JPH11236518A - Surface treating agent for automotive body and method for forming photocatalytic coating film on automotive body by using same - Google Patents
Surface treating agent for automotive body and method for forming photocatalytic coating film on automotive body by using sameInfo
- Publication number
- JPH11236518A JPH11236518A JP10039041A JP3904198A JPH11236518A JP H11236518 A JPH11236518 A JP H11236518A JP 10039041 A JP10039041 A JP 10039041A JP 3904198 A JP3904198 A JP 3904198A JP H11236518 A JPH11236518 A JP H11236518A
- Authority
- JP
- Japan
- Prior art keywords
- treating agent
- water
- automobile body
- surface treating
- automotive body
- 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
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 20
- 239000011248 coating agent Substances 0.000 title claims abstract description 19
- 238000000576 coating method Methods 0.000 title claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000084 colloidal system Substances 0.000 claims abstract description 9
- 150000004756 silanes Chemical class 0.000 claims abstract description 5
- 125000005372 silanol group Chemical group 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003868 ammonium compounds Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000011941 photocatalyst Substances 0.000 claims description 30
- 239000012756 surface treatment agent Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005051 trimethylchlorosilane Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 125000005466 alkylenyl group Chemical group 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- MWRUIIQJFZKJTH-UHFFFAOYSA-M methyl sulfate;trimethyl(octyl)azanium Chemical compound COS([O-])(=O)=O.CCCCCCCC[N+](C)(C)C MWRUIIQJFZKJTH-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- -1 trimethyl lauryl ammonium toluene sulfonate Chemical compound 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- WJQZZLQMLJPKQH-UHFFFAOYSA-N 2,4-dichloro-6-methylphenol Chemical compound CC1=CC(Cl)=CC(Cl)=C1O WJQZZLQMLJPKQH-UHFFFAOYSA-N 0.000 description 1
- DXQIEHOBXIEJFN-UHFFFAOYSA-N 3-(dodecanoylamino)propyl-trimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC(=O)NCCC[N+](C)(C)C DXQIEHOBXIEJFN-UHFFFAOYSA-N 0.000 description 1
- PLXLQGPXPXIVKM-UHFFFAOYSA-N 3-chloropropyl(tripropoxy)silane Chemical compound CCCO[Si](CCCCl)(OCCC)OCCC PLXLQGPXPXIVKM-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- SXRINEDQNBUOLP-GMFCBQQYSA-N CCCCCCCCC/C=C\CCCCCCCC[NH+](CCO)CCO.COP(=O)([O-])OC Chemical compound CCCCCCCCC/C=C\CCCCCCCC[NH+](CCO)CCO.COP(=O)([O-])OC SXRINEDQNBUOLP-GMFCBQQYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- QJLDTVCWUDCBME-UHFFFAOYSA-K aluminum;trithiocyanate Chemical compound [Al+3].[S-]C#N.[S-]C#N.[S-]C#N QJLDTVCWUDCBME-UHFFFAOYSA-K 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PNCQLRYMHQOAOR-UHFFFAOYSA-N bis(2-hydroxyethyl)-methyl-octadecylazanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(CCO)CCO PNCQLRYMHQOAOR-UHFFFAOYSA-N 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- YWUMSTQPHOGYIB-UHFFFAOYSA-M decyl-ethyl-dimethylazanium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CCCCCCCCCC[N+](C)(C)CC YWUMSTQPHOGYIB-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- YFRSIZIOCKDXNY-UHFFFAOYSA-N dimethyl(octyl)azanium;acetate Chemical compound CC(O)=O.CCCCCCCCN(C)C YFRSIZIOCKDXNY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、既に使用に供され
ている自動車のボディに防汚性の光触媒被膜を形成する
ための表面処理剤と、この表面処理剤を用いた光触媒被
膜の形成方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent for forming an antifouling photocatalytic film on an automobile body already in use, and a method for forming a photocatalytic film using the surface treatment agent. About.
【０００２】[0002]
【従来の技術】自動車のボディは、煤塵や排気ガス等の
燃焼生成物等の付着により汚れやすい。具体的にはサイ
ドボディには筋状の黒い汚れが、またボンネット（フロ
ントボディ）には水玉状の黒い汚れが生じやすく、これ
らの汚れの除去には時間がかかる。2. Description of the Related Art The body of an automobile is easily contaminated by the adhesion of combustion products such as dust and exhaust gas. Specifically, streak-like black dirt is likely to be generated on the side body, and polka dot-like black dirt is likely to be generated on the bonnet (front body), and it takes time to remove these dirt.
【０００３】ここで、自動車のボディに視覚的に目立つ
汚れが生じるのは以下のメカニズムに基づくと考えられ
る。先ず、大気中に浮遊する煤塵等が晴天時にボンネッ
トやサイドボディに堆積する。この堆積物の大部分は降
雨の際に雨水により流されるが、自動車のボディは塗装
によって疎水性表面となっているので、ボンネットでは
水滴が残留し、サイドボディでは雨筋状に水滴が残留す
る。そして、表面が乾燥すると、水滴が残留した部分に
黒い汚れが付着し、ボンネットには水玉状の黒い汚れが
生じ、サイドボディには筋状の黒い汚れが生じる。Here, it is considered that the appearance of visually noticeable dirt on the body of the automobile is based on the following mechanism. First, dust and the like floating in the atmosphere accumulate on the bonnet and side bodies in fine weather. Most of this sediment is washed away by rainwater during rainfall, but since the body of the car has been painted with a hydrophobic surface, water droplets remain on the bonnet and rain streaks on the side body. . Then, when the surface is dried, black stains adhere to portions where the water droplets remain, polka dot-like black stains occur on the hood, and streak-like black stains occur on the side bodies.
【０００４】燃焼生成物等の付着による汚れに対する従
来の対策は、一般的に撥水性ワックスをボディに塗布
し、ボディ表面に水滴が残留しないようにしている。[0004] Conventional countermeasures against contamination due to adhesion of combustion products and the like generally apply a water-repellent wax to a body so that water droplets do not remain on the body surface.
【０００５】ところで、本発明者らは、ＰＣＴ／ＷＯ９
６／２９３７５号に開示したように、基材表面に光触媒
層を形成すると、光触媒の光励起に応じて前記光触媒層
表面が、水との接触角に換算して１０°以下という高度
の親水性を呈することを見出し、さらにそれによりガラ
ス、レンズ、鏡等の透明部材の防曇・視界確保性向上、
自動車ボディ、物品表面の水洗浄性・降雨洗浄性向上な
どの効果が得られることを見出した。By the way, the present inventors have proposed PCT / WO9
As disclosed in JP-A-6 / 29375, when a photocatalyst layer is formed on the surface of a substrate, the surface of the photocatalyst layer exhibits a high degree of hydrophilicity of 10 ° or less in terms of a contact angle with water in response to photoexcitation of the photocatalyst. To improve the anti-fog and visibility securing of transparent members such as glass, lenses and mirrors.
It has been found that effects such as improved water washability and rainfall washability on the surface of automobile bodies and articles can be obtained.
【０００６】また、光触媒層に紫外線を照射すると、価
電子帯にあった電子（ｅ-）が伝導帯に励起され、価電
子帯には正孔（ｈ+）が生じ、これら電子（ｅ-）及び正
孔（ｈ+）が酸化還元反応を促進することで、汚れ成分
を分解する作用があることは従来から知られている。When the photocatalyst layer is irradiated with ultraviolet rays, electrons (e − ) in the valence band are excited to the conduction band, and holes (h + ) are generated in the valence band, and these electrons (e − ) are generated. ) And holes (h + ) have been known to promote the oxidation-reduction reaction, thereby decomposing dirt components.
【０００７】[0007]
【発明が解決しようとする課題】上述した光触媒層を既
に使用に供している自動車のボディ表面に形成しようと
すると、ボディ表面には既に汚染物質が付着している場
合が多く、汚染物質の影響で光触媒層を形成するための
コーティング液が弾かれたり、光触媒層のボディ表面に
対する固着力が不足してしまう。When the photocatalyst layer described above is to be formed on the surface of a body of an automobile which is already in use, pollutants are often already adhered to the body surface. As a result, the coating liquid for forming the photocatalyst layer is repelled, or the photocatalytic layer is insufficiently fixed to the body surface.
【０００８】また、ボディ表面に付着している汚れ成分
を洗浄によって除去したとしても、ボディ表面は疎水性
であるので、光触媒コーティング液をムラなく塗布する
ことは困難である。[0008] Even if dirt components adhering to the body surface are removed by washing, it is difficult to apply the photocatalyst coating liquid evenly because the body surface is hydrophobic.
【０００９】[0009]
【課題を解決するための手段】本発明は、上記事情に鑑
みてなされたものであり、既に使用に供されている自動
車ボディの表面に光触媒層を形成する前に、予めボディ
表面に塗布することで当該表面を親水化し、最外側とな
る光触媒層のボディ表面への結合強度を向上させる表面
処理剤を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is applied to the surface of an automobile body which has already been used before forming a photocatalytic layer on the surface of the body. Accordingly, an object of the present invention is to provide a surface treatment agent that makes the surface hydrophilic and improves the bonding strength of the outermost photocatalytic layer to the body surface.
【００１０】上記課題を解決すべく本発明に係る自動車
ボディ用表面処理剤は、水中で負の表面電荷を有する水
分散無機コロイドを部分的に疎水化した水性ゾルから構
成される。In order to solve the above problems, the surface treating agent for an automobile body according to the present invention comprises an aqueous sol obtained by partially hydrophobizing a water-dispersed inorganic colloid having a negative surface charge in water.
【００１１】前記水分散無機コロイドとしては、シリカ
ゾルやリチウムシリケート、酸化アンチモン等が挙げら
れるが、シリカゾルが最適である。酸性シリカゾルとし
ては例えば、カタロイドＳＮ（触媒化成社製）、スノー
テックスＯ（日産化学社製）、スノーテックスＯＬ（日
産化学社製）があり、塩基性シリカゾルとしては例え
ば、カタロイドＳ−２０Ｌ（触媒化成社製）、スノーテ
ックス２０（日産化学社製）、スノーテックスＣ（日産
化学社製）及びスノーテックスＮ（日産化学社製）があ
る。Examples of the water-dispersed inorganic colloid include silica sol, lithium silicate, antimony oxide and the like, and silica sol is most suitable. Examples of the acidic silica sol include Cataloid SN (manufactured by Catalyst Kasei Co., Ltd.), Snowtex O (manufactured by Nissan Chemical Co., Ltd.) and Snowtex OL (manufactured by Nissan Chemical Co., Ltd.). Chemical Co., Ltd.), Snowtex 20 (Nissan Chemical), Snowtex C (Nissan Chemical) and Snowtex N (Nissan Chemical).
【００１２】また、シリカゾルの部分的な疎水化は、分
子内に少なくとも１個のシラノール基を有するシラン誘
導体及び／又はその縮合物との接触反応、或いは、正の
イオン種との接触反応にてなすことができる。ここで、
正のイオン種としては、炭素数４〜１８のアルキル基又
はアルケニル基を有するアンモニウム化合物、若しくは
水溶性アルミニウム塩が挙げられる。Further, the silica sol is partially hydrophobized by a contact reaction with a silane derivative having at least one silanol group in the molecule and / or a condensate thereof, or a contact reaction with a positive ionic species. I can do it. here,
Examples of the positive ion species include an ammonium compound having an alkyl group or an alkenyl group having 4 to 18 carbon atoms, or a water-soluble aluminum salt.
【００１３】分子内に少なくとも１個のシラノール基を
有するシラン誘導体及び／又はその縮合物としては、ト
リメチルクロルシラン、トリメチルモノメトキシシラ
ン、ジメチルジメトキシシラン、γ−クロロプロピルメ
チルジメトキシシラン、γ−グリシドキシプロピルメチ
ルジメトキシシラン、メチルトリメトキシシラン、メチ
ルトリエトキシシラン、ビニルトリクロルシラン、ビニ
ルトリエトキシシラン、ビニルトリ（メトキシエトキ
シ）シラン、ビニルトリアセトキシシラン、γ−クロロ
プロピルトリプロポキシシラン、γ−メルカプトプロピ
ルトリエトキシシラン、γ−グリシドキシプロピルトリ
メトキシシラン、γ−メタクリロキシトリエトキシシラ
ン、フェニルトリメトキシシラン、テトラメトキシシラ
ン、テトラエトキシシランが挙げられる。The silane derivative having at least one silanol group in the molecule and / or a condensate thereof include trimethylchlorosilane, trimethylmonomethoxysilane, dimethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycide Xypropylmethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, vinyltriacetoxysilane, γ-chloropropyltripropoxysilane, γ-mercaptopropyltri Ethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxytriethoxysilane, phenyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane And the like.
【００１４】炭素数４〜１８のアルキル基又はアルケニ
ル基を有するアンモニウム化合物としては、トリメチル
オクチルアンモニウムメチルサルフェート、ジメチルエ
チルデシルアンモニウムエチルサルフェート、トリメチ
ルラウリルアンモニウムトルエンスルホネート、ビス
（２−ヒドロキシエチル）メチルステアリルアンモニウ
ムジメチルホスフェート、ビス（２−ヒドロキシエチ
ル）メチルオレイルアンモニウムジメチルホスフェー
ト、γ−ラウロイルアミノプロピルトリメチルアンモニ
ウムクロライド、ジメチルオクチルアミン酢酸塩、ラウ
リルアミン−Ｐ−トルエンスルホン酸塩等が挙げられ
る。また、水溶性アルミニウム塩としては、硫酸アルミ
ニウム、塩化アルミニウム、硝酸アルミニウム、チオシ
アン酸アルミニウム、酢酸アルミニウム、乳酸アルミニ
ウム、酒石酸アルミニウム、硫酸カリウムアルミニウム
等が挙げられる。Examples of the ammonium compound having an alkyl group or an alkenyl group having 4 to 18 carbon atoms include trimethyloctyl ammonium methyl sulfate, dimethyl ethyl decyl ammonium ethyl sulfate, trimethyl lauryl ammonium toluene sulfonate, and bis (2-hydroxyethyl) methyl stearyl ammonium. Examples include dimethyl phosphate, bis (2-hydroxyethyl) methyloleyl ammonium dimethyl phosphate, γ-lauroylaminopropyltrimethyl ammonium chloride, dimethyloctylamine acetate, and laurylamine-P-toluenesulfonate. Examples of the water-soluble aluminum salt include aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum thiocyanate, aluminum acetate, aluminum lactate, aluminum tartrate, and potassium aluminum sulfate.
【００１５】また、光触媒コーティング液を構成する光
触媒粒子としては、アナターゼ型酸化チタン、ルチル型
酸化チタン、酸化亜鉛、酸化錫、酸化第二鉄、三酸化二
ビスマス、三酸化タングステン、チタン酸ストロンチウ
ム等が挙げられる。The photocatalyst particles constituting the photocatalyst coating solution include anatase type titanium oxide, rutile type titanium oxide, zinc oxide, tin oxide, ferric oxide, bismuth trioxide, tungsten trioxide, strontium titanate, and the like. Is mentioned.
【００１６】光触媒層の形成方法としては、図１に示す
ように、自動車のボディ表面を洗浄して汚れを落とした
後、当該表面に上記構成の表面処理剤を塗布する。する
と、ボディ表面にはシリカ粒子が沈着して親水化せしめ
られる。そこで、この親水化された表面に光触媒コーテ
ィング液を塗布し乾燥せしめることで、ボディ表面に対
する結合力に優れた光触媒層が得られる。As a method of forming the photocatalyst layer, as shown in FIG. 1, after cleaning the surface of the body of an automobile to remove dirt, the surface treatment agent having the above structure is applied to the surface. Then, the silica particles are deposited on the body surface and are made hydrophilic. Then, a photocatalyst coating solution is applied to this hydrophilic surface and dried to obtain a photocatalyst layer having excellent bonding strength to the body surface.
【００１７】因みに、特公昭６２−１８２２４号公報に
は、合成樹脂成形物等の疎水性固体表面に水系高分子液
を塗布するための前処理剤として、水中で負の表面電荷
を有する水分散無機コロイドを部分的に疎水化した水性
ゾルが提案されているが、自動車のボディ表面に光触媒
層を形成するための前処理剤としては何ら示唆されてい
ない。Incidentally, Japanese Patent Publication No. 62-18224 discloses an aqueous dispersion having a negative surface charge in water as a pretreatment agent for applying an aqueous polymer liquid to the surface of a hydrophobic solid such as a synthetic resin molded product. Although an aqueous sol in which an inorganic colloid is partially hydrophobized has been proposed, it has not been suggested as a pretreatment agent for forming a photocatalytic layer on the surface of an automobile body.
【００１８】また、本出願人は、コロイダルシリカと界
面活性剤を含有する表面処理剤を提案している。しかし
ながら、界面活性剤を含む場合には、界面活性剤の添加
量にもよるが、その上に形成する光触媒層の特性に悪影
響を及ぼしたり、光触媒層の剥離を引き起こすことが考
えられる。The present applicant has proposed a surface treatment agent containing colloidal silica and a surfactant. However, when a surfactant is contained, it depends on the amount of the surfactant to be added, which may adversely affect the properties of the photocatalyst layer formed thereon or cause peeling of the photocatalyst layer.
【００１９】[0019]
【発明の実施の形態】（実施例１）水分散シリカゾル
（有効濃度２０重量％）とトリメチルクロルシランとを
混合し、２０℃で１時間攪拌して加水分解し、接触反応
させた後、水で希釈して表面処理剤を調製した。この表
面処理剤を、既に使用に供されている自動車のボンネッ
ト表面にスポンジ拭きにより塗布した後、石原産業製光
触媒コーティング液ＳＴＫ０１（酸化チタン粒子８重量
部とアルキルシリケート２重量部と硝酸水溶液５４．８
重量部とメタノール２８重量部とプロパノール７．２重
量部からなる組成物）を溶媒（２−プロパノール９重量
部とジアセトンアルコール１重量部との混合液）で１０
０倍に希釈して得た光触媒コーティング液を、直径８ｍ
ｍのエアガンを用いて１０５ｍ2／ｇスプレーコーティ
ング法により塗布後、２０℃で２０分乾燥させることに
より、塗膜を硬化させて試料を得た。上記試料につい
て、塗膜形成後、３時間太陽光に晒すことにより、紫外
線が照射されるようにした後、水を噴霧したところ、水
滴が形成されず、水が一様に広がる様子が観察された。(Example 1) A water-dispersed silica sol (effective concentration: 20% by weight) and trimethylchlorosilane were mixed, stirred at 20 ° C for 1 hour, hydrolyzed, contacted and reacted. To prepare a surface treatment agent. This surface treating agent is applied to the surface of the bonnet of an automobile already in use by wiping with a sponge, and then a photocatalyst coating solution STK01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, and 54.times. 8
Parts by weight of a solvent (composition comprising 9 parts by weight of 2-propanol and 1 part by weight of diacetone alcohol) in a solvent.
The photocatalyst coating solution obtained by diluting 0-fold was 8 m in diameter.
After applying by a spray coating method of 105 m 2 / g using an air gun of m, the coating film was cured by drying at 20 ° C. for 20 minutes to obtain a sample. The above sample was exposed to sunlight for 3 hours after coating film formation, was irradiated with ultraviolet rays, and then was sprayed with water. As a result, it was observed that water droplets were not formed and water spread uniformly. Was.
【００２０】（実施例２）水分散シリカゾル（有効濃度
２０重量％）とトリメチルオクチルアンモニウムメチル
サルフェートとを混合し、２０℃で１時間攪拌して加水
分解し、接触反応させた後、水で希釈して表面処理剤を
調製した。この表面処理剤を、既に使用に供されている
自動車のボンネット表面に塗布した後、前記実施例１と
同様に光触媒コーティング液を塗布・乾燥させることに
より、光触媒層を硬化させて試料を得た。上記試料につ
いて、前記実施例１と同様に、３時間太陽光に晒すこと
により、紫外線が照射されるようにした後、水を噴霧し
たところ、水滴が形成されず、水が一様に広がる様子が
観察された。Example 2 A water-dispersed silica sol (effective concentration 20% by weight) and trimethyloctylammonium methyl sulfate were mixed, stirred at 20 ° C. for 1 hour, hydrolyzed, contact-reacted, and diluted with water. Thus, a surface treatment agent was prepared. After applying this surface treatment agent to the surface of the hood of an automobile already in use, the photocatalyst layer was cured by applying and drying a photocatalyst coating liquid in the same manner as in Example 1 to obtain a sample. . The above sample was exposed to sunlight for 3 hours to be irradiated with ultraviolet light, and then sprayed with water, as in the case of Example 1. When the water was sprayed, water droplets were not formed and the water spread uniformly. Was observed.
【００２１】（実施例３）先ず、水分散シリカゾル（有
効濃度２０重量％）とトリメチルクロルシランとを混合
し、更にトリメチルオクチルアンモニウムメチルサルフ
ェートの希釈液を加えて表面処理剤を調製した。この表
面処理剤を、既に使用に供されている自動車のボンネッ
ト表面に塗布した後、前記実施例１と同様に光触媒コー
ティング液を塗布・乾燥させることにより、光触媒層を
硬化させて試料を得た。上記試料について、前記実施例
１と同様に、３時間太陽光に晒すことにより、紫外線が
照射されるようにした後、水を噴霧したところ、水滴が
形成されず、水が一様に広がる様子が観察された。Example 3 First, a water-dispersed silica sol (effective concentration: 20% by weight) and trimethylchlorosilane were mixed, and a diluting solution of trimethyloctyl ammonium methyl sulfate was added to prepare a surface treating agent. After applying this surface treatment agent to the surface of the hood of an automobile already in use, the photocatalyst layer was cured by applying and drying a photocatalyst coating liquid in the same manner as in Example 1 to obtain a sample. . The above sample was exposed to sunlight for 3 hours to be irradiated with ultraviolet light, and then sprayed with water, as in the case of Example 1. When the water was sprayed, water droplets were not formed and the water spread uniformly. Was observed.
【００２２】（実施例４）先ず、水分散シリカゾル（有
効濃度２０重量％）とトリメチルクロルシランとを混合
し、更に硫酸アルミニウムの希釈液を加えて表面処理剤
を調製した。この表面処理剤を、既に使用に供されてい
る自動車のボンネット表面に塗布した後、前記実施例１
と同様に光触媒コーティング液を塗布・乾燥させること
により、光触媒層を硬化させて試料を得た。上記試料に
ついて、前記実施例１と同様に、３時間太陽光に晒すこ
とにより、紫外線が照射されるようにした後、水を噴霧
したところ、水滴が形成されず、水が一様に広がる様子
が観察された。Example 4 First, a water-dispersed silica sol (effective concentration: 20% by weight) and trimethylchlorosilane were mixed, and a diluting solution of aluminum sulfate was added to prepare a surface treating agent. After applying this surface treatment agent to the surface of the hood of an automobile already in use, the surface treatment agent of Example 1 was used.
The photocatalyst layer was cured by applying and drying the photocatalyst coating liquid in the same manner as in Example 2 to obtain a sample. The above sample was exposed to sunlight for 3 hours to be irradiated with ultraviolet light, and then sprayed with water, as in the case of Example 1. When the water was sprayed, water droplets were not formed and the water spread uniformly. Was observed.
【００２３】（比較例１）既に使用に供されている自動
車のボンネット表面に、洗浄処理をせずに、石原産業製
光触媒コーティング液ＳＴＫ０１（酸化チタン粒子８重
量部とアルキルシリケート２重量部と硝酸水溶液５４．
８重量部とメタノール２８重量部とプロパノール７．２
重量部からなる組成物）を溶媒（２−プロパノール９重
量部とジアセトンアルコール１重量部との混合液）で１
００倍に希釈して得た光触媒コーティング液を、直径８
ｍｍのエアガンを用いて１０５ｍ2／ｇスプレーコーテ
ィング法により塗布後、２０℃で２０分乾燥させること
により、光触媒層を硬化させて試料を得た。上記試料に
ついて、光触媒層形成後、３時間太陽光に晒すことによ
り、紫外線が照射されるようにした後、水を噴霧してみ
たが、所々水滴が弾かれたり付着してしまい、充分に親
水化されていない様子が観察された。これは、光触媒が
均一に塗布されていないためと考えられる。Comparative Example 1 A photocatalyst coating solution STK01 manufactured by Ishihara Sangyo (8 parts by weight of titanium oxide particles, 2 parts by weight of alkyl silicate, nitric acid, Aqueous solution 54.
8 parts by weight, 28 parts by weight of methanol and 7.2 of propanol
Parts by weight) of a solvent (a mixture of 9 parts by weight of 2-propanol and 1 part by weight of diacetone alcohol) in a solvent.
The photocatalyst coating liquid obtained by diluting it by a factor of 00 was
After coating by a spray coating method of 105 m 2 / g using an air gun of mm, the photocatalyst layer was cured by drying at 20 ° C. for 20 minutes to obtain a sample. After the photocatalyst layer was formed, the sample was exposed to sunlight for 3 hours after being exposed to ultraviolet light, and then sprayed with water. An unconverted state was observed. This is probably because the photocatalyst was not uniformly applied.
【００２４】（比較例２）コロイダルシリカを２２重量
％、ドデシルトリメチルアンモニウムクロライドを０．
０２重量％含有する表面処理剤を調製したが、凝集が起
こり表面処理剤としては不安定であることが確認され
た。Comparative Example 2 22% by weight of colloidal silica and 0.2% of dodecyltrimethylammonium chloride were used.
Although a surface treatment agent containing 02% by weight was prepared, it was confirmed that aggregation occurred and the surface treatment agent was unstable.
【００２５】（比較例３）コロイダルシリカを２．０重
量％、ドデシルトリメチルアンモニウムクロライドを
０．２重量％含有する表面処理剤を調製したが、凝集が
起こり保存性が悪く、表面処理剤としては使用できない
ことが判明した。(Comparative Example 3) A surface treatment agent containing 2.0% by weight of colloidal silica and 0.2% by weight of dodecyltrimethylammonium chloride was prepared. However, aggregation occurred and storage stability was poor. It turned out to be unusable.
【００２６】以上の実施例及び比較例より、水中で負の
表面電荷を有する水分散無機コロイドを部分的に疎水化
した水性ゾルを表面処理剤を既に使用に供されている自
動車のボンネット表面に塗布してから、光触媒性親水性
被膜を形成すると、親水性が発現しやすいことが確認さ
れた。According to the above Examples and Comparative Examples, an aqueous sol obtained by partially hydrophobizing a water-dispersed inorganic colloid having a negative surface charge in water is applied to the surface of a hood of an automobile already using a surface treating agent. It was confirmed that when a photocatalytic hydrophilic film was formed after coating, hydrophilicity was easily developed.
【００２７】[0027]
【発明の効果】以上に説明した如く、自動車のボディ表
面に本発明に係る表面処理剤を予め塗布した後に、光触
媒コーティング液を塗布して光触媒被膜を形成すること
で、安定的に光触媒の光励起に応じた防汚効果が発現さ
れるようになる。As described above, the surface treatment agent according to the present invention is applied to the surface of an automobile body in advance, and then the photocatalytic coating solution is applied to form a photocatalytic film, thereby stably exciting the photocatalyst. The antifouling effect according to the condition is exhibited.
【図１】自動車のボディに光触媒被膜を形成する方法の
一例を示すブロック図FIG. 1 is a block diagram showing an example of a method for forming a photocatalytic film on an automobile body.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｋ 3/36 Ｃ０８Ｋ 3/36 9/06 9/06 Ｃ０９Ｄ 1/00 Ｃ０９Ｄ 1/00 5/16 5/16 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C08K 3/36 C08K 3/36 9/06 9/06 C09D 1/00 C09D 1/00 5/16 5/16
Claims (7)
する前に、当該表面の前処理を行うために塗布する表面
処理剤であって、この表面処理剤は水中で負の表面電荷
を有する水分散無機コロイドを部分的に疎水化した水性
ゾルからなることを特徴とする自動車ボディ用表面処理
剤。1. A surface treatment agent applied to perform a pretreatment of a photocatalytic film on a body surface of an automobile before forming the photocatalytic film on the surface of the body, wherein the surface treatment agent is a water having a negative surface charge in water. A surface treating agent for an automobile body, comprising an aqueous sol in which a dispersed inorganic colloid is partially hydrophobized.
理剤において、前記水分散無機コロイドがシリカゾルで
あることを特徴とする自動車ボディ用表面処理剤。2. The surface treating agent for an automobile body according to claim 1, wherein the water-dispersed inorganic colloid is a silica sol.
理剤において、前記シリカゾルの部分的な疎水化は、分
子内に少なくとも１個のシラノール基を有するシラン誘
導体及び／又はその縮合物との接触反応にてなされたこ
とを特徴とする自動車ボディ用表面処理剤。3. The surface treating agent for an automobile body according to claim 2, wherein the silica sol is partially hydrophobized with a silane derivative having at least one silanol group in a molecule and / or a condensate thereof. A surface treating agent for an automobile body, which is produced by a contact reaction.
理剤において、前記シリカゾルの部分的な疎水化は、正
のイオン種によってなされたことを特徴とする自動車ボ
ディ用表面処理剤。4. The surface treating agent for an automobile body according to claim 2, wherein said silica sol is partially hydrophobized by a positive ionic species.
理剤において、前記正のイオン種は、炭素数４〜１８の
アルキル基又はアルケニル基を有するアンモニウム化合
物、若しくは水溶性アルミニウム塩であることを特徴と
する自動車ボディ用表面処理剤。5. The surface treating agent for an automobile body according to claim 4, wherein the positive ion species is an ammonium compound having an alkyl group or an alkenyl group having 4 to 18 carbon atoms, or a water-soluble aluminum salt. A surface treating agent for an automobile body, characterized by the following.
理剤において、この表面処理剤は、シリカゾルに分子内
に少なくとも１個のシラノール基を有するシラン誘導体
及び／又はその縮合物を接触反応せしめた後、正のイオ
ン種を接触せしめて部分的に疎水化せしめたものである
ことを特徴とする自動車ボディ用表面処理剤。6. The surface treating agent for an automobile body according to claim 2, wherein the surface treating agent is obtained by contacting a silica sol with a silane derivative having at least one silanol group in a molecule and / or a condensate thereof. A surface treatment agent for an automobile body, wherein the surface treatment agent is partially hydrophobized by contact with a positive ion species after the contact.
コロイドを部分的に疎水化した水性ゾルを自動車のボデ
ィ表面に塗布して親水化せしめた後に、当該自動車のボ
ディ表面に光触媒コーティング液を塗布するようにした
ことを特徴とする自動車ボディに対する光触媒被膜の形
成方法。7. A photocatalyst coating solution is applied to the surface of an automobile body after applying an aqueous sol obtained by partially hydrophobizing an aqueous dispersion inorganic colloid having a negative surface charge in water to the surface of the automobile body to make it hydrophilic. A method for forming a photocatalytic film on an automobile body, characterized in that a photocatalyst film is applied to the vehicle body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10039041A JPH11236518A (en) | 1998-02-20 | 1998-02-20 | Surface treating agent for automotive body and method for forming photocatalytic coating film on automotive body by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10039041A JPH11236518A (en) | 1998-02-20 | 1998-02-20 | Surface treating agent for automotive body and method for forming photocatalytic coating film on automotive body by using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11236518A true JPH11236518A (en) | 1999-08-31 |
Family
ID=12542050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10039041A Pending JPH11236518A (en) | 1998-02-20 | 1998-02-20 | Surface treating agent for automotive body and method for forming photocatalytic coating film on automotive body by using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11236518A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005063899A1 (en) * | 2003-12-25 | 2005-07-14 | Sk Kaken Co., Ltd. | Aqueous coating composition |
| CN100436551C (en) * | 2003-12-25 | 2008-11-26 | Sk化研株式会社 | Aqueous coating composition |
| US7893659B2 (en) | 2002-01-09 | 2011-02-22 | Quallion Llc | Method and apparatus for amplitude limiting battery temperature spikes |
-
1998
- 1998-02-20 JP JP10039041A patent/JPH11236518A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7893659B2 (en) | 2002-01-09 | 2011-02-22 | Quallion Llc | Method and apparatus for amplitude limiting battery temperature spikes |
| WO2005063899A1 (en) * | 2003-12-25 | 2005-07-14 | Sk Kaken Co., Ltd. | Aqueous coating composition |
| KR100850537B1 (en) * | 2003-12-25 | 2008-08-05 | 에스케 카켄 가부시키가이샤 | Aqueous coating composition |
| CN100436551C (en) * | 2003-12-25 | 2008-11-26 | Sk化研株式会社 | Aqueous coating composition |
| US7683123B2 (en) | 2003-12-25 | 2010-03-23 | Sk Kaken Co., Ltd. | Aqueous coating composition |
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