a mixture thereof. The content of the photocatalyst is preferably in the range of 50 to 95% by weight, more preferably in the range of 70 to 95% by weight, based on the solid content of the paint.
分散媒には重合性ケイ素化合物との相溶性に応じ、水、またはアルコール類等の有機溶剤、あるいはそれらの混合物から選択する。 The dispersion medium is selected from water, an organic solvent such as alcohols, or a mixture thereof according to the compatibility with the polymerizable silicon compound.
本発明の塗料には、光触媒、重合性ケイ素化合物、リン酸アンモニウム、分散媒以外にも、本発明の効果を損ねない範囲で、ｐＨ調整剤、分散剤、消泡剤、乳化剤、着色剤、増量剤、防カビ剤、硬化助剤、増粘助剤等の各種添加剤、充填剤等が含まれていても良い。これらの添加剤または充填剤が不揮発性であれば、光触媒作用により分解され難い無機系のものを選択するのが好ましい。 In the paint of the present invention, in addition to the photocatalyst, polymerizable silicon compound, ammonium phosphate and dispersion medium, a pH adjuster, a dispersant, an antifoaming agent, an emulsifier, a colorant, as long as the effects of the present invention are not impaired. Various additives such as extenders, fungicides, curing aids, thickening aids, fillers and the like may be included. If these additives or fillers are non-volatile, it is preferable to select an inorganic material that is difficult to be decomposed by the photocatalytic action.
本発明の塗料を得るには、先ず、サンドミル、ディスパー、ボールミル、ペイントシェイカー、２本ロールミル、３本ロールミル等の分散機を用いて光触媒を分散媒中に分散させる。前記重合性ケイ素化合物、リン酸アンモニウム、その他の各種添加剤、充填剤は、分散の前または後で加える。 In order to obtain the paint of the present invention, first, the photocatalyst is dispersed in a dispersion medium using a dispersing machine such as a sand mill, a disper, a ball mill, a paint shaker, a two-roll mill, or a three-roll mill. The polymerizable silicon compound, ammonium phosphate, other various additives and fillers are added before or after dispersion.
次に、本発明は光触媒体であって、前記塗料を用い、基体表面に光触媒を担持させたものである。前記塗料は塗装適性が優れており、厚膜の塗膜を形成できるので、本発明の光触媒体は特に脱臭、ＮＯｘ除去等の強い光触媒活性を要する用途に適している。基材には、例えば、金属、タイル、ホーロー、セメント、コンクリート、ガラス、プラスチック、繊維、木材、紙等の種々の材質からなる素材を用いることができ、その形状も板状、波板状、ハニカム状、球状、曲面状等、特に制限はない。塗料の塗布方法にはスプレー塗装、ローラーコート、ディップコート、フローコート、ナイフコート、静電塗装、バーコート、ダイコート、ハケ塗り、スピンコート等の公知の方法を用いることができる。塗料の塗工量は、塗膜の膜厚に応じて設定するが、例えば、前記の脱臭、ＮＯｘ除去等の厚膜を要する用途には、０．１ｇ／ｃｍ２以上塗布することが好ましい。前記塗料は基材の耐熱性に応じて、塗布した後、８０〜１５０℃の範囲の温度で加熱すると、乾燥が促進されるので好ましい。 Next, the present invention is a photocatalyst body, wherein the coating material is used and the photocatalyst is supported on the surface of the substrate. Since the paint has excellent paintability and can form a thick film, the photocatalyst of the present invention is particularly suitable for applications requiring strong photocatalytic activity such as deodorization and NOx removal. For the base material, for example, materials made of various materials such as metal, tile, enamel, cement, concrete, glass, plastic, fiber, wood, paper, etc. can be used, and the shape is also plate-like, corrugated, There is no particular limitation on the shape of a honeycomb, a sphere, a curved surface, or the like. As a method for applying the paint, known methods such as spray coating, roller coating, dip coating, flow coating, knife coating, electrostatic coating, bar coating, die coating, brush coating, and spin coating can be used. The coating amount of the paint is set according to the film thickness of the coating film. For example, for applications requiring a thick film such as deodorization and NOx removal, it is preferable to apply 0.1 g / cm 2 or more. The coating is preferably heated at a temperature in the range of 80 to 150 ° C. after application, depending on the heat resistance of the substrate, since drying is accelerated.
以下に本発明の実施例を示すが、本発明はこれらに制限されるものではない。 Examples of the present invention are shown below, but the present invention is not limited thereto.
実施例１
光触媒酸化チタンの水性分散体（ＳＴＳ−０１、石原産業製）を水酸化ナトリウムを用いてｐＨを７に調整した後ろ過して、酸化チタンの含水ケーキを得た。この含水ケーキを酸化チタン濃度が５０ｇ／リットルになるように、分散媒として純水を用い、ディスパーで撹拌して再分散させスラリー化した。再分散スラリー６０ｇに無機系バインダーとして３号水ガラス３．５６ｇ、２００ｇ／リットルのリン酸２水素アンモニウム水溶液１ｃｃを加えた後、固形分濃度が２０重量％になるように純水で調整し、本発明の光触媒担持用塗料を得た。これを試料Ａとする。光触媒は固形分中に９０重量％含まれ、リン酸アンモニウム／３号水ガラスの重量比は１／１８である。
Example 1
An aqueous dispersion of photocatalytic titanium oxide (STS-01, manufactured by Ishihara Sangyo Co., Ltd.) was adjusted to pH 7 with sodium hydroxide and then filtered to obtain a water-containing titanium oxide cake. This water-containing cake was slurried by being redispersed by stirring with a disper using pure water as a dispersion medium so that the titanium oxide concentration becomes 50 g / liter. After adding 3.56 g of No. 3 water glass as an inorganic binder and 1 cc of 200 g / liter of ammonium dihydrogen phosphate aqueous solution as an inorganic binder to 60 g of the redispersed slurry, it was adjusted with pure water so that the solid content concentration was 20% by weight, A paint for carrying a photocatalyst of the present invention was obtained. This is designated as sample A. The photocatalyst is contained 90% by weight in the solid content, and the weight ratio of ammonium phosphate / 3 water glass is 1/18.
比較例１
リン酸アンモニウムを用いないこと以外は、実施例１と同様にして光触媒担持用塗料を得た。これを試料Ｂとする。
Comparative Example 1
A photocatalyst-supporting paint was obtained in the same manner as in Example 1 except that ammonium phosphate was not used. This is designated as Sample B.
評価１：粘度、塗料安定性
実施例１及び比較例１で得られた試料Ａ、Ｂの粘度を測定した。また、試料を１週間静置し、目視により分散状態を評価した。
Evaluation 1: Viscosity and paint stability The viscosities of Samples A and B obtained in Example 1 and Comparative Example 1 were measured. Moreover, the sample was left still for one week and the dispersion state was evaluated visually.
評価２：アセトアルデヒド除去能力
実施例１及び比較例１で得られた試料Ａ、Ｂを、１１０℃の温度で１２時間加熱して硬化させ、ライカイ機で粉砕して光触媒粉末を得た。この光触媒粉末０．１ｇを６ｃｍ２のシャーレ上に秤量し、０．５ミリリットルの純水を加えて均一に広げ、１１０℃の温度で３０分間乾燥した後、デシケーター中で放冷した。このシャーレを０．８リットルのパイレックス(登録商標)製ガラス容器に挿入し、容器を密閉した。空気で希釈したアセトアルデヒドガスをバッグに入れ、これを容器に接続し、ポンプを用いて希釈ガスを３リットル／分の速度で循環させた。循環系内のアセトアルデヒド濃度は、約１００ｐｐｍであった。次いで、暗所で３０分間安定させた後、ブラックライト（波長３００〜４００ｎｍ）を用い、試料表面の照度が０．５ｍＷ／ｃｍ２となるように紫外線を１時間照射した。紫外線照射開始から１５分毎に、循環系内のガスを分取し、ガスクロマトグラフ（ＧＣ−１４Ｂ型、島津製作所製）を用いてアセトアルデヒド濃度を測定した。紫外線照射時間に対し、照射時間毎のアセトアルデヒドの濃度減少を対数軸にプロットし、得られた直線の傾き、即ち１次反応速度定数を算出した。１次反応速度定数が大きい程、アセトアルデヒドの分解能力が大きい。
Evaluation 2: Acetaldehyde removal ability Samples A and B obtained in Example 1 and Comparative Example 1 were cured by heating at a temperature of 110 ° C. for 12 hours, and pulverized with a lye mill to obtain a photocatalyst powder. 0.1 g of this photocatalyst powder was weighed on a 6 cm 2 petri dish, uniformly added with 0.5 ml of pure water, dried at 110 ° C. for 30 minutes, and then allowed to cool in a desiccator. This petri dish was inserted into a 0.8 liter Pyrex (registered trademark) glass container, and the container was sealed. Acetaldehyde gas diluted with air was placed in a bag, connected to a container, and the dilution gas was circulated at a rate of 3 liters / minute using a pump. The concentration of acetaldehyde in the circulatory system was about 100 ppm. Subsequently, after stabilizing for 30 minutes in a dark place, using a black light (wavelength 300-400 nm), the sample surface was irradiated with ultraviolet rays for 1 hour so that the illuminance on the sample surface was 0.5 mW / cm 2 . Every 15 minutes from the start of ultraviolet irradiation, the gas in the circulation system was collected, and the acetaldehyde concentration was measured using a gas chromatograph (GC-14B type, manufactured by Shimadzu Corporation). The acetaldehyde concentration decrease for each irradiation time was plotted on the logarithmic axis against the ultraviolet irradiation time, and the slope of the obtained straight line, that is, the first-order reaction rate constant was calculated. The larger the first-order reaction rate constant, the greater the ability to decompose acetaldehyde.
評価１、２の結果を表１に示す。本発明の塗料は粘度が高く、塗料安定性が優れていることが判る。また、リン酸アンモニウムを加えても反応速度定数は同等であり、光触媒活性を阻害しないことが判った。 The results of evaluations 1 and 2 are shown in Table 1. It can be seen that the paint of the present invention has high viscosity and excellent paint stability. Further, it was found that even when ammonium phosphate was added, the reaction rate constant was the same, and the photocatalytic activity was not inhibited.
更に、実施例１で得られた試料Ａをガラス板に塗布し、乾燥して、光触媒体を得た。この光触媒体を観察したところ耐久性に優れており、また、前記と同様な方法で測定したところ光触媒活性は高いことを確認した。 Furthermore, the sample A obtained in Example 1 was applied to a glass plate and dried to obtain a photocatalyst body. When this photocatalyst was observed, it was excellent in durability, and it was confirmed that the photocatalytic activity was high when measured by the same method as described above.
本発明の光触媒担持用塗料は塗料安定性が優れており、耐久性が優れ厚膜で光触媒活性の高い光触媒体を得ることができる。この光触媒体は、特に脱臭、ＮＯｘ除去の用途に有用である。
The photocatalyst-supporting coating material of the present invention has excellent paint stability, and can provide a photocatalyst having excellent durability and a thick film and high photocatalytic activity. This photocatalyst is particularly useful for deodorization and NOx removal.
Claims (4)
A photocatalyst comprising a photocatalyst supported on the surface of a substrate using the paint according to claim 1.
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| JP2010115635A (en) * | 2008-06-05 | 2010-05-27 | Sumitomo Chemical Co Ltd | Photocatalyst dispersion, its method of manufacturing the same and application thereof |
| KR101153784B1 (en) | 2010-07-27 | 2012-06-13 | 주식회사 젠트로 | Functional paint composition and manufacturing method for the same |
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