JPH11267518A - Photocatalyst-supporting thermoplastic resin molding - Google Patents
Photocatalyst-supporting thermoplastic resin moldingInfo
- Publication number
- JPH11267518A JPH11267518A JP10316430A JP31643098A JPH11267518A JP H11267518 A JPH11267518 A JP H11267518A JP 10316430 A JP10316430 A JP 10316430A JP 31643098 A JP31643098 A JP 31643098A JP H11267518 A JPH11267518 A JP H11267518A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- thermoplastic resin
- molding
- weight
- resin plate
- 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
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 147
- 238000000465 moulding Methods 0.000 title claims abstract description 71
- 239000011941 photocatalyst Substances 0.000 claims abstract description 106
- 239000012790 adhesive layer Substances 0.000 claims abstract description 73
- 239000010410 layer Substances 0.000 claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 6
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 4
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 4
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 4
- 229920001225 polyester resin Polymers 0.000 claims abstract description 4
- 239000004645 polyester resin Substances 0.000 claims abstract description 4
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 77
- 239000011248 coating agent Substances 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 55
- 230000001699 photocatalysis Effects 0.000 claims description 28
- -1 polysiloxane Polymers 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 24
- 230000001681 protective effect Effects 0.000 claims description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 150000004706 metal oxides Chemical class 0.000 claims description 15
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 12
- 150000004692 metal hydroxides Chemical class 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 6
- 229920006267 polyester film Polymers 0.000 claims description 6
- 239000008119 colloidal silica Substances 0.000 claims description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920001955 polyphenylene ether Polymers 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims 1
- 238000007731 hot pressing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000003856 thermoforming Methods 0.000 abstract description 3
- 238000004332 deodorization Methods 0.000 abstract description 2
- 239000000088 plastic resin Substances 0.000 abstract description 2
- 239000004417 polycarbonate Substances 0.000 abstract description 2
- 229920000515 polycarbonate Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 41
- 238000011156 evaluation Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229920002050 silicone resin Polymers 0.000 description 7
- 241000588724 Escherichia coli Species 0.000 description 6
- 230000003373 anti-fouling effect Effects 0.000 description 6
- 230000000843 anti-fungal effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000007666 vacuum forming Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 240000008415 Lactuca sativa Species 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- 238000007646 gravure printing Methods 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 235000012045 salad Nutrition 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000002504 physiological saline solution Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000005956 Cosmos caudatus Nutrition 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910019899 RuO Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000007759 kiss coating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- PFWZXDDTAYMUPE-UHFFFAOYSA-N propan-2-ol;1,2-xylene Chemical compound CC(C)O.CC1=CC=CC=C1C PFWZXDDTAYMUPE-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、消臭、防汚、抗
菌、防カビ、防曇、防滴等の効果を有する光触媒担持熱
可塑性樹脂板を成形加工することにより得られる光触媒
担持熱可塑性樹脂成形体、その製造方法、光触媒担持熱
可塑性樹脂板及び電気製品用等の操作パネルに関する。The present invention relates to a photocatalyst-supporting thermoplastic resin plate obtained by molding and processing a photocatalyst-supporting thermoplastic resin plate having effects such as deodorization, antifouling, antibacterial, antifungal, antifogging, and dripproofing. The present invention relates to a resin molded product, a method for producing the same, a photocatalyst-supporting thermoplastic resin plate, and an operation panel for an electric appliance.
【０００２】[0002]
【従来の技術】紫外線のエネルギーによって、殺菌、有
機物の分解等の各種の化学反応を進行させる光触媒とし
て、ｎ型半導体の酸化チタンが知られている。光触媒を
ガラス、金属、プラスチック、タイル等に担持する方法
は種々提案されている（特開昭６２−６６８６１、特開
平５−３０９２６７、ＥＰ６３３０６４、ＵＳＰ４８８
８１０１）。しかし、光触媒活性を低下させることなく
光触媒を担持した熱可塑性樹脂板を１００〜３００℃の
温度範囲で成形加工した光触媒担持熱可塑性樹脂成形体
は知られておらず、また、かかる光触媒担持熱可塑性樹
脂板を成形加工した光触媒担持熱可塑性樹脂成形体の光
触媒作用を有効に利用して消臭、防汚、抗菌、防カビ、
防曇、防滴性を長期にわたって維持する方法についても
報告されていない。2. Description of the Related Art Titanium oxide as an n-type semiconductor is known as a photocatalyst which causes various chemical reactions such as sterilization and decomposition of organic substances by the energy of ultraviolet rays. Various methods for supporting a photocatalyst on glass, metal, plastic, tile, and the like have been proposed (JP-A-62-68661, JP-A-5-309267, EP633064, USP488).
8101). However, there is no known photocatalyst-supported thermoplastic resin molded body obtained by molding a thermoplastic resin plate supporting a photocatalyst at a temperature range of 100 to 300 ° C. without lowering the photocatalytic activity. Effective use of the photocatalytic action of the photocatalyst-supported thermoplastic resin molded article formed from a resin plate to deodorize, stain-proof, antibacterial, anti-mold,
There is no report on a method for maintaining the anti-fog and drip-proof properties over a long period of time.
【０００３】従来、屋外設置したポリカーボネート製遮
音壁などの樹脂構造体、ポリ塩化ビニルを含浸させた繊
維強化樹脂は外気中の埃やばい煙を付着しやすく通常２
〜３ケ月で黒く変色し汚染が進むため、美観を損ねると
いう大きな欠点を有していた。また、ポリ塩化ビニル樹
脂に大量に含まれる可塑剤成分などのためにカビが発生
しやすく、その対策として表面にフッ素樹脂をコートし
たりする方法が取られている。しかしながら、フッ素樹
脂のコートは従来から言われているように、表面の撥水
性を増加させ親油性を増加させるため、ばい煙等の油分
の汚れが付着しやすいものとなる欠点があった。また、
酸化チタンは大気中で紫外線を照射されると親水性を発
現するという性質を本来有しているが、この効果を利用
して屋外設置構造体の表面を親水性にし、付着したオイ
ルミストなどの油分を水（特に雨水）で洗い流し易くす
る方法も公開されている（特開昭６３−１０００４２号
公報、ＷＯ９６／２９３７５）。これらは構造体表面の
物性を親水性にすることにより、水が表面に濡れ易くな
り、結果として油分が表面から浮き上がって流れ落ちる
という現象を利用したものである。しかしながら、公開
された技術による方法では表面に付着した油分の光触媒
分解作用が乏しいため、ディーゼル車の排気ガス等の汚
れが強固に大量に付着するという道路遮音壁では実用化
に際して使用範囲の制約を受けるという大きな問題があ
った。Conventionally, resin structures such as sound insulation walls made of polycarbonate installed outdoors and fiber-reinforced resins impregnated with polyvinyl chloride are apt to adhere to dust and soot in the outside air.
In three months, the color changed to black and contamination proceeded. In addition, mold is easily generated due to a plasticizer component contained in a large amount in the polyvinyl chloride resin, and a method of coating the surface with a fluororesin has been adopted as a countermeasure. However, the fluororesin coat has a drawback that oil stains such as soot and smoke easily adhere to the surface because it increases the water repellency of the surface and increases the lipophilicity, as is conventionally known. Also,
Titanium oxide inherently has the property of exhibiting hydrophilicity when irradiated with ultraviolet light in the atmosphere, but this effect is used to make the surface of the outdoor installation structure hydrophilic, and to prevent oil mist and the like from adhering. A method of making it easy to wash off oil with water (especially rainwater) is also disclosed (JP-A-63-100042, WO96 / 29375). These methods utilize a phenomenon in which water is easily wetted on the surface by making the physical properties of the surface of the structure hydrophilic, and as a result, an oil component floats off the surface and flows down. However, in the method according to the disclosed technology, the photocatalytic decomposition action of the oil attached to the surface is poor, so that a large amount of dirt such as exhaust gas of a diesel vehicle is strongly adhered to a road noise barrier, which is limited in practical use in practical use. There was a big problem.
【０００４】また、ＷＯ９７−１３４にはディップ法や
スプレー法で樹脂基体上に、ポリシロキサンを添加した
アクリルシリコン樹脂からなる接着層を介して、金属酸
化物ゲルを含む光触媒粒子複合体からなる光触媒層を設
けることにより、高い光触媒活性と優れた耐久性を維持
した例が開示されている。また、ポリエステルフィルム
上にポリシロキサンを添加したアクリルシリコン樹脂か
らなる接着層を介して、金属酸化物ゲルを含む光触媒粒
子複合体からなる光触媒層を設けることにより、高い光
触媒活性と優れた耐久性を維持した光触媒担持熱可塑性
樹脂板も上記ＷＯ９７−１３４に公開されているが、ポ
リエステルフィルムを加熱下に成形することは何ら開示
されていない。さらに、この公開された塗布液の組成で
は、接着層に硬化剤としてシランカップリング剤を使用
していないので、フィルムの高速成膜時に乾燥硬化が不
十分となり易く塗布面が裏面に張りつき易いという問題
があった。また、特開平９−２３０１１８号公報には、
光触媒を担持した親水性を示すフィルムが開示されてい
るが、上記公報に記載された光触媒層の光触媒活性は低
いものであるため、加熱成形工程によって熱可塑性樹脂
の成分や樹脂添加剤などが光触媒層に浸透して光触媒活
性を低下させるため、得られる光触媒活性やそれに付随
する親水性や親水性の維持性も極めて低いものであっ
た。[0004] WO97-134 has a photocatalyst composed of a photocatalyst particle composite containing a metal oxide gel via a bonding layer made of an acrylic silicon resin added with polysiloxane on a resin substrate by a dipping method or a spray method. An example in which a layer is provided to maintain high photocatalytic activity and excellent durability is disclosed. In addition, by providing a photocatalyst layer made of a photocatalyst particle composite containing a metal oxide gel via an adhesive layer made of an acrylic silicone resin added with polysiloxane on a polyester film, high photocatalytic activity and excellent durability are provided. The maintained photocatalyst-carrying thermoplastic resin plate is also disclosed in the above-mentioned WO 97-134, but there is no disclosure of forming a polyester film under heating. Furthermore, in the composition of this published coating solution, since a silane coupling agent is not used as a curing agent for the adhesive layer, drying and curing are likely to be insufficient during high-speed film formation and the coated surface tends to stick to the back surface. There was a problem. Also, JP-A-9-230118 discloses that
Although a hydrophilic film carrying a photocatalyst is disclosed, since the photocatalytic activity of the photocatalyst layer described in the above publication is low, the components of the thermoplastic resin and the resin additives are subjected to the photocatalyst by the heat molding step. Since the photocatalytic activity is reduced by penetrating into the layer, the obtained photocatalytic activity and the accompanying hydrophilicity and maintenance of hydrophilicity are extremely low.
【０００５】[0005]
【発明が解決しようとする課題】従来、熱可塑性樹脂板
に、光触媒を担持させる方法としては、光触媒層塗布液
をスクリーン印刷やグラビア印刷等の印刷法、スプレー
吹き付け法、ディップコーティング法、スピンコーティ
ング法等でコートし、乾燥する方法が一般的であるが、
熱可塑性樹脂成形体の形状によってはスプレー吹き付け
法、ディップコーティング法を採用せざるを得ない場合
があり、かかるコーティング方法では、塗膜層の均一性
に欠け、美観に欠けるだけでなく、乾燥工程による手間
が大きく、経済性に乏しいという問題点があった。にも
かかわらず、これらの方法が採用されていたのは、これ
に代わる方法が知られていなかったからに他ならない。
本発明の課題は、種々の立体的な形状に成形加工したに
もかかわらず、その光触媒活性の低下がない光触媒担持
熱可塑性樹脂成形体を提供することにある。Conventionally, as a method of supporting a photocatalyst on a thermoplastic resin plate, a printing method such as screen printing or gravure printing, a spray spraying method, a dip coating method, a spin coating method, etc. The method of coating with a method etc. and drying is common,
Depending on the shape of the thermoplastic resin molded article, a spray spraying method or a dip coating method may have to be adopted, and such a coating method lacks uniformity of a coating layer, lacks aesthetics, and also causes a drying process. However, there is a problem in that it requires a lot of trouble and is not economical. Nevertheless, these methods have been adopted only because no alternative was known.
An object of the present invention is to provide a photocatalyst-supported thermoplastic resin molded article that does not decrease its photocatalytic activity despite being formed into various three-dimensional shapes.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために、光触媒を担持した熱可塑性樹脂板を
効率良く高速で熱成形加工できること、光触媒活性が光
触媒を担持した熱可塑性樹脂板を熱成形加工することに
より低下しないこと、高速成形加工が可能な材質の熱可
塑性樹脂板に光触媒を生産性良く担持できること、など
の検討項目について鋭意研究を重ね、１００〜３００℃
の加熱下に成形加工した場合であっても、光触媒担持層
が展性に富み、基材樹脂の伸びに追従し機能的にも劣ら
ないことを見出し、本発明を完成するに至った。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have found that a thermoplastic resin plate carrying a photocatalyst can be efficiently thermoformed at a high speed, and the photocatalytic activity of the thermoplastic resin plate carrying the photocatalyst can be improved. We have been conducting intensive research on the study items such as not being reduced by thermoforming the resin plate, and being able to support the photocatalyst on a thermoplastic resin plate of a material that can be molded at high speed with high productivity.
It was found that the photocatalyst-supporting layer was rich in malleability even when it was molded under the above-mentioned heating, followed the elongation of the base resin and was not inferior in function, and completed the present invention.
【０００７】すなわち本発明は、接着層を介して光触媒
層が担持された熱可塑性樹脂板からなる光触媒担持熱可
塑性樹脂板を、成形温度１００〜３００℃の範囲で成形
加工することにより得られる光触媒担持熱可塑性樹脂成
形体に関する。That is, the present invention provides a photocatalyst obtained by molding a photocatalyst-supporting thermoplastic resin plate comprising a thermoplastic resin plate carrying a photocatalyst layer via an adhesive layer at a molding temperature of 100 to 300 ° C. The present invention relates to a supported thermoplastic resin molded article.
【０００８】また本発明は、上記熱可塑性樹脂板が単層
又は多層の積層体で、ポリスチレン系樹脂、ポリエステ
ル樹脂、ポリカーボネート樹脂、ポリオレフィン樹脂、
ポリアミド樹脂、ポリ塩化ビニル樹脂、ＡＢＳ樹脂、ア
クリル系樹脂、ポリフェニレンエーテル樹脂の中から選
ばれた樹脂からなること、熱可塑性樹脂板の厚みが５０
μｍ〜１０ｍｍであること、接着層が硬化剤としてシラ
ンカップリング剤を含有する接着層塗布液の塗布により
形成されること、接着層塗布液としてポリシロキサンを
１０〜５０重量％含有するシリコン変性樹脂、又は、コ
ロイダルシリカを５〜３０重量％含有するシリコン変性
樹脂を２〜２０重量％含む塗布液に、硬化剤としてシラ
ンカップリング剤を塗布液に対して０．１〜５重量％添
加した接着層塗布液を用いること、接着層塗布液として
モノアルキルトリメトキシシラン又はその加水分解生成
物であるポリシロキサンを１〜１０重量％とシリカゾル
を０．１〜５重量％含む塗布液に、硬化剤としてシラン
カップリング剤を塗布液に対して０．１〜５重量％添加
した接着層塗布液を用いること、接着層の厚みが０．５
〜５μｍであること、光触媒層が金属酸化物又は金属水
酸化物のゾルを固形分として１〜１０重量％、酸化チタ
ンゾルを固形分として１〜１０重量％含有すること、光
触媒層がシリカゾルを１〜１０重量％、モノアルキルト
リメトキシシラン又はその加水分解生成物を１〜１０重
量％、及び酸化チタンゾルを１〜１０重量％含有するこ
と、光触媒層の厚みが０．１〜５μｍであること、ある
いは成形加工がインサート成形、真空成形、圧空成形、
真空圧空成形、プレス成形により行われることをそれぞ
れ特徴とする上記光触媒担持熱可塑性樹脂成形体に関す
る。[0008] The present invention also relates to a laminate of the thermoplastic resin plate having a single layer or a multilayer, wherein the thermoplastic resin plate is a polystyrene resin, a polyester resin, a polycarbonate resin, a polyolefin resin,
It is made of a resin selected from polyamide resin, polyvinyl chloride resin, ABS resin, acrylic resin, and polyphenylene ether resin, and the thickness of the thermoplastic resin plate is 50
μm to 10 mm, the adhesive layer is formed by applying an adhesive layer coating solution containing a silane coupling agent as a curing agent, and a silicon-modified resin containing 10 to 50% by weight of polysiloxane as the adhesive layer coating solution Or a coating liquid containing 2 to 20% by weight of a silicon-modified resin containing 5 to 30% by weight of colloidal silica, and a silane coupling agent as a curing agent added in an amount of 0.1 to 5% by weight based on the coating liquid. A layer coating solution is used. A coating agent containing 1 to 10% by weight of monoalkyltrimethoxysilane or a polysiloxane which is a hydrolysis product thereof and 0.1 to 5% by weight of silica sol is used as a coating solution for the adhesive layer. As the adhesive layer coating solution, a silane coupling agent is added in an amount of 0.1 to 5% by weight based on the coating solution, and the thickness of the adhesive layer is 0.5
The photocatalyst layer contains 1 to 10% by weight of a metal oxide or metal hydroxide sol as a solid content, and the titanium oxide sol contains 1 to 10% by weight as a solid content. 10 to 10% by weight, 1 to 10% by weight of a monoalkyltrimethoxysilane or a hydrolysis product thereof, and 1 to 10% by weight of a titanium oxide sol, and the photocatalyst layer has a thickness of 0.1 to 5 μm. Or molding process is insert molding, vacuum molding, pressure molding,
The present invention relates to the photocatalyst-supported thermoplastic resin molded article, which is performed by vacuum pressure forming and press molding, respectively.
【０００９】また本発明は、熱可塑性樹脂板に、硬化剤
としてシランカップリング剤が添加された接着層塗布液
を塗布・乾燥した後、この接着層に光触媒層塗布液を塗
布・乾燥して、熱可塑性樹脂板上に接着層を介して光触
媒層を担持した光触媒担持熱可塑性樹脂板を調製し、こ
の光触媒担持熱可塑性樹脂板を、成形温度１００〜３０
０℃の範囲で成形加工する光触媒担持熱可塑性樹脂成形
体の製造方法に関する。In the present invention, a coating solution of an adhesive layer containing a silane coupling agent as a curing agent is applied to a thermoplastic resin plate and dried, and then a coating solution of a photocatalyst layer is applied to the adhesive layer and dried. Preparing a photocatalyst-supporting thermoplastic resin plate having a photocatalyst layer supported on a thermoplastic resin plate via an adhesive layer, and forming the photocatalyst-supporting thermoplastic resin plate at a molding temperature of 100 to 30.
The present invention relates to a method for producing a photocatalyst-supported thermoplastic resin molded article that is molded at a temperature of 0 ° C.
【００１０】また本発明は、熱可塑性樹脂板に前述のシ
ランカップリング剤が添加された接着層塗布液、又は、
シランカップリング剤が添加されていない接着層塗布
液、すなわちテトラアルコキシシラン又はその加水分解
生成物を１〜１０重量％とシリカゾル０．１〜１０重量
％及びシリコン含有量１〜１０重量％のアクリルシリコ
ン樹脂等からなる接着層塗布液を、塗布・乾燥した後、
該接着層に前述の光触媒層塗布液を塗布・乾燥して得ら
れる、光触媒担持熱可塑性樹脂板の光触媒塗布面にさら
に保護フィルムが耐熱性粘着剤などで貼り付けて得られ
る加熱成形加工用の光触媒担持熱可塑性樹脂板に関する
ものである。また本発明は、この保護フィルムを付けた
光触媒担持熱可塑性樹脂板を使用し、インサート成形、
真空成形、圧空成形、真空圧空成形、プレス成形によっ
て同一もしくは相異なる種類の熱可塑性樹脂を光触媒担
持熱可塑性樹脂板の光触媒担持面の反対面に成形温度１
００〜３００℃で成形積層した光触媒担持熱可塑性樹脂
成形体に関するものである。また本発明は、この光触媒
担持熱可塑性樹脂板に使用する保護フィルムとして厚さ
１０〜１００μｍのポリエステルフィルム、フッ素樹脂
フィルム、ポリエチレンフィルム又はポリプロピレンフ
ィルムなどのポリオレフィンフィルムを使用し、熱成形
加工前に光触媒担持面の反対側に図柄もしくは文字を印
刷した後、その印刷面に更に熱可塑性樹脂をインサート
成形、真空成形、圧空成形、真空圧空成形、プレス成形
によって積層して得られる光触媒担持熱可塑性樹脂成形
体に関するものである。さらに本発明は、保護フィルム
が剥がされた、上記いずれかの光触媒担持熱可塑性樹脂
成形体を用いる電気製品用等の操作パネルに関するもの
である。[0010] The present invention also provides an adhesive layer coating solution obtained by adding a silane coupling agent to a thermoplastic resin plate, or
Coating solution for adhesive layer to which no silane coupling agent is added, that is, acrylic having 1 to 10% by weight of tetraalkoxysilane or its hydrolysis product, 0.1 to 10% by weight of silica sol, and 1 to 10% by weight of silicon. After applying and drying the adhesive layer coating solution composed of silicone resin, etc.,
Obtained by applying and drying the above-described photocatalyst layer coating solution on the adhesive layer, for a heat molding process obtained by further applying a protective film to the photocatalyst-coated surface of the photocatalyst-supporting thermoplastic resin plate with a heat-resistant adhesive or the like. The present invention relates to a thermoplastic resin plate supporting a photocatalyst. Also, the present invention uses a photocatalyst-supporting thermoplastic resin plate with this protective film, insert molding,
The same or different kinds of thermoplastic resin are formed on the opposite surface of the photocatalyst-supporting thermoplastic resin plate from the photocatalyst-supporting surface by vacuum forming, pressure forming, vacuum forming, and press forming.
The present invention relates to a photocatalyst-supported thermoplastic resin molded article formed and laminated at 00 to 300 ° C. Further, the present invention uses a polyolefin film such as a polyester film, a fluororesin film, a polyethylene film or a polypropylene film having a thickness of 10 to 100 μm as a protective film used for the photocatalyst-supporting thermoplastic resin plate, and the photocatalyst before thermoforming. After printing a pattern or character on the opposite side of the supporting surface, the photocatalyst carrying thermoplastic resin molded by laminating thermoplastic resin on the printed surface by insert molding, vacuum forming, air pressure forming, vacuum pressure forming, press forming It is about the body. Furthermore, the present invention relates to an operation panel for an electric appliance or the like using the photocatalyst-supported thermoplastic resin molded article from which the protective film has been peeled off.
【００１１】[0011]
【発明の実施の形態】本発明の光触媒担持熱可塑性樹脂
成形体は、例えば熱可塑性樹脂板に、硬化剤としてシラ
ンカップリング剤が添加された接着層塗布液を塗布・乾
燥した後、この接着層に光触媒層塗布液を塗布・乾燥し
て、熱可塑性樹脂板上に接着層を介して光触媒層を担持
した光触媒担持熱可塑性樹脂板を調製し、この光触媒担
持熱可塑性樹脂板を、成形温度１００〜３００℃の範囲
で所望の形に成形加工することにより製造することがで
きる。BEST MODE FOR CARRYING OUT THE INVENTION The photocatalyst-supported thermoplastic resin molded article of the present invention is obtained by applying and drying an adhesive layer coating solution containing a silane coupling agent as a curing agent on a thermoplastic resin plate, for example, and then drying the same. The layer is coated with a photocatalyst layer coating solution and dried to prepare a photocatalyst-supporting thermoplastic resin plate carrying a photocatalyst layer on a thermoplastic resin plate via an adhesive layer, and the photocatalyst-supporting thermoplastic resin plate is heated at a molding temperature. It can be manufactured by molding into a desired shape in the range of 100 to 300 ° C.
【００１２】本発明における熱可塑性樹脂板には、一般
に、フィルム、シート及びプレートと呼ばれている種々
の厚さの樹脂板が含まれる。通常、フィルムとは厚さ
０．２ｍｍ未満のものを、シートとは厚さ０．２ｍｍ以
上３ｍｍ未満のものを、プレートとは厚さ３ｍｍ以上の
ものをいい、本発明における熱可塑性樹脂板の厚さとし
ては、本発明における１００〜３００℃の温度下で成形
加工しうるものであればどのような厚さのものでも使用
でき、樹脂の種類にもよるが、５０μｍ〜１０ｍｍの範
囲のものが好ましく、１００μｍ〜５ｍｍの範囲のもの
がより好ましい。厚さが５０μｍ未満であると実用的な
塗工機では困難であり、厚さが１０ｍｍを超えると成形
加工における加熱時間を長くする必要があり、樹脂板表
面が変色することがあるので好ましくない。The thermoplastic resin plate in the present invention includes resin plates of various thicknesses generally called films, sheets and plates. Usually, a film refers to a sheet having a thickness of less than 0.2 mm, a sheet refers to a sheet having a thickness of 0.2 mm or more and less than 3 mm, and a plate refers to a sheet having a thickness of 3 mm or more. As the thickness, any thickness can be used as long as it can be formed at a temperature of 100 to 300 ° C. in the present invention, and depending on the type of resin, it is in a range of 50 μm to 10 mm. Is preferable, and those having a range of 100 μm to 5 mm are more preferable. When the thickness is less than 50 μm, it is difficult with a practical coating machine, and when the thickness exceeds 10 mm, it is necessary to lengthen the heating time in the molding process, and the resin plate surface may be discolored, which is not preferable. .
【００１３】本発明における熱可塑性樹脂板の基材とな
る熱可塑性樹脂としては、ポリスチレン系樹脂、ポリエ
ステル樹脂、ポリカーボネート樹脂、ポリオレフィン樹
脂、ポリアミド樹脂、ポリ塩化ビニル樹脂、ＡＢＳ樹
脂、アクリル系樹脂、ポリフェニレンエーテル樹脂等を
例示することができるが、これらの樹脂に限定されるこ
とはなく、光触媒活性を低下させることなく１００〜３
００℃の温度下で成形加工しうるものであれば、他の樹
脂を使用することもできる。しかし、接着層や光触媒層
を塗布成膜する際に、熱可塑性樹脂板が伸びたりシワが
よったりして均一で均質な光触媒担持熱可塑性樹脂板が
得られない場合は好ましくないため、塗布加工時の成膜
機械のテンションに耐える引張強度と弾性率を維持でき
る厚みと材質である必要がある。The thermoplastic resin used as the base material of the thermoplastic resin plate in the present invention includes polystyrene resin, polyester resin, polycarbonate resin, polyolefin resin, polyamide resin, polyvinyl chloride resin, ABS resin, acrylic resin, and polyphenylene. Examples thereof include ether resins, but are not limited to these resins, and may be 100 to 3 without lowering the photocatalytic activity.
Other resins that can be molded at a temperature of 00 ° C. can be used. However, when the adhesive layer or the photocatalyst layer is formed by coating, it is not preferable to obtain a uniform and homogeneous photocatalyst-supporting thermoplastic resin plate due to stretching or wrinkling of the thermoplastic resin plate. The thickness and the material must be able to maintain the tensile strength and elastic modulus that can withstand the tension of the film forming machine at the time.
【００１４】本発明において光触媒担持熱可塑性樹脂板
は、単層であっても多層の積層体であってもよい。ここ
で多層とは、複数の熱可塑性樹脂板が接着した積層体で
あり、熱可塑性樹脂の種類が異なる組合わせであって
も、全て同樹脂であってもよい。そして、積層体を得る
方法としては、熱可塑性樹脂を押出成形し、高温の該板
と光触媒担持熱可塑性樹脂をロールで圧着させ接着する
方法、光触媒担持熱可塑性樹脂板又は熱可塑性樹脂板の
少なくとも一方に接着剤を塗布して接着する方法、又は
各々の熱可塑性樹脂板を接着後に光触媒を担持させる方
法、多層押出機で熱可塑性樹脂板を押出成形し、得られ
る積層体に光触媒を担持する方法等を挙げることができ
る。また、多層の光触媒担持熱可塑性樹脂板の厚みが１
ｍｍを超える場合にあっては、接着する前に一方の熱可
塑性樹脂板に光触媒を担持させてから積層した方が経済
的である。さらに、異なる２種以上の樹脂から成形加工
して得られる多層の積層体使用することにより、光触媒
を担持する熱可塑性樹脂板の有すべき特性、特に耐候
性、耐熱性、透湿性などを大きく向上させることも可能
で、使用する環境に応じて光触媒を担持する熱可塑性樹
脂板の特性を設計し変更できることは実用上極めて有利
である。In the present invention, the photocatalyst-supporting thermoplastic resin plate may be a single layer or a multilayer laminate. Here, the multilayer is a laminate in which a plurality of thermoplastic resin plates are bonded, and may be a combination of different types of thermoplastic resins, or may be the same resin. Then, as a method of obtaining a laminate, a method of extruding a thermoplastic resin, bonding the high-temperature plate and the photocatalyst-supporting thermoplastic resin by pressure bonding with a roll, and bonding at least a photocatalyst-supporting thermoplastic resin plate or a thermoplastic resin plate A method of applying an adhesive to one side and bonding, or a method of supporting a photocatalyst after bonding each thermoplastic resin plate, extruding a thermoplastic resin plate with a multilayer extruder, and supporting the photocatalyst on the obtained laminate. Methods and the like can be mentioned. The thickness of the multilayer photocatalyst-supporting thermoplastic resin plate is 1
In the case where the thickness exceeds 1 mm, it is more economical to carry the photocatalyst on one of the thermoplastic resin plates before bonding and then laminate them. Furthermore, by using a multilayer laminate obtained by molding from two or more different resins, the properties to be possessed by the thermoplastic resin plate supporting the photocatalyst, in particular, the weather resistance, heat resistance, moisture permeability, etc. are greatly increased. It can be improved, and it is extremely advantageous in practice to be able to design and change the characteristics of the thermoplastic resin plate supporting the photocatalyst according to the environment in which it is used.
【００１５】本発明において、光触媒担持熱可塑性樹脂
板は、光触媒層と熱可塑性樹脂板との間に接着層を設け
た構造を有している。そして、この光触媒層と熱可塑性
樹脂板との間に設けられる接着層は、接着層塗布液を熱
可塑性樹脂板上に塗布・乾燥することにより形成され、
光触媒層を熱可塑性樹脂板に強固に接着させる作用と、
熱可塑性樹脂板もしくは熱可塑性樹脂板をラミネートし
た高分子樹脂から拡散する可塑剤成分による光触媒活性
の低下を防ぐとともに、光触媒作用による熱可塑性樹脂
板の劣化を防ぐ作用を有しており、また接着層自身が光
触媒作用による劣化を受けにくいという特徴を有してい
る。In the present invention, the photocatalyst-supporting thermoplastic resin plate has a structure in which an adhesive layer is provided between the photocatalyst layer and the thermoplastic resin plate. An adhesive layer provided between the photocatalyst layer and the thermoplastic resin plate is formed by applying and drying an adhesive layer coating solution on the thermoplastic resin plate,
The action of firmly bonding the photocatalyst layer to the thermoplastic resin plate,
It prevents the degradation of photocatalytic activity due to the plasticizer component diffused from the thermoplastic resin plate or the polymer resin laminated with the thermoplastic resin plate, and also has the function of preventing the deterioration of the thermoplastic resin plate due to the photocatalytic action. The layer itself is characterized in that it is less susceptible to degradation due to photocatalysis.
【００１６】本発明における接着層塗布液としては、硬
化剤としてのシランカップリング剤を含むものが特に好
ましく、シランカップリング剤を接着層塗布液に含有せ
しめることにより、接着層の硬化を促進させ熱可塑性樹
脂板がフィルム状の場合には、裏面に張り付くことなく
巻取ることを可能とし、高速成膜が可能になる。さら
に、熱可塑性樹脂板が二層の場合であって、熱可塑性樹
脂を押出成形し、高温の該板と光触媒担持熱可塑性樹脂
板をロールで圧着させ接着する場合においては、光触媒
活性を低下させることなく、積層体を得ることができ
る。The adhesive layer coating liquid in the present invention is particularly preferably a liquid containing a silane coupling agent as a curing agent. By incorporating the silane coupling agent into the adhesive layer coating liquid, the curing of the adhesive layer is promoted. When the thermoplastic resin plate is in the form of a film, it can be wound up without sticking to the back surface, and high-speed film formation becomes possible. Further, when the thermoplastic resin plate has two layers, the thermoplastic resin is extruded, and when the high-temperature plate and the photocatalyst-supporting thermoplastic resin plate are pressed and bonded by a roll, the photocatalytic activity is reduced. Without this, a laminate can be obtained.
【００１７】本発明における接着層塗布液として、例え
ば、ポリシロキサンを１０〜５０重量％含有するシリコ
ン変性樹脂、又は、コロイダルシリカを５〜３０重量％
含有するシリコン変性樹脂を２〜２０重量％含む塗布液
に、硬化剤としてシランカップリング剤を塗布液に対し
て０．１〜５重量％添加してなる塗布液を例示すること
ができる。As the adhesive layer coating solution in the present invention, for example, a silicon-modified resin containing 10 to 50% by weight of polysiloxane or 5 to 30% by weight of colloidal silica is used.
Examples of the coating liquid include a coating liquid containing 2 to 20% by weight of a silicon-modified resin to which a silane coupling agent is added in an amount of 0.1 to 5% by weight based on the coating liquid.
【００１８】ポリシロキサン含有量が１０重量％未満の
アクリルシリコン樹脂やエポキシシリコン樹脂などのシ
リコン変性樹脂からなる塗布液、もしくは、コロイダル
シリカ含有量が５重量％未満のシリコン変性樹脂からな
る塗布液を塗布乾燥して得られる接着層では、光照射時
の光触媒層の接着が悪くなり、また、屋外などの紫外線
強度が強い場所では接着層が光触媒により劣化し、光触
媒層が剥離し易くなる。他方、ポリシロキサン含有量が
５０重量％を超えたり、あるいは、コロイダルシリカ含
有量が３０重量％を超えるシリコン変性樹脂では、接着
層と担体との接着が悪くなったり、接着層が多孔質とな
ったりして、光触媒が熱可塑性樹脂板より剥離し易くな
る。A coating liquid composed of a silicon-modified resin such as an acrylic silicone resin or an epoxy silicon resin having a polysiloxane content of less than 10% by weight, or a coating liquid composed of a silicon-modified resin having a colloidal silica content of less than 5% by weight. In the adhesive layer obtained by coating and drying, the adhesion of the photocatalyst layer at the time of light irradiation becomes poor, and the adhesive layer is deteriorated by the photocatalyst in a place having a strong ultraviolet intensity such as outdoors, and the photocatalyst layer is easily peeled off. On the other hand, in the case of a silicon-modified resin having a polysiloxane content of more than 50% by weight or a colloidal silica content of more than 30% by weight, the adhesion between the adhesive layer and the carrier becomes poor or the adhesive layer becomes porous. As a result, the photocatalyst is easily peeled off from the thermoplastic resin plate.
【００１９】また、本発明における接着層塗布液とし
て、モノアルキルトリメトキシシラン又はその加水分解
生成物であるポリシロキサンとシリカゾルとの塗布液
に、硬化剤としてシランカップリング剤を塗布液に対し
て０．１〜５重量％添加してなる塗布液を例示すること
ができる。使用できるモノアルキルトリメトキシシラン
としては、モノメチルトリメトキシシラン、モノエチル
トリメトキシシランが好ましい。また、シリカゾルとし
ては一次粒子径の細かいものが好ましく、特に透明な熱
可塑性樹脂板を得る場合には２０ｎｍ以下のものが好ま
しい。塗布液には、モノアルキルトリメトキシシラン又
はその加水分解生成物であるポリシロキサンを１〜１０
重量％とシリカゾルを０．１〜５重量％を含有させるこ
とが、接着性、触媒活性の面から好ましい。モノアルキ
ルトリメトキシシラン又はその加水分解生成物とシリカ
ゾルとの割合は、重量比で２０／８０〜６０／４０が好
ましく、また硬化促進のため鉱酸などの酸触媒を添加す
ることもできる。In the present invention, a coating solution of a monoalkyltrimethoxysilane or a polysiloxane which is a hydrolysis product thereof and a silica sol are used as a coating solution for the adhesive layer, and a silane coupling agent is used as a curing agent for the coating solution. An example of the coating liquid is 0.1 to 5% by weight. As the monoalkyltrimethoxysilane that can be used, monomethyltrimethoxysilane and monoethyltrimethoxysilane are preferable. Further, the silica sol preferably has a fine primary particle diameter, and particularly preferably 20 nm or less when a transparent thermoplastic resin plate is obtained. The coating solution contains 1 to 10 polyalkyltrimethoxysilanes or polysiloxanes as hydrolysis products thereof.
It is preferable to contain 0.1% to 5% by weight of silica sol in terms of adhesiveness and catalytic activity. The ratio of the monoalkyltrimethoxysilane or a hydrolysis product thereof to the silica sol is preferably 20/80 to 60/40 by weight, and an acid catalyst such as a mineral acid can be added to promote curing.
【００２０】そして、接着層塗布液が、ポリシロキサン
−シリコン変性樹脂やコロイダルシリカ−シリコン変性
樹脂の場合でも、またモノアルキルトリメトキシシラン
−シリカゾルの場合でも、硬化剤として添加するシラン
カップリング剤はこれら塗布液に対して０．１〜５重量
％添加することが望ましい。シランカップリング剤の添
加量が塗布液に対して０．１重量％未満では、硬化が緩
慢となり、他方、シランカップリング剤の添加量が塗布
液に対して５重量％以上では、硬化が速くなりすぎた
り、成膜途中に液がゲル化するなどの現象が生ずるため
好ましくない。Regardless of whether the adhesive layer coating solution is a polysiloxane-silicon modified resin or colloidal silica-silicon modified resin, or a monoalkyltrimethoxysilane-silica sol, the silane coupling agent added as a curing agent is It is desirable to add 0.1 to 5% by weight to these coating solutions. When the added amount of the silane coupling agent is less than 0.1% by weight based on the coating solution, the curing becomes slow. On the other hand, when the added amount of the silane coupling agent is 5% by weight or more based on the coating solution, the curing is fast. It is not preferable because phenomena such as excessive formation and gelation of the liquid during film formation occur.
【００２１】シランカップリング剤としては、一般式：
ＲＳｉ(Ｘ)3や (Ｒ)2Ｓｉ(Ｘ)2など（但し、Ｒは有機性
官能基を、Ｘは塩素原子又はアルコキシ基を示す。）で
示されるものが使用可能であり、式中Ｒは、メチル基、
エチル基、ビニル基、γ−グリシドキシプロピル基、γ
−メタクリロキシプロピル基、γ−（２−アミノエチ
ル）アミノプロピル基、γ−クロロプロピル基、γ−メ
ルカプトプロピル基、γ−アミノプロピル基、γ−アク
リロキシプロピル基などを表し、式中Ｘは、塩素原子の
他、メトキシ基、エトキシ基、β−メトキシエトキシ基
などのＣ1 〜Ｃ5のアルコキシ基などを表す。The silane coupling agent has the general formula:
A compound represented by RSi (X) 3 or (R) 2 Si (X) 2 (where R represents an organic functional group and X represents a chlorine atom or an alkoxy group) can be used. R is a methyl group,
Ethyl group, vinyl group, γ-glycidoxypropyl group, γ
-A methacryloxypropyl group, a γ- (2-aminoethyl) aminopropyl group, a γ-chloropropyl group, a γ-mercaptopropyl group, a γ-aminopropyl group, a γ-acryloxypropyl group, and the like, wherein X is , A chlorine atom, and a C1 -C5 alkoxy group such as a methoxy group, an ethoxy group, and a β-methoxyethoxy group.
【００２２】接着層塗布液としては、テトラアルコキシ
シラン又はその加水分解生成物を１〜１０重量％とシリ
カゾルを０．１〜１０重量％及びシリコン含有量１〜１
０重量％のアクリルシリコン樹脂からなる接着層塗布液
も好ましく使用することができる。テトラアルコキシシ
ランの加水分解生成物とシリカゾルが共存することによ
り、硬度、耐摩耗性、耐久性に優れた光触媒担持熱可塑
性樹脂成形体とすることが可能である。テトラアルコキ
シシランの加水分解生成物は、あらかじめアクリルシリ
コン樹脂に加えられているものが好ましく、中でもモノ
マーのテトラアルコキシシランが加水分解生成物中に３
％以下であるものが特に好ましい。また、使用するシリ
カゾルとしては、水中に分散したものでも使用できる
が、アルコールなどの有機溶剤に分散したタイプのもの
がより好ましく使用できる。The coating liquid for the adhesive layer includes tetraalkoxysilane or its hydrolysis product in an amount of 1 to 10% by weight, silica sol in an amount of 0.1 to 10% by weight, and a silicon content of 1 to 1%.
An adhesive layer coating liquid composed of 0% by weight of an acrylic silicone resin can also be preferably used. The coexistence of the hydrolysis product of tetraalkoxysilane and silica sol makes it possible to obtain a photocatalyst-supported thermoplastic resin molded article having excellent hardness, abrasion resistance and durability. The hydrolysis product of tetraalkoxysilane is preferably added to the acrylic silicone resin in advance.
% Is particularly preferred. As the silica sol to be used, those dispersed in water can be used, but those dispersed in an organic solvent such as alcohol can be more preferably used.
【００２３】また、接着層に、光触媒作用による劣化を
抑える目的で、光安定化剤及び／又は紫外線吸収剤等を
混合することにより、その耐久性を向上させることがで
きる。光安定化剤としてはヒンダードアミン系が好まし
いが、その他の光安定化剤も使用することができる。紫
外線吸収剤としてはトリアゾール系などの紫外線吸収剤
が使用できる。添加量は、接着層塗布液に対して０．０
０５重量％以上１０重量％以下、好ましくは０．０１重
量％以上５重量％以下である。接着層中に光安定化剤も
しくは紫外線吸収剤を添加することにより、光触媒を担
持する熱可塑性樹脂板の耐候性を向上させることも可能
となり、特に屋外で使用する成形体の場合は有利であ
る。The durability of the adhesive layer can be improved by mixing a light stabilizer and / or an ultraviolet absorber for the purpose of suppressing deterioration due to photocatalysis. As the light stabilizer, a hindered amine type is preferable, but other light stabilizers can also be used. As the ultraviolet absorber, a triazole-based ultraviolet absorber or the like can be used. The amount of addition is 0.0
It is from 0.05% by weight to 10% by weight, preferably from 0.01% by weight to 5% by weight. By adding a light stabilizer or an ultraviolet absorber in the adhesive layer, it becomes possible to improve the weather resistance of the thermoplastic resin plate supporting the photocatalyst, and it is particularly advantageous for a molded article used outdoors. .
【００２４】接着層を熱可塑性樹脂板に塗布する方法と
しては、接着層塗布液をグラビア印刷法、マイクログラ
ビア印刷法、コンマコート法、ロールコート法、リバー
スロールコート法、バーコート法、キスコート法、フロ
ーコート法、スプレー吹き付け法、ディップコート法、
スピンコーティング法等でコートし、乾燥する方法を例
示することができる。乾燥温度は、塗布方法や溶媒や熱
可塑性樹脂板の樹脂の種類や熱可塑性樹脂板の厚みによ
っても異なるが、一般的には１５０℃以下が望ましい。As a method for applying the adhesive layer to the thermoplastic resin plate, a coating solution for the adhesive layer is applied by a gravure printing method, a microgravure printing method, a comma coating method, a roll coating method, a reverse roll coating method, a bar coating method, a kiss coating method. , Flow coat method, spray spray method, dip coat method,
A method of coating with a spin coating method or the like and then drying can be exemplified. The drying temperature varies depending on the coating method, the solvent, the type of resin of the thermoplastic resin plate, and the thickness of the thermoplastic resin plate, but is generally preferably 150 ° C. or lower.
【００２５】また、接着層の厚さは、０．５μｍ以上が
望ましい。０．５μｍより薄い場合は、光触媒層を強固
に熱可塑性樹脂板に接着させる効果に乏しく、長期間の
使用において光触媒層が剥離したりしやすくなるため好
ましくない。また、接着層の厚みが厚い場合は特に問題
はないものの、成膜時の乾燥が不十分になるため、成膜
のムラが発生しやすくなったり、成膜コストが上昇する
ため実際的には５μｍ以下が好ましい。The thickness of the adhesive layer is desirably 0.5 μm or more. When the thickness is less than 0.5 μm, the effect of firmly adhering the photocatalyst layer to the thermoplastic resin plate is poor, and the photocatalyst layer is likely to peel off during long-term use. In addition, although there is no particular problem when the thickness of the adhesive layer is large, drying during film formation is insufficient, so that unevenness in film formation is likely to occur or the film formation cost is increased. 5 μm or less is preferable.
【００２６】本発明における光触媒担持熱可塑性樹脂板
は、接着層の上に光触媒層を設けた構造を有している。
光触媒層は、例えば、金属酸化物又は金属水酸化物のゾ
ルを固形分として１〜１０重量％、酸化チタンゾルを固
形分として１〜１０重量％含有する光触媒層塗布液を接
着層上に塗布乾燥して形成することができる。光触媒層
塗布液中の金属酸化物又は金属水酸化物のゾルは、酸化
チタンゾルを固着し接着層と強固に接着させるだけでな
く、金属酸化物又は金属水酸化物のゾルを乾燥して得ら
れるゲルが多孔質であることから吸着性をもっており、
光触媒活性を高める効果も有している。この金属酸化物
又は金属水酸化物のゾルと酸化チタンゾルの光触媒塗布
液中での比率は、２５／７５〜９５／５が好ましい。金
属酸化物又は金属水酸化物のゾルが２５％以下では接着
層との接着が不十分となり、他方９５％以上では光触媒
活性が不十分となる。また、金属酸化物又は金属水酸化
物のゾルを乾燥して得られるゲルの比表面積が１００ｍ
2 ／ｇ以上あると、接着性はより強固になり、触媒活性
も向上する。材質としては、ケイ素、アルミニウム、チ
タニウム、ジルコニウム、マグネシウム、ニオビウム、
タンタラム、タングステンの金属の酸化物ゾルがよく、
また、これらを混合したゾルや、共沈法などの方法で作
られる複合酸化物ゾルを使用してもよい。The photocatalyst-supporting thermoplastic resin plate of the present invention has a structure in which a photocatalyst layer is provided on an adhesive layer.
The photocatalyst layer is, for example, coated and dried on the adhesive layer with a photocatalyst layer coating solution containing 1 to 10% by weight of a metal oxide or metal hydroxide sol as a solid content and 1 to 10% by weight of a titanium oxide sol as a solid content. Can be formed. The metal oxide or metal hydroxide sol in the photocatalyst layer coating solution is obtained not only by fixing the titanium oxide sol and firmly adhering to the adhesive layer, but also by drying the metal oxide or metal hydroxide sol. Because the gel is porous, it has adsorptivity,
It also has the effect of increasing photocatalytic activity. The ratio of the metal oxide or metal hydroxide sol to the titanium oxide sol in the photocatalyst coating liquid is preferably 25/75 to 95/5. If the sol of the metal oxide or metal hydroxide is less than 25%, the adhesion to the adhesive layer will be insufficient, while if it is more than 95%, the photocatalytic activity will be insufficient. The specific surface area of the gel obtained by drying the metal oxide or metal hydroxide sol is 100 m.
When it is 2 / g or more, the adhesiveness becomes stronger and the catalytic activity is improved. Materials include silicon, aluminum, titanium, zirconium, magnesium, niobium,
Tantalum, tungsten metal oxide sol is good,
Further, a sol obtained by mixing these or a composite oxide sol prepared by a method such as a coprecipitation method may be used.
【００２７】金属酸化物又は金属水酸化物のゾルを酸化
チタンゾルと混合する場合、ゾルの状態で混合するか、
あるいはゾルを調製する前の原料の段階で混合するのが
望ましい。ゾルを調製する方法には、金属塩を加水分解
する方法、中和分解する方法、イオン交換する方法、金
属アルコキシドを加水分解する方法等があるが、ゾルの
中に酸化チタンゾルが均一に分散された状態で得られる
ものであればいずれの方法も使用可能である。しかし、
ゾル中に多量の不純物が存在すると、光触媒の接着性や
触媒活性に悪影響を与えるので、不純物の少ないゾルを
用いる方が好ましい。When a metal oxide or metal hydroxide sol is mixed with a titanium oxide sol,
Alternatively, it is desirable to mix at the stage of raw materials before preparing the sol. Methods for preparing the sol include a method of hydrolyzing a metal salt, a method of neutralizing and decomposing, a method of performing ion exchange, a method of hydrolyzing a metal alkoxide, and the like. Titanium oxide sol is uniformly dispersed in the sol. Any method can be used as long as it can be obtained in a state where it is placed. But,
The presence of a large amount of impurities in the sol adversely affects the adhesion and catalytic activity of the photocatalyst. Therefore, it is preferable to use a sol containing a small amount of impurities.
【００２８】また、光触媒層として、シリカゾルを１〜
１０重量％、モノアルキルトリメトキシシラン又はその
加水分解生成物を１〜１０重量％、及び、酸化チタンゾ
ルを１〜１０重量％含む混合液からなる光触媒層塗布液
を接着層上に塗布乾燥して得られるものも特に好ましく
使用できる。モノアルキルトリメトキシシランとして
は、メチルトリメトキシシラン、メチルトリエトキシシ
ランが特に好ましく使用できる。シリカゾルと、モノア
ルキルトリメトキシシラン又はその加水分解生成物との
混合比率は、重量比で１００／０〜６０／４０が好まし
く、酸化チタンゾルとこれらの珪素化合物成分の比率
は、酸化チタン／珪素化合物の重量比で５／９５〜７５
／２５が好ましい。珪素化合物の比率が９５％以上では
光触媒活性が低下するし、２５％以下では接着層への接
着性が低下する。Further, as the photocatalyst layer, silica sol was
A photocatalyst layer coating solution comprising a mixture containing 10% by weight, 1 to 10% by weight of a monoalkyltrimethoxysilane or a hydrolysis product thereof, and 1 to 10% by weight of a titanium oxide sol is applied to the adhesive layer and dried. Those obtained can also be particularly preferably used. As the monoalkyltrimethoxysilane, methyltrimethoxysilane and methyltriethoxysilane can be particularly preferably used. The mixing ratio of the silica sol to the monoalkyltrimethoxysilane or its hydrolysis product is preferably 100/0 to 60/40 by weight, and the ratio of the titanium oxide sol to the silicon compound component is titanium oxide / silicon compound. 5 / 95-75 by weight ratio
/ 25 is preferred. When the ratio of the silicon compound is 95% or more, the photocatalytic activity decreases, and when the ratio is 25% or less, the adhesiveness to the adhesive layer decreases.
【００２９】光触媒層中の光触媒としては、ＴｉＯ2 、
ＺｎＯ、ＳｒＴｉＯ3 、ＣｄＳ、ＧａＰ、ＩｎＰ、Ｇａ
Ａｓ、ＢａＴｉＯ3 、Ｋ2ＮｂＯ3 、Ｆｅ2Ｏ3 、Ｔａ2
Ｏ5、ＷＯ3 、ＳｎＯ2 、Ｂｉ2Ｏ3 、ＮｉＯ、Ｃｕ
2Ｏ、ＳｉＣ、ＳｉＯ2 、ＭｏＳ 2 、ＩｎＰｂ、ＲｕＯ
2 、ＣｅＯ2 などを例示することができ、またこれらの
光触媒にＰｔ、Ｒｈ、ＲｕＯ2 、Ｎｂ、Ｃｕ、Ｓｎ、Ｎ
ｉＯなどの金属及び金属酸化物を添加した公知のものが
全て使用できる。光触媒層中の光触媒の含有量は、多く
なるほど触媒活性が高くなるが、接着性の点から７５重
量％以下が好ましい。抗菌性や防カビ性をさらに向上さ
せるため、光触媒層中に酸化チタン光触媒に対して０．
０５〜５重量％の銀や銅の金属もしくは金属化合物を添
加することもできる。添加量が０．０５重量％以下では
抗菌／防カビ性の向上効果に乏しく、５重量％以上では
光触媒層が変色したりするという現象が生じるため熱可
塑性樹脂板をラミネートした樹脂の色や柄によっては使
用が困難になる場合もある。The photocatalyst in the photocatalyst layer is TiO.Two,
ZnO, SrTiOThree, CdS, GaP, InP, Ga
As, BaTiOThree, KTwoNbOThree, FeTwoOThree, TaTwo
OFive, WOThree, SnOTwo, BiTwoOThree, NiO, Cu
TwoO, SiC, SiOTwo, MoS Two, InPb, RuO
Two, CeOTwoAnd the like.
Pt, Rh, RuO for photocatalystTwo, Nb, Cu, Sn, N
Known materials to which metals and metal oxides such as iO are added
All can be used. The photocatalyst content in the photocatalyst layer is high
Although the catalytic activity becomes higher, 75
% Or less is preferred. Improved antibacterial and antifungal properties
To make the photocatalyst layer contain 0.1% of titanium oxide photocatalyst.
0.5 to 5% by weight of a metal or metal compound of silver or copper
Can be added. If the addition amount is less than 0.05% by weight,
Poor antibacterial / antifungal effect
The phenomenon of discoloration of the photocatalyst layer occurs and heat
Depending on the color and pattern of the resin on which the plastic resin plate is laminated,
It can be difficult to use.
【００３０】光触媒層を接着層上に形成するには、金属
酸化物ゾル又は金属水酸化物ゾル溶液中に光触媒を分散
した懸濁液を用い、前記接着層を形成するのと同様のコ
ート法でコートすることができる。金属酸化物ゾル又は
金属水酸化物ゾルの前駆体溶液の状態で光触媒を分散
し、コート時に加水分解や中和分解してゾル化もしくは
ゲル化させてもよい。ゾルを使用する場合には、安定化
のために、酸やアルカリの解膠剤等が添加されていても
よい。また、ゾル懸濁液中に光触媒に対し、５重量％以
下の界面活性剤やシランカップリング剤などを添加し
て、接着性や操作性をよくすることもできる。光触媒層
形成時の乾燥温度としては、塗布方法や熱可塑性樹脂板
の樹脂の材質及び接着層中の樹脂材質によっても異なる
が、一般的に１５０℃以下が好ましい。In order to form the photocatalyst layer on the adhesive layer, a suspension in which the photocatalyst is dispersed in a metal oxide sol or metal hydroxide sol solution is used, and a coating method similar to that for forming the adhesive layer is used. Can be coated. The photocatalyst may be dispersed in a state of a precursor solution of the metal oxide sol or the metal hydroxide sol, and may be hydrolyzed or neutralized and decomposed at the time of coating to form a sol or a gel. When using a sol, an acid or alkali peptizer may be added for stabilization. In addition, a surfactant or a silane coupling agent of 5% by weight or less with respect to the photocatalyst may be added to the sol suspension to improve adhesion and operability. The drying temperature at the time of forming the photocatalyst layer varies depending on the coating method, the resin material of the thermoplastic resin plate and the resin material in the adhesive layer, but is generally preferably 150 ° C. or lower.
【００３１】光触媒層は、その厚みが厚いほど活性が高
いが、５μｍ以上になるとほとんど変わらなくなる。５
μｍ以下であっても高い触媒活性を示し、透光性を示し
て触媒層が目立たなくなるが、厚さが０．１μｍ以下に
なると透光性はよくなるものの、光触媒が利用する紫外
線をも透過してしまうために、高い活性は望めなくな
る。光触媒層の厚さを０．１μｍ以上５μｍ以下にし、
しかも結晶粒子径が４０ｎｍ以下の光触媒粒子及び比表
面積１００ｍ2 ／ｇ以上の金属酸化物ゲル又は金属水酸
化物ゲルを用いると、高い光触媒活性が得られる。ま
た、光触媒担持熱可塑性樹脂板の成形加工時には光触媒
層が伸びて膜厚が薄くなるので、成形加工の観点からす
ると０．３μｍ以上の方がより好ましい。The photocatalytic layer has a higher activity as the thickness is larger, but hardly changes when the thickness exceeds 5 μm. 5
Even when the thickness is 0.1 μm or less, the catalyst layer exhibits high catalytic activity and shows light-transmitting properties, so that the catalyst layer becomes inconspicuous. Therefore, high activity cannot be expected. The thickness of the photocatalyst layer is set to 0.1 μm or more and 5 μm or less,
In addition, high photocatalytic activity can be obtained by using photocatalyst particles having a crystal particle diameter of 40 nm or less and a metal oxide gel or metal hydroxide gel having a specific surface area of 100 m 2 / g or more. Further, at the time of forming the photocatalyst-supporting thermoplastic resin plate, the photocatalyst layer is elongated and the film thickness is reduced. Therefore, from the viewpoint of the forming process, the thickness is preferably 0.3 μm or more.
【００３２】本発明における成形加工法としては、単層
の熱可塑性樹脂板から形成された光触媒担持熱可塑性樹
脂板を、そのまま成形する真空成形法、圧空成形法、真
空・圧空成形法と、光触媒担持熱可塑性樹脂板を金型の
キャビティに予め固定し、熱可塑性樹脂を成形して積層
させるインサート方式、フィルム方法を採用する射出成
形法等を挙げることができる。成形温度としては、１０
０〜３００℃の範囲が好ましく、１５０〜２５０℃がよ
り好ましい。基材の熱可塑性樹脂の材質や厚さによって
も、成形に適切な温度範囲は変わるが、１００℃以下で
あると成形した際、熱可塑性樹脂に担持した接着層、光
触媒層が十分に展伸することがなく、ヒビが発生し、他
方３００℃を越えると基材の熱可塑性樹脂表面が変色す
ることがあるので好ましくない。The molding method in the present invention includes a vacuum forming method, a pressure forming method, a vacuum / pressure forming method for directly forming a photocatalyst-supporting thermoplastic resin plate formed from a single-layer thermoplastic resin plate. An insert method in which a supported thermoplastic resin plate is fixed in a mold cavity in advance and a thermoplastic resin is molded and laminated, and an injection molding method employing a film method can be exemplified. The molding temperature is 10
The range is preferably from 0 to 300 ° C, more preferably from 150 to 250 ° C. The temperature range suitable for molding also varies depending on the material and thickness of the thermoplastic resin of the base material. However, when molding is performed at a temperature of 100 ° C or less, the adhesive layer and the photocatalyst layer carried on the thermoplastic resin are sufficiently expanded. When the temperature exceeds 300 ° C., the surface of the thermoplastic resin may be discolored, which is not preferable.
【００３３】本発明における光触媒担持熱可塑性樹脂板
の成形加工時においては、光触媒担持面の成形加工時の
キズつきやハンドリング時のキズつきを防止するため、
光触媒担持面に耐熱性の粘着剤をつけた保護フィルムを
貼り合わせた光触媒担持熱可塑性樹脂板が好ましく使用
できる。特に透明な光触媒担持熱可塑性樹脂板の光触媒
担持面の反対側に図柄や文字を印刷した後、更に該印刷
面に熱可塑性樹脂をインサート成形や真空成形などで積
層する場合には、光触媒担持面の欠陥の発生を防止する
効果があり好ましい。耐熱性の粘着剤としては、光触媒
担持面の反対側に熱可塑性樹脂を積層成形する際の処理
条件である１００〜３００℃で２秒から数分間の間に、
光触媒層と接着して剥離できない状態になったり、光触
媒層に移行してしまって光触媒活性が極端に低下したり
することがないものであればいずれも使用可能である
が、通常使用されているアクリクル系の耐熱性粘着剤が
使用可能である。また、保護フィルムの材質としては成
形時の伸びと上述の成形温度と時間に耐えるものであれ
ばいずれも使用できるが、厚さ１０〜１００μｍのポリ
エステルフィルム、ポリエチレンフィルム又はポリプロ
ピレンフィルムなどのポリオレフィンフィルムが特に好
ましく使用できる。At the time of molding the photocatalyst-carrying thermoplastic resin plate of the present invention, in order to prevent scratches at the time of molding at the photocatalyst carrying surface and scratches at the time of handling,
A photocatalyst-carrying thermoplastic resin plate in which a protective film having a heat-resistant adhesive attached to the photocatalyst-carrying surface is preferably used. In particular, after printing a pattern or a character on the opposite side of the photocatalyst supporting surface of the transparent photocatalyst supporting thermoplastic resin plate, and further laminating the thermoplastic resin on the printing surface by insert molding or vacuum molding, the photocatalyst supporting surface This is preferable because it has the effect of preventing the occurrence of defects. As the heat-resistant adhesive, the processing conditions when laminating and molding a thermoplastic resin on the opposite side of the photocatalyst carrying surface at 100 to 300 ° C. for 2 seconds to several minutes,
Any material can be used as long as it does not adhere to the photocatalyst layer and cannot be peeled off or migrates to the photocatalyst layer and the photocatalytic activity does not extremely decrease, but is usually used Acryle-based heat-resistant adhesives can be used. As the material of the protective film, any material can be used as long as it can withstand the elongation at the time of molding and the molding temperature and time described above, but a polyester film having a thickness of 10 to 100 μm, a polyolefin film such as a polyethylene film or a polypropylene film can be used. It can be particularly preferably used.
【００３４】光触媒担持熱可塑性樹脂板の加熱成形加工
によって、表面へ塗布・乾燥した光触媒層と接着層はよ
り硬化が進行し、強固に基材の樹脂に接着するという優
れた効果がある。加熱成形加工処理によって、硬度、耐
久性、耐候性が大きく向上するため、頻繁に指触される
環境下で使用されるタッチパネルや操作指示パネルの材
料として特に好ましく使用できる。The photocatalyst-carrying thermoplastic resin plate has an excellent effect that the photocatalyst layer and the adhesive layer, which are applied and dried on the surface, are further hardened by the heat molding process, and are strongly adhered to the base resin. Since the hardness, durability, and weather resistance are greatly improved by the heat-forming processing, it can be particularly preferably used as a material for a touch panel or an operation instruction panel used in an environment where the user frequently touches.
【００３５】本発明において、光触媒担持熱可塑性樹脂
成形体の形状としては、既存の樹脂成型品の形状、例え
ば洗面化粧台、ユニットバス、システムキッチン、便
器、冷蔵庫、洗濯機、パソコン、ラジオ・テレビなどの
家庭用電気製品の樹脂製の筐体表面、及び食器カゴや調
味料ケースなどの各種プラスチックケース等における形
状を例示することができるが、これに限られるわけでは
ない。また、本発明の光触媒担持熱可塑性樹脂成形体
は、消臭、防汚、抗菌、防カビの作用を必要とする多く
の箇所に使用することができ、その優れた消臭性、防汚
性、抗菌性、防カビ性により、長期にわたって表面を美
麗な状態に維持することができる。In the present invention, the shape of the photocatalyst-carrying thermoplastic resin molded product may be the shape of an existing resin molded product, for example, a bathroom vanity, a unit bath, a system kitchen, a toilet, a refrigerator, a washing machine, a personal computer, a radio / TV. For example, the shapes of the surface of a resin-made housing of household electric appliances and various plastic cases such as a tableware basket and a seasoning case can be exemplified, but the present invention is not limited thereto. Further, the photocatalyst-supported thermoplastic resin molded article of the present invention can be used in many places where deodorizing, antifouling, antibacterial, and antifungal action is required, and its excellent deodorizing and antifouling properties Due to its antibacterial and antifungal properties, the surface can be maintained in a beautiful state for a long time.
【００３６】本発明における耐熱性粘着剤を塗布した保
護フィルムを貼り合わせた光触媒担持熱可塑性樹脂成形
体は透明であるため裏面に印刷した文字や図柄を容易に
読み取ることができる。特に、可視光直線透過率が６０
％以上の光触媒担持熱可塑性樹脂成形体を使用したもの
や、あるいは該光触媒担持熱可塑性樹脂成形体の光触媒
担持面の裏面に図柄や文字を印刷後、更に、熱可塑性樹
脂を積層成形したものは、透明であるため裏面に印刷し
た文字や図柄を読み取ることが容易であり、電気釜や電
子レンジ、電気冷蔵庫や電気洗濯機、電気掃除機、電話
機、ファクシミリ、携帯電話、温水洗浄便座、ガス給湯
器などに広く取り付けられている操作パネルや指示表示
板、タッチパネルに幅広く使用でき、長期にわたって、
防汚、抗菌作用を有するだけでなく、光触媒による親水
性を有しているため、付着した油や手指の汚れを水で容
易に拭き取ることが可能である。またその表面は光触媒
によって長期に親水性を維持しているため、表面は曇り
にくく湿気や水蒸気によって表示が曇って見えにくくな
るということもないため、操作パネルや指示表示板、タ
ッチパネルとして非常に好ましい。The photocatalyst-carrying thermoplastic resin molded article of the present invention to which the protective film coated with the heat-resistant adhesive is adhered is transparent, so that characters and designs printed on the back surface can be easily read. In particular, the visible light linear transmittance is 60
% Or more using a photocatalyst-carrying thermoplastic resin molded article, or after printing a pattern or a character on the back surface of the photocatalyst-carrying surface of the photocatalyst-carrying thermoplastic resin molded article, and further laminating the thermoplastic resin. Because it is transparent, it is easy to read characters and designs printed on the back side, electric kettles, microwave ovens, electric refrigerators and electric washing machines, vacuum cleaners, telephones, facsimile machines, mobile phones, hot water flush toilet seats, gas hot water supply It can be widely used for operation panels, instruction display boards, and touch panels that are widely attached to devices, etc.
In addition to having antifouling and antibacterial effects, it has hydrophilicity due to a photocatalyst, so that it is possible to easily wipe off attached oil and dirt on fingers with water. In addition, since the surface maintains hydrophilicity over a long period of time by the photocatalyst, the surface is hardly clouded and the display is not clouded by moisture or water vapor and is not difficult to see, so it is very preferable as an operation panel, an instruction display panel, and a touch panel. .
【００３７】[0037]
【実施例】以下実施例により本発明を具体的に説明する
が、本発明はこれらの実施例に限定されるものではな
い。 試験例１（光触媒担持シートの製造例） 接着層塗布液として、アクリル−シリコン樹脂１５重量
％及びエタノール等の溶剤８５重量％からなる「ＮＤＣ
−１００Ａ」（日本曹達株式会社製）を、グラビア印刷
機で版深４０μベタ版を使用して、膜厚０．５ｍｍのア
クリル系フィルム「ハイペットＨＢＳ００１」（三菱レ
イヨン株式会社製）に塗布し、１２０℃で乾燥した。次
に、光触媒層塗布液として、酸化チタン５重量％、酸化
ケイ素５重量％及びエタノール水９０重量％からなる
「ＮＤＣ−１００Ｃ」（日本曹達株式会社製）を上記と
同じ条件で塗布、乾燥した。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Test Example 1 (Production Example of Photocatalyst Supporting Sheet) As an adhesive layer coating solution, “NDC” comprising 15% by weight of an acryl-silicone resin and 85% by weight of a solvent such as ethanol was used.
-100A "(manufactured by Nippon Soda Co., Ltd.) on a 0.5 mm-thick acrylic film" HIPET HBS001 "(manufactured by Mitsubishi Rayon Co., Ltd.) using a gravure printing machine using a 40 .mu. Solid plate. And dried at 120 ° C. Next, as a photocatalyst layer coating solution, "NDC-100C" (manufactured by Nippon Soda Co., Ltd.) comprising 5% by weight of titanium oxide, 5% by weight of silicon oxide and 90% by weight of ethanol water was applied and dried under the same conditions as above. .
【００３８】試験例２（光触媒担持シートの製造例） 東洋紡製ポリエステルシートコスモシャインＡ４３００
の厚み１８８μｍのポリエステルシートを使用し、接着
層塗布液として、テトラメトキシシランの加水分解生成
物で重合度が３から１０のものを９０％以上含むポリシ
ロキサンを３５重量部、粒子径１０ｎｍのシリカゾルを
固形分として１重量部、シリコン含有量３重量％のアク
リルシリコン樹脂を６５重量部、キシレン−イソプロパ
ノール（５／５重量比）混合液１１０重量部との混合溶
液を、エタノール−酢酸エチル（４／６重量比）混合液
で不揮発残分濃度で１０重量％になるように希釈した接
着層塗布液を使用して、グラビア印刷機で版深４０μｍ
のベタ版を使用して、塗布し、１２０℃で乾燥し、接着
層を成膜した。さらに、この接着層の上に、光触媒層塗
布液として、溶液のｐＨを３に調整した粒子径１０ｎｍ
のシリカゾルを固形分として３重量％、溶液のｐＨが
１．５の粒子径７ｎｍの酸化チタンゾルを固形分として
３重量％、メチルトリメトキシシランの加水分解生成物
を不揮発残分として０．３重量％、界面活性剤を０．０
０１重量％になるように混合した光触媒層塗布液を使用
して、上記と同様の条件で光触媒層を成膜し、光触媒担
持熱可塑性樹脂シートとした。Test Example 2 (Example of manufacturing photocatalyst supporting sheet) Polyester sheet Cosmoshine A4300 manufactured by Toyobo
A polyester sol having a thickness of 188 μm is used as a coating solution for the adhesive layer, and 35 parts by weight of a polysiloxane containing 90% or more of a hydrolysis product of tetramethoxysilane having a degree of polymerization of 3 to 10 is used as a silica sol having a particle diameter of 10 nm. A solid solution containing 1 part by weight, 65 parts by weight of an acrylic silicone resin having a silicon content of 3% by weight, and 110 parts by weight of a xylene-isopropanol (5/5 weight ratio) mixed solution was mixed with ethanol-ethyl acetate (4%). / 6 weight ratio) Using an adhesive layer coating solution diluted to a non-volatile residue concentration of 10% by weight with the mixed solution, a plate depth of 40 μm was obtained using a gravure printing machine.
Was applied and dried at 120 ° C. to form an adhesive layer. Further, on this adhesive layer, as a photocatalyst layer coating liquid, the pH of the solution was adjusted to 3 and the particle diameter was 10 nm.
3% by weight of silica sol as solid content, 3% by weight of titanium oxide sol having a particle diameter of 7 nm and a solution pH of 1.5 as solid content, and 0.3% by weight of hydrolysis product of methyltrimethoxysilane as non-volatile residue %, Surfactant 0.0%
A photocatalyst layer was formed under the same conditions as described above using the photocatalyst layer coating solution mixed so as to be 01% by weight to obtain a photocatalyst-supporting thermoplastic resin sheet.
【００３９】実施例１ 試験例１で得た光触媒担持アクリル系フィルムを真空成
形機（ＦＯＲＭＥＣＨ４５０：ＦＯＲＭＥＣＨ社製）を
用い、１７０℃の温度で成形し、約２００ｍｍ×２００
ｍｍの正方形で深さが３０ｍｍの箱状の光触媒担持熱可
塑性樹脂成形体を得た。Example 1 The photocatalyst-carrying acrylic film obtained in Test Example 1 was molded at a temperature of 170 ° C. using a vacuum molding machine (FORMECH450: manufactured by FORMECH) to obtain a film of about 200 mm × 200 mm.
A box-shaped thermoplastic resin-carrying thermoplastic resin article having a square shape of mm and a depth of 30 mm was obtained.
【００４０】実施例２（保護フィルム付き光触媒担持シ
ート） 試験例２で得られた光触媒担持ポリエステルシートの光
触媒塗布面に、アクリル系の耐熱性粘着剤を３０μｍの
厚みで塗布した東洋紡製ポリエステルフィルムコスモシ
ャインＡ４１００の２５μｍ厚み品を貼り合わせ、保護
フィルムを貼り合わせた光触媒担持ポリエステルシート
とした。以下の実施例では、保護フィルムは全て製品検
査と特性評価には剥がして行った。Example 2 (Photocatalyst-carrying sheet with protective film) A polyester film Cosmo manufactured by Toyobo, in which an acrylic heat-resistant adhesive was applied to the photocatalyst-coated surface of the photocatalyst-carrying polyester sheet obtained in Test Example 2 to a thickness of 30 μm. A photocatalyst-supporting polyester sheet in which a 25 μm-thick product of Shine A4100 was stuck and a protective film was stuck. In the following examples, all the protective films were peeled off for product inspection and characteristic evaluation.
【００４１】実施例３（インサート成形） 実施例２で得られた光触媒担持ポリエステルシートを６
０ｃｍ角に裁断し、保護フィルムと反対面にスクリーン
印刷法で、操作指示と機種名、型番号を印刷し、打ち抜
き型で所定の形状に打ち抜いた。この打ち抜いたシート
をインサート成形用の金型に保護フィルムを付けた面を
下にして挿入し、金型を加温後、樹脂注入口よりアクリ
ロニトリルスチレン樹脂を加圧注入し、インサート成形
した。所定時間後、金型から樹脂と一体となった光触媒
担持シートを取り出し、電気炊飯器の操作パネルとし
た。Example 3 (Insert Molding) The photocatalyst-carrying polyester sheet obtained in Example 2 was
The sheet was cut into a 0 cm square, the operation instructions, the model name, and the model number were printed on the surface opposite to the protective film by a screen printing method, and punched into a predetermined shape by a punching die. The punched sheet was inserted into a mold for insert molding with the surface with the protective film attached down, and after heating the mold, acrylonitrile styrene resin was injected under pressure from a resin injection port to perform insert molding. After a predetermined time, the photocatalyst-carrying sheet integrated with the resin was removed from the mold and used as an operation panel of an electric rice cooker.
【００４２】実施例４（インサート成形） 実施例２で得られた光触媒担持ポリエステルシートを６
０ｃｍ角に裁断し、保護フィルムと反対面にスクリーン
印刷法で、操作指示と機種名、型番号を印刷し、打ち抜
き型で所定の形状に打ちぬいた。この打ち抜いたシート
を射出成形機（日本製鋼所株式会社製Ｎ４０ＢＩＩ）の
成形金型に保護フィルムを付けた面が金型キャビティ面
になるよう装着し、冷却水温を６０℃に温調した状態
で、シリンダー温度１７０〜２２０℃の条件で、樹脂注
入口より変性ポリスチレン樹脂を加圧注入し、射出成形
した。所定時間後、金型から樹脂と一体となった光触媒
担持シートを取り出し、電子レンジ用の操作パネルとし
た。Example 4 (Insert Molding) The photocatalyst-carrying polyester sheet obtained in Example 2 was
The sheet was cut into a 0 cm square, the operation instructions, the model name, and the model number were printed by a screen printing method on the surface opposite to the protective film, and punched into a predetermined shape with a punching die. The punched sheet was mounted on a molding die of an injection molding machine (N40BII manufactured by Nippon Steel Works Co., Ltd.) so that the surface on which the protective film was attached was the mold cavity surface, and the cooling water temperature was adjusted to 60 ° C. Under a condition of a cylinder temperature of 170 to 220 ° C., a modified polystyrene resin was injected under pressure from a resin injection port to perform injection molding. After a predetermined time, the photocatalyst-carrying sheet integrated with the resin was taken out of the mold and used as an operation panel for a microwave oven.
【００４３】実施例５（インサート成形） 実施例２で得られた光触媒担持ポリエステルシートを６
０ｃｍ角に裁断し、保護フィルムと反対面にスクリーン
印刷法で、操作指示と機種名、型番号を印刷し、打ち抜
き型で所定の形状に打ちぬいた。この打ち抜いたシート
を成形用の金型に保護フィルムを付けた面を下に挿入
し、金型を加温後、樹脂注入口よりＡＢＳ樹脂を加圧注
入し、インサート成形した。所定時間後、金型から樹脂
と一体となった光触媒担持シートを取り出し、電気温水
洗浄便座用の操作パネルとした。Example 5 (Insert molding) The photocatalyst-carrying polyester sheet obtained in Example 2 was replaced with 6
The sheet was cut into a 0 cm square, the operation instructions, the model name, and the model number were printed by a screen printing method on the surface opposite to the protective film, and punched into a predetermined shape with a punching die. The punched sheet was inserted into a mold for molding with the surface with the protective film attached below, and after heating the mold, ABS resin was injected under pressure from a resin injection port to perform insert molding. After a predetermined time, the photocatalyst-carrying sheet integrated with the resin was taken out of the mold and used as an operation panel for an electric hot water flush toilet seat.
【００４４】実施例６（真空成形） 厚さ０．８ｍｍの変性ポリスチレンシートの片面に試験
例３と同様の条件と方法により、接着層と光触媒層を担
持し、光触媒層塗布面に実施例２と同様の材料と方法で
保護フィルムを貼り付けた。この保護フィルムを貼り付
けた変性ポリスチレンシートを６０ｃｍ角に裁断し、保
護フィルムと反対面にスクリーン印刷法で、白濁模様と
なる図柄を白色顔料を含む塗料で印刷し、打ち抜き型で
所定の形状に打ち抜いた。この打ち抜いたシートを真空
成形用の金型に挿入し、真空成形機（三和興業株式会社
製ＦＥ−３６ＰＨ型）を使用し金型を３０秒加温後、保
護フィルムを付けた面に設けた真空吸入口より吸引し、
真空成形した。所定時間後、金型から光触媒担持シート
を取り出し、照明器具の前面に設ける光拡散板とした。Example 6 (Vacuum molding) An adhesive layer and a photocatalyst layer were carried on one surface of a modified polystyrene sheet having a thickness of 0.8 mm under the same conditions and in the same manner as in Test Example 3, and Example 2 was applied to the photocatalyst layer-coated surface. A protective film was affixed with the same material and method. The modified polystyrene sheet to which the protective film is adhered is cut into a 60 cm square, and a pattern that becomes a cloudy pattern is printed with a paint containing a white pigment on a surface opposite to the protective film by a screen printing method. Punched out. The punched sheet is inserted into a mold for vacuum forming, and the mold is heated for 30 seconds using a vacuum forming machine (manufactured by Sanwa Kogyo Co., Ltd., FE-36PH). Suction from the vacuum suction port
Vacuum formed. After a predetermined time, the photocatalyst-carrying sheet was taken out of the mold and used as a light diffusion plate provided on the front surface of the lighting fixture.
【００４５】比較例１ 試験例２で使用したポリエステルシートに光触媒を塗布
しないものを使用して、実施例３に示す方法で同様にア
クリロニトリルスチレン樹脂をインサート成形により貼
り合わせ、電気炊飯器用の操作パネルとした。Comparative Example 1 Using the polyester sheet used in Test Example 2 to which no photocatalyst was applied, an acrylonitrile styrene resin was similarly bonded by insert molding in the same manner as in Example 3 to obtain an operation panel for an electric rice cooker. And
【００４６】比較例２ 試験例２で使用したポリエステルシートに光触媒を塗布
しないものを使用して、実施例４に示す方法で同様に変
性ポリスチレン樹脂をインサート成形により貼り合わ
せ、電子レンジ用の操作パネルとした。Comparative Example 2 Using a polyester sheet used in Test Example 2 to which no photocatalyst was applied, a modified polystyrene resin was similarly bonded by insert molding according to the method shown in Example 4, and an operation panel for a microwave oven was used. And
【００４７】（光触媒活性の評価）比較例、実施例の試
料を使用して、以下に示すような光触媒活性の評価を行
い、表１に示す結果を得た。表１からもわかるように、
成形加工による光触媒活性の低下は認められなかった。(Evaluation of Photocatalytic Activity) Using the samples of Comparative Examples and Examples, the following photocatalytic activities were evaluated, and the results shown in Table 1 were obtained. As can be seen from Table 1,
No decrease in photocatalytic activity due to molding was observed.
【００４８】１）アセトアルデヒド分解活性 大きさ７０ｍｍ×７０ｍｍ角に切り出した試料を容積４
Ｌのパイレックス製ガラス容器中に設置した。この容器
中に空気とアルデヒドの混合ガスを、アルデヒド濃度が
５００ｐｐｍになるように加えた。試料に紫外線強度２
ｍＷ／ｃｍ2 のブラックライト（ＦＬ １５ＢＬ−Ｂ
松下電器株式会社製）の光を２時間照射後、容器内部の
アルデヒドガス濃度をガスクロマトグラフにより測定
し、その減少量より光触媒活性を評価した。評価基準
は、２時間照射後のアルデヒドガス濃度が、５０ｐｐｍ
以下のとき評価「Ａ」、５０〜２００ｐｐｍのとき評価
「Ｂ」、２００〜３００ｐｐｍのとき評価「Ｃ」、３０
０〜４５０ｐｐｍのとき評価「Ｄ」、４５０ｐｐｍ以上
のとき評価「Ｅ」とした。1) Acetaldehyde-decomposing activity A sample cut into a size of 70 mm × 70 mm square has a capacity of 4
L was placed in a Pyrex glass container. A mixed gas of air and aldehyde was added to this container so that the aldehyde concentration became 500 ppm. UV intensity 2 on the sample
mW / cm 2 black light (FL 15BL-B
After irradiation with light from Matsushita Electric Industrial Co., Ltd. for 2 hours, the concentration of aldehyde gas inside the container was measured by gas chromatography, and the photocatalytic activity was evaluated from the decrease. The evaluation criteria were that the aldehyde gas concentration after irradiation for 2 hours was 50 ppm
Evaluation "A" at the following times, evaluation "B" at 50 to 200 ppm, evaluation "C" at 200 to 300 ppm, 30
When it was 0 to 450 ppm, the evaluation was "D", and when it was 450 ppm or more, it was "E".
【００４９】２）サラダ油分解活性（防汚特性） 大きさ５０ｍｍ×５０ｍｍ角に切り出した試料の表面に
市販のサラダ油（日清精油株式会社製）をティッシュペ
ーパーを使用して塗布量が０．１ｍｇ／ｃｍ2になるよ
う塗布し調整した試料に、１５Ｗブラックライトブルー
蛍光灯３本を並べてＵＶ−Ａ領域の紫外線強度が３ｍＷ
／ｃｍ2 になるよう試料との距離を調節して光照射し、
照射中の重量変化を０．１ｍｇまで測定可能な精密天秤
で秤量して記録した。２４時間後における塗布サラダ油
の重量残存率により評価し、評価基準は、２４時間照射
後のサラダ油残存率が、１０％以下のとき評価「Ａ」、
１０〜３０％のとき評価「Ｂ」、３０〜５０％のとき評
価「Ｃ」、５０〜８０％のとき評価「Ｄ」、８０％以上
のとき評価「Ｅ」とした。2) Salad oil decomposition activity (antifouling properties) Commercially available salad oil (manufactured by Nisshin Seimitsu Co., Ltd.) was applied to the surface of a sample cut to a size of 50 mm × 50 mm using tissue paper in an amount of 0.1 mg. / 15 cm3 / cm 2, and three 15 W black light blue fluorescent lamps are arranged on the sample to adjust the UV intensity in the UV-A region to 3 mW.
/ Cm 2 and adjust the distance to the sample to irradiate light,
The change in weight during irradiation was weighed and recorded on a precision balance capable of measuring up to 0.1 mg. Evaluation was made based on the residual weight of the applied salad oil after 24 hours, and the evaluation criteria were “A” when the residual ratio of salad oil after irradiation for 24 hours was 10% or less,
The evaluation was "B" at 10 to 30%, "C" at 30 to 50%, "D" at 50 to 80%, and "E" at 80% or more.
【００５０】３）抗菌性評価 大きさ５０ｍｍ×５０ｍｍ角に切り出した試料を、８０
％エタノールで消毒し１５０℃で乾燥して滅菌後、予め
前培養と希釈を行って菌濃度を１０5 個／ｍｌに調節し
ておいた大腸菌の菌液を０．２ｍｌ試料面に滴下しイン
キュベーター内にセットした。白色蛍光灯（１５Ｗ×２
本、光源との距離１０ｃｍ）の光を照射したもの、及び
光照射を全く行わなかったものの、２種の光照射条件で
各々４個の試料をセットした。所定時間後（１、２、
３、４時間後）に試料を取り出し、滅菌生理食塩水に浸
した滅菌ガーゼで試料上の菌液を拭き取り、拭き取った
滅菌ガーゼを１０ｍｌの滅菌生理食塩水に入れ十分撹拌
した。この上澄み菌液をオートクレーブ滅菌した９５ｍ
ｍφのシャーレ寒天培地に植え付け、３６℃２４時間培
養後大腸菌のコロニー数を計数した。インキュベーター
に入れるまでの操作を全く同一にした基準菌数測定用試
料を同一の方法により調整し、滅菌生理食塩水の上澄み
液をシャーレ寒天培地に植え付けて２４時間培養後の大
腸菌のコロニー数を計数し、その数値を基準にして各試
料の所定時間後における大腸菌の生存数を算出した。４
時間経過後の蛍光灯の光を照射した試料の大腸菌の残存
率により抗菌性を評価した。評価基準は、４時間後の大
腸菌残存率が、２０％以下のとき評価「Ａ」、２０〜４
０％のとき評価「Ｂ」、４０〜６０％のとき評価
「Ｃ」、６０〜８０％のとき評価「Ｄ」、８０％以上の
とき評価「Ｅ」とした。3) Evaluation of antibacterial activity A sample cut into a size of 50 mm × 50 mm square was
After sterilizing by drying at 150 ° C. with 0.2% ethanol, 0.2 ml of a bacterial solution of Escherichia coli which had been precultured and diluted to adjust the bacterial concentration to 10 5 cells / ml was dropped on the sample surface, and the solution was placed in an incubator. Set inside. White fluorescent lamp (15W × 2
Four specimens were set under two kinds of light irradiation conditions, each of which was irradiated with light at a distance of 10 cm from the light source and a light source was not irradiated at all. After a predetermined time (1, 2,
After 3 or 4 hours), the sample was taken out, the bacterial solution on the sample was wiped off with sterile gauze dipped in sterile physiological saline, and the wiped sterile gauze was put in 10 ml of sterile physiological saline and stirred sufficiently. The supernatant was autoclaved and sterilized to 95 m.
The cells were inoculated on an mφ Petri dish agar medium, cultured at 36 ° C. for 24 hours, and the number of E. coli colonies was counted. A sample for measuring the standard number of bacteria was prepared in exactly the same manner until the operation was put into the incubator, and the supernatant of sterilized saline was inoculated on a Petri dish agar medium, and the number of E. coli colonies after 24 hours of culture was counted. Then, the surviving number of E. coli after a predetermined time of each sample was calculated based on the numerical value. 4
The antimicrobial activity was evaluated based on the residual ratio of Escherichia coli in the sample irradiated with the light of the fluorescent lamp after a lapse of time. The evaluation criteria were "A" when the residual ratio of Escherichia coli after 4 hours was 20% or less.
When it was 0%, the evaluation was "B", when it was 40 to 60%, it was "C", when it was 60 to 80%, it was "D", and when it was 80% or more, it was "E".
【００５１】４）付着性評価 ＪＩＳ Ｋ ５４００に規定する碁盤目テープ法試験に
より、付着性の評価を行った。切り傷の間隔を２ｍｍと
し、ます目の数を２５コとした。評価点数は、ＪＩＳ
Ｋ ５４００に記載の基準で行った。4) Evaluation of Adhesion Adhesion was evaluated by a cross-cut tape test specified in JIS K5400. The interval between cuts was 2 mm, and the number of squares was 25. Evaluation score is JIS
Performed according to the standard described in K5400.
【００５２】５）耐久性評価 担持した試料にブラックライトで紫外線強度３ｍＷ／ｃ
ｍ2 の光を温度４０℃、相対湿度９０％の恒温恒湿槽内
で５００時間照射後、ＪＩＳ Ｋ ５４００に規定の碁
盤目テープ法による付着性を測定し、耐久性の評価とし
た。評価点数は、付着性評価と同じである。5) Evaluation of durability The supported sample was irradiated with black light at an ultraviolet intensity of 3 mW / c.
After irradiating with m 2 light for 500 hours in a thermo-hygrostat at a temperature of 40 ° C. and a relative humidity of 90%, the adhesion was measured by a grid tape method specified in JIS K 5400, and the durability was evaluated. The evaluation score is the same as the evaluation of adhesion.
【００５３】 ６）耐摩耗性評価大平理化工業株式会社製の擦り摩耗試
験器ラビングテスターを使用して同社から市販されてい
る摩耗試験用フェルトで荷重２００ｇ、摩耗回数５００
回で耐摩耗試験を実施した。評価基準は以下の基準で行
った。 肉眼で傷がほとんど見えないもの Ａ 筋や摩耗傷が明らかに見えるもの Ｂ 摩耗試験部分が白くなっているもの Ｃ 光触媒層がほとんど剥離したもの Ｄ6) Evaluation of abrasion resistance Using a rubbing tester manufactured by Ohira Rika Kogyo Co., Ltd. with a wear test felt commercially available from the company using a rubbing tester with a load of 200 g and a wear frequency of 500
An abrasion resistance test was performed each time. The evaluation criteria were as follows. Scratches with barely visible damage to the naked eye A Streaks and wear scars are clearly visible B Wear test parts are white C Photocatalyst layers are almost peeled D
【００５４】[0054]
【表１】 [Table 1]
【００５５】[0055]
【発明の効果】本発明によると、種々の形状をした光触
媒担持熱可塑性樹脂成形体をその光触媒活性を低下させ
ることなく効率良く製造することができることから、防
汚、抗菌、防カビ等高い光触媒活性と優れた耐久性と相
俟って、既知の光触媒の用途は勿論のこと、光触媒の新
たな用途も期待できる。According to the present invention, a photocatalyst-supported thermoplastic resin molded article having various shapes can be efficiently produced without lowering its photocatalytic activity, so that high photocatalysts such as antifouling, antibacterial and antifungal can be obtained. Combined with the activity and the excellent durability, not only applications of known photocatalysts but also new applications of photocatalysts can be expected.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｂ２９Ｋ 101:12 Ｂ２９Ｌ 31:00 (72)発明者 小野 和男 千葉県市原市五井南海岸12−54日本曹達株 式会社機能製品研究所内 (72)発明者 片岡 征之 東京都千代田区大手町２−２−１日本曹達 株式会社内 (72)発明者 岡部 和次 茨城県北茨城市磯原町磯原1274 ニッソー 樹脂株式会社内 (72)発明者 古茂田 義春 茨城県北茨城市磯原町磯原1274 ニッソー 樹脂株式会社内──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification symbol FI // B29K 101: 12 B29L 31:00 (72) Inventor Kazuo Ono 12-54 Goi Minamikaigan, Ichihara-shi, Chiba Pref. Inside the Functional Products Research Laboratory (72) Inventor Masayuki Kataoka 2-2-1 Otemachi, Chiyoda-ku, Tokyo Inside Nippon Soda Co., Ltd. (72) Inventor Kazuji Okabe 1274 Isohara, Isohara-cho, Kitaibaraki-shi, Ibaraki Inventor Yoshiharu Komoda 1274 Isohara, Isohara-cho, Kitaibaraki-city, Ibaraki Pref.
Claims (20)
１００〜３００℃の範囲で成形加工することにより得ら
れる光触媒担持熱可塑性樹脂成形体。1. A photocatalyst-carrying thermoplastic resin molded article obtained by molding a photocatalyst-carrying thermoplastic resin plate at a molding temperature of 100 to 300 ° C.
介して光触媒層が担持された熱可塑性樹脂板からなる請
求項１記載の光触媒担持熱可塑性樹脂成形体。2. The photocatalyst-supported thermoplastic resin article according to claim 1, wherein the photocatalyst-supported thermoplastic resin plate is a thermoplastic resin plate on which the photocatalyst layer is supported via an adhesive layer.
脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリオ
レフィン樹脂、ポリアミド樹脂、ポリ塩化ビニル樹脂、
ＡＢＳ樹脂、アクリル系樹脂、ポリフェニレンエーテル
樹脂の中から選ばれた樹脂からなる請求項１又は２記載
の光触媒担持熱可塑性樹脂成形体。3. A thermoplastic resin plate comprising a polystyrene resin, a polyester resin, a polycarbonate resin, a polyolefin resin, a polyamide resin, a polyvinyl chloride resin,
3. The photocatalyst-supported thermoplastic resin molded body according to claim 1, comprising a resin selected from an ABS resin, an acrylic resin, and a polyphenylene ether resin.
体である請求項１〜３のいずれか記載の光触媒担持熱可
塑性樹脂成形体。4. The photocatalyst-supported thermoplastic resin molded article according to claim 1, wherein the thermoplastic resin plate is a single-layer or multilayer laminate.
は多層押出しにより形成される請求項４記載の光触媒担
持熱可塑性樹脂成形体。5. The photocatalyst-supported thermoplastic resin molded article according to claim 4, wherein the laminate is formed by hot pressing, bonding with an adhesive, or multilayer extrusion.
０ｍｍである請求項１〜５のいずれか記載の光触媒担持
熱可塑性樹脂成形体。6. The thermoplastic resin plate has a thickness of 50 μm to 1 μm.
The photocatalyst-supported thermoplastic resin molded article according to any one of claims 1 to 5, which has a thickness of 0 mm.
ング剤を含有する接着層塗布液の塗布により形成される
請求項２〜６のいずれか記載の光触媒担持熱可塑性樹脂
成形体。7. The photocatalyst-supporting thermoplastic resin molded article according to claim 2, wherein the adhesive layer is formed by applying an adhesive layer coating solution containing a silane coupling agent as a curing agent.
１０〜５０重量％含有するシリコン変性樹脂、又は、コ
ロイダルシリカを５〜３０重量％含有するシリコン変性
樹脂を２〜２０重量％含む塗布液に、硬化剤としてシラ
ンカップリング剤を塗布液に対して０．１〜５重量％添
加した接着層塗布液を用いる請求項７記載の光触媒担持
熱可塑性樹脂成形体。8. A coating liquid containing a silicone-modified resin containing 10 to 50% by weight of polysiloxane or 2 to 20% by weight of a silicon-modified resin containing 5 to 30% by weight of colloidal silica as an adhesive layer coating liquid. The photocatalyst-supported thermoplastic resin molded article according to claim 7, wherein an adhesive layer coating liquid containing 0.1 to 5% by weight of a silane coupling agent added to the coating liquid as a curing agent is used.
メトキシシラン又はその加水分解生成物であるポリシロ
キサンを１〜１０重量％とシリカゾルを０．１〜５重量
％含む塗布液に、硬化剤としてシランカップリング剤を
塗布液に対して０．１〜５重量％添加した接着層塗布液
を用いる請求項７記載の光触媒担持熱可塑性樹脂成形
体。9. A coating solution containing 1 to 10% by weight of monoalkyltrimethoxysilane or a polysiloxane as a hydrolysis product thereof and 0.1 to 5% by weight of silica sol as a coating solution for the adhesive layer, The photocatalyst-carrying thermoplastic resin molded article according to claim 7, wherein an adhesive layer coating liquid in which a silane coupling agent is added in an amount of 0.1 to 5% by weight based on the coating liquid is used.
る請求項７〜９のいずれか記載の光触媒担持熱可塑性樹
脂成形体。10. The photocatalyst-supporting thermoplastic resin molded article according to claim 7, wherein the thickness of the adhesive layer is 0.5 to 5 μm.
化物のゾルを固形分として１〜１０重量％、酸化チタン
ゾルを固形分として１〜１０重量％含有する光触媒層塗
布液の塗布により形成されることを特徴とする請求項２
〜１０のいずれか記載の光触媒担持熱可塑性樹脂成形
体。11. A photocatalyst layer is formed by applying a photocatalyst layer coating solution containing 1 to 10% by weight of a metal oxide or metal hydroxide sol as a solid content and 1 to 10% by weight of a titanium oxide sol as a solid content. 3. The method according to claim 2, wherein
The photocatalyst-supported thermoplastic resin molded article according to any one of items 10 to 10.
て１〜１０重量％、モノアルキルトリメトキシシラン又
はその加水分解生成物を０．１〜５重量％、及び酸化チ
タンゾルを固形分として１〜１０重量％含有する光触媒
層塗布液の塗布により形成されることを特徴とする請求
項２〜１０のいずれか記載の光触媒担持熱可塑性樹脂成
形体。12. The photocatalyst layer comprises silica sol at a solid content of 1 to 10% by weight, monoalkyltrimethoxysilane or a hydrolysis product thereof at 0.1 to 5% by weight, and titanium oxide sol at a solid content of 1 to 10% by weight. The photocatalyst-carrying thermoplastic resin molded article according to any one of claims 2 to 10, which is formed by applying a photocatalyst layer coating liquid containing the photocatalyst layer by weight.
ある請求項１１又は１２記載の光触媒担持熱可塑性樹脂
成形体。13. The photocatalyst-carrying thermoplastic resin molded article according to claim 11, wherein the thickness of the photocatalyst layer is 0.1 to 5 μm.
形、圧空成形、真空圧空成形、プレス成形により行われ
る請求項１〜１３記載の光触媒担持熱可塑性樹脂成形
体。14. The photocatalyst-supported thermoplastic resin molded article according to claim 1, wherein the molding is performed by insert molding, vacuum molding, air pressure molding, vacuum pressure molding, or press molding.
ンカップリング剤が添加された接着層塗布液を塗布・乾
燥した後、この接着層に光触媒層塗布液を塗布・乾燥し
て、熱可塑性樹脂板上に接着層を介して光触媒層を担持
した光触媒担持熱可塑性樹脂板を調製し、この光触媒担
持熱可塑性樹脂板を、成形温度１００℃〜３００℃の範
囲で成形加工することを特徴とする光触媒担持熱可塑性
樹脂成形体の製造方法。15. An adhesive layer coating solution containing a silane coupling agent as a curing agent is applied to a thermoplastic resin plate and dried, and then a photocatalytic layer coating solution is applied to the adhesive layer and dried. A photocatalyst-supporting thermoplastic resin plate having a photocatalyst layer supported on a resin plate via an adhesive layer is prepared, and the photocatalyst-supporting thermoplastic resin plate is molded at a molding temperature of 100 ° C to 300 ° C. For producing a photocatalyst-supported thermoplastic resin molded article.
樹脂板に、請求項７〜９のいずれかに記載された接着層
塗布液、又は、テトラアルコキシシラン又はその加水分
解生成物を１〜１０重量％とシリカゾルを０．１〜１０
重量％及びシリコン含有量１〜１０重量％のアクリルシ
リコン樹脂からなる接着層塗布液を、塗布・乾燥した
後、該接着層上に請求項１１又は１２に記載された光触
媒層塗布液を塗布・乾燥して得られる光触媒担持熱可塑
性樹脂板の光触媒塗布面にさらに保護フィルムが貼り付
けられてなる加熱成形加工用の光触媒担持熱可塑性樹脂
板。16. A thermoplastic resin plate having a thickness of 100 μm to 10 mm, wherein the adhesive layer coating liquid according to claim 7 or tetraalkoxysilane or a hydrolysis product thereof is 1 to 10% by weight. % And silica sol from 0.1 to 10
An adhesive layer coating solution comprising an acrylic silicon resin having a weight percentage of 1 to 10% by weight and a silicon content of 1 to 10% by weight is applied and dried, and then the photocatalyst layer coating solution according to claim 11 or 12 is applied on the adhesive layer. A photocatalyst-supporting thermoplastic resin plate for heat molding, wherein a protective film is further attached to a photocatalyst-coated thermoplastic resin plate obtained by drying.
り付けてなる光触媒担持熱可塑性樹脂板の光触媒担持面
の反対面に、インサート成形、真空成形、圧空成形、真
空圧空成形、プレス成形によって、同一もしくは相異な
る種類の熱可塑性樹脂を１００〜３００℃の成形温度で
成形積層することにより得られる光触媒担持熱可塑性樹
脂成形体。17. The photocatalyst-supporting thermoplastic resin plate, to which the protective film according to claim 16 is attached, on the surface opposite to the photocatalyst-supporting surface, by insert molding, vacuum molding, air pressure molding, vacuum air pressure molding, and press molding. A photocatalyst-supported thermoplastic resin molded article obtained by molding and laminating the same or different kinds of thermoplastic resins at a molding temperature of 100 to 300 ° C.
媒担持熱可塑性樹脂板の光触媒担持面に、保護フィルム
を貼り付けた後、光触媒担持面の反対面に、図柄及び文
字を印刷した後、インサート成形、真空成形、圧空成
形、真空圧空成形、プレス成形によって、同一もしくは
相異なる種類の熱可塑性樹脂を光触媒担持熱可塑性樹脂
板の光触媒担持面の反対面に１００〜３００℃の成形温
度で成形積層することにより得られる光触媒担持熱可塑
性樹脂成形体。18. After attaching a protective film to the photocatalyst-carrying surface of the photocatalyst-carrying thermoplastic resin plate having a visible light linear transmittance of 60% or more, after printing a pattern and characters on the surface opposite to the photocatalyst-carrying surface. The same or different types of thermoplastic resins are formed on the opposite side of the photocatalyst-carrying thermoplastic resin plate at a molding temperature of 100 to 300 ° C. by insert molding, vacuum molding, air pressure molding, vacuum air pressure molding, and press molding. A photocatalyst-supported thermoplastic resin molded article obtained by molding and laminating.
ｍのポリエステルフィルム、フッ素樹脂フィルム、ポリ
エチレンフィルム又はポリプロピレンフィルムのいずれ
かであることを特徴とする請求項１６〜１８に記載の光
触媒担持熱可塑性樹脂成形体。19. The protective film has a thickness of 10 to 100 μm.
The photocatalyst-supported thermoplastic resin molded article according to any one of claims 16 to 18, which is any one of a polyester film, a fluororesin film, a polyethylene film, and a polypropylene film.
７〜１９のいずれかに記載の光触媒担持熱可塑性樹脂成
形体を用いることを特徴とする操作パネル。20. The method according to claim 1, wherein the protective film has been peeled off.
An operation panel using the photocatalyst-supporting thermoplastic resin molded article according to any one of 7 to 19.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10316430A JPH11267518A (en) | 1997-11-07 | 1998-11-06 | Photocatalyst-supporting thermoplastic resin molding |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-322249 | 1997-11-07 | ||
| JP32224997 | 1997-11-07 | ||
| JP10316430A JPH11267518A (en) | 1997-11-07 | 1998-11-06 | Photocatalyst-supporting thermoplastic resin molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11267518A true JPH11267518A (en) | 1999-10-05 |
Family
ID=26568656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10316430A Pending JPH11267518A (en) | 1997-11-07 | 1998-11-06 | Photocatalyst-supporting thermoplastic resin molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11267518A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001286766A (en) * | 2000-04-11 | 2001-10-16 | Nippon Soda Co Ltd | Photocatalyst-bearing structure body, production method of the same, composition for intermediate layer |
| JP2001327872A (en) * | 2000-05-24 | 2001-11-27 | Cleanup Corp | Photocatalytic coating film and method for preparing the same |
| JP2010253466A (en) * | 2009-03-28 | 2010-11-11 | Bekku Kk | Coating method |
| JP2010253465A (en) * | 2009-03-28 | 2010-11-11 | Bekku Kk | Coating method |
-
1998
- 1998-11-06 JP JP10316430A patent/JPH11267518A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001286766A (en) * | 2000-04-11 | 2001-10-16 | Nippon Soda Co Ltd | Photocatalyst-bearing structure body, production method of the same, composition for intermediate layer |
| JP2001327872A (en) * | 2000-05-24 | 2001-11-27 | Cleanup Corp | Photocatalytic coating film and method for preparing the same |
| JP2010253466A (en) * | 2009-03-28 | 2010-11-11 | Bekku Kk | Coating method |
| JP2010253465A (en) * | 2009-03-28 | 2010-11-11 | Bekku Kk | Coating method |
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