JP4859099B2 - Painting method - Google Patents
Painting method Download PDFInfo
- Publication number
- JP4859099B2 JP4859099B2 JP2005368868A JP2005368868A JP4859099B2 JP 4859099 B2 JP4859099 B2 JP 4859099B2 JP 2005368868 A JP2005368868 A JP 2005368868A JP 2005368868 A JP2005368868 A JP 2005368868A JP 4859099 B2 JP4859099 B2 JP 4859099B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- coating
- component
- water
- weight
- 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.)
- Expired - Fee Related
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- 238000000034 method Methods 0.000 title description 13
- 238000010422 painting Methods 0.000 title description 3
- 238000000576 coating method Methods 0.000 claims description 58
- 239000003973 paint Substances 0.000 claims description 53
- 239000011248 coating agent Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 21
- 229920003002 synthetic resin Polymers 0.000 claims description 15
- 239000000057 synthetic resin Substances 0.000 claims description 15
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 150000004756 silanes Chemical class 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000000178 monomer Substances 0.000 description 27
- -1 2-ethylhexyl Chemical group 0.000 description 26
- 230000000694 effects Effects 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000011109 contamination Methods 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
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- 238000001035 drying Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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- 239000000377 silicon dioxide Substances 0.000 description 3
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- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
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- 125000002252 acyl group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
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- 239000004567 concrete Substances 0.000 description 2
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- 238000006482 condensation reaction Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
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- 230000035515 penetration Effects 0.000 description 2
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- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JWCDUUFOAZFFMX-UHFFFAOYSA-N 2-ethenoxy-n,n-dimethylethanamine Chemical compound CN(C)CCOC=C JWCDUUFOAZFFMX-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- WDQKICIMIPUDBL-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]prop-2-enamide Chemical compound CN(C)CCNC(=O)C=C WDQKICIMIPUDBL-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-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
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- DEKZKCDJQLBBRA-UHFFFAOYSA-N tributoxy(butyl)silane Chemical compound CCCCO[Si](CCCC)(OCCCC)OCCCC DEKZKCDJQLBBRA-UHFFFAOYSA-N 0.000 description 1
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- WAAWAIHPWOJHJJ-UHFFFAOYSA-N tributoxy(propyl)silane Chemical compound CCCCO[Si](CCC)(OCCCC)OCCCC WAAWAIHPWOJHJJ-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-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
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は、耐汚染性に優れた塗膜が形成可能な塗装方法に関するものである。さらに詳しくはコンクリート、モルタル、金属、ガラス、磁器タイル、サイディングボード、押出成型板、プラスチック等の各種素材の表面仕上げに使用することができ、主に建築物、土木構造物等の躯体保護に寄与する塗装方法に関するものである。 The present invention relates to a coating method capable of forming a coating film excellent in stain resistance. More specifically, it can be used for surface finishing of various materials such as concrete, mortar, metal, glass, porcelain tiles, siding boards, extrusion boards, plastics, etc., and mainly contributes to the protection of structural bodies such as buildings and civil engineering structures. It is related to the painting method.
近年、建築・土木構造物に使用する塗料分野においては有機溶剤を溶媒とする溶剤型塗料から、水を溶媒とする水性塗料への転換が図られつつある。これは、塗装作業者や居住者の健康被害を低減するためや、大気環境汚染を低減する目的で行われているものであり、年々水性化が進んできている。 In recent years, in the field of paints used for construction and civil engineering structures, a shift from solvent-based paints using organic solvents to water-based paints using water as a solvent is being attempted. This is performed for the purpose of reducing the health hazards of painters and residents, and for the purpose of reducing air pollution.
公知の水性塗料の中には、耐候性、耐水性等に関しては溶剤型塗料と同等レベルの性能を有するものもある。しかし、特に汚染性に着目してみると、低汚染型と唱われる水性塗料でさえ、溶剤型の低汚染型塗料のレベルには及ばないのが現状である。また、水性塗料による塗膜は一般的に溶剤型の塗料による塗膜に比べて、塗膜硬度が低く、汚染物質が付着した時の染み込み性が高い傾向にある。従って、一度汚染物質が付着すると、塗膜表面からその汚れを除去することは困難な場合が多い。 Some known water-based paints have the same level of performance as solvent-based paints in terms of weather resistance, water resistance, and the like. However, with particular attention to contamination, even water-based paints that are said to be low-contamination are not as high as solvent-type low-contamination paints. In addition, a coating film made of a water-based paint generally has a coating film hardness lower than a coating film made of a solvent-type paint, and tends to have a high penetration when contaminated substances adhere. Therefore, once a contaminant has adhered, it is often difficult to remove the dirt from the coating surface.
このような問題に対し、WO94/06870(特許文献1)には、塗料中に低汚染化剤としてオルガノシリケート及び/又はその縮合物を配合する技術が開示されている。この特許文献1に記載の技術は、オルガノシリケート及び/又はその縮合物を塗料に配合し、その塗料によって形成される塗膜を酸処理することによって塗膜表面を親水性にし、油性の汚染物質を付着しにくくし、また付着した汚染物質を降雨等の水滴とともに洗い流してしまうことを特徴とするものである。 In order to deal with such problems, WO94 / 06870 (Patent Document 1) discloses a technique of blending organosilicate and / or a condensate thereof as a low-contamination agent in a paint. The technique described in Patent Document 1 includes an organosilicate and / or a condensate thereof in a paint, and acid-treats the paint film formed by the paint to make the paint film surface hydrophilic, thereby producing an oily contaminant. It is characterized in that the adhering contaminants are washed away together with water droplets such as rain.
しかしながら、単にオルガノシリケート及び/又はその縮合物を添加する上記特許文献1の場合においては、オルガノシリケート及び/又はその縮合物を水性塗料に添加した際に起こる加水分解縮合反応を制御できないために、短時間で急激に塗料粘度が上昇し、さらには塗料全体がゲル化してしまい、通常の塗装作業をすることさえできないものであった。さらに、たとえ混合後直ちに塗装を行い、塗膜を形成した場合においても、汚染物質の染み込み抵抗性に劣るという欠点があった。 However, in the case of Patent Document 1 in which an organosilicate and / or a condensate thereof are simply added, the hydrolysis condensation reaction that occurs when an organosilicate and / or a condensate thereof is added to an aqueous paint cannot be controlled. The viscosity of the paint suddenly increased in a short time, and the whole paint was gelled, so that it was not possible to perform normal painting work. Furthermore, even when coating is performed immediately after mixing and a coating film is formed, there is a disadvantage that the resistance to penetration of contaminants is poor.
これに対し、特開平11−343462号公報(特許文献2)には、オルガノシリケート及び/又はその縮合物にポリアルキレングリコール系化合物を反応させてなる変性オルガノシリケートを配合した塗料が開示されている。この特許文献2に記載の水性塗料では、オルガノシリケートを変性して水性樹脂との相溶性を高めることによって、特許文献1における問題点が改善されている。 On the other hand, JP-A-11-343462 (Patent Document 2) discloses a coating material containing a modified organosilicate obtained by reacting a polyalkylene glycol compound with an organosilicate and / or a condensate thereof. . In the water-based paint described in Patent Document 2, the problem in Patent Document 1 is improved by modifying the organosilicate to enhance the compatibility with the water-based resin.
しかしながら、特許文献2に記載の水性塗料を塗装して塗膜を乾燥させた後、その塗膜上に再度同じ塗料を塗装しても、十分な密着性が得られ難いために、結局のところ重ね塗り工程の許容範囲が制限される場合がある。また、このような水性塗料において、より高度な安定した耐汚染性を発揮させるにはさらなる改善の余地がある。 However, after applying the water-based paint described in Patent Document 2 and drying the coating film, it is difficult to obtain sufficient adhesion even if the same paint is applied again on the coating film. The allowable range of the overcoating process may be limited. Further, in such a water-based paint, there is room for further improvement in order to exhibit a higher level of stable contamination resistance.
本発明は上述の如き問題点に鑑みなされたもので、水性塗料を重ね塗りして、耐汚染性を具備する塗膜を得る塗装方法において、相互の塗膜密着性を十分に確保すること、及び形成塗膜の耐汚染性を高めることを目的とするものである。 The present invention has been made in view of the above-mentioned problems, and in a coating method for obtaining a coating film having stain resistance by repeatedly applying a water-based paint, sufficiently ensuring mutual coating film adhesion, And it aims at improving the stain resistance of the formed coating film.
本発明者は、上記目的を達成するため鋭意検討を行った結果、重ね塗り工程に供する塗料として、それぞれ特定の合成樹脂エマルション、ヒドラジド化合物、及びアルコキシシラン変性縮合物を組み合わせたものが好適であることを見出し、本発明の完成に到った。 As a result of intensive studies to achieve the above-mentioned object, the present inventor preferably uses a combination of a specific synthetic resin emulsion, a hydrazide compound, and an alkoxysilane-modified condensate as a coating material used for the overcoating step. As a result, the present invention has been completed.
即ち、本発明は以下の塗装方法に関するものである。 That is, the present invention relates to the following coating method.
1.同種の水性塗料を重ね塗りする塗装方法において、当該水性塗料として、エポキシ基含有合成樹脂エマルション(A)、ヒドラジド基とヒドラジド基以外の含窒素骨格とを有するヒドラジド化合物(B)、及びポリオキシアルキレン基を有するアルコキシシランの変性縮合物(C)を含有し、前記合成樹脂エマルション(A)の固形分100重量部に対して、前記ヒドラジド化合物(B)が0.1〜20重量部、前記アルコキシシランの変性縮合物(C)がSiO2換算で1〜40重量部配合された塗料を使用することを特徴とする塗装方法。2.同種の水性塗料を重ね塗りする塗装方法において、当該水性塗料として、エポキシ基含有合成樹脂エマルション(A)、ヒドラジド基とヒドラジド基以外の含窒素骨格とを有するヒドラジド化合物(B)、及びポリオキシアルキレン基を有するアルコキシシランの変性縮合物(C)を含有し、前記合成樹脂エマルション(A)の固形分100重量部に対して、前記ヒドラジド化合物(B)が0.1〜20重量部、前記アルコキシシランの変性縮合物(C)がSiO 2 換算で1〜40重量部配合された塗料を使用し、当該水性塗料の第1回目の塗装を行って下層塗膜を形成させ、該下層塗膜が硬化乾燥した後に、当該水性塗料の第2回目の塗装を行って上層塗膜を形成させることを特徴とする塗装方法。 1. In the coating method in which the same kind of water-based paint is repeatedly applied, the water-based paint includes an epoxy group-containing synthetic resin emulsion (A), a hydrazide compound (B) having a hydrazide group and a nitrogen-containing skeleton other than the hydrazide group, and polyoxyalkylene. A modified condensate (C) of an alkoxysilane having a group, and 0.1 to 20 parts by weight of the hydrazide compound (B) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (A). A coating method characterized by using a paint in which 1 to 40 parts by weight of a modified silane condensate (C) in terms of SiO 2 is used. 2. In the coating method in which the same kind of water-based paint is repeatedly applied, the water-based paint includes an epoxy group-containing synthetic resin emulsion (A), a hydrazide compound (B) having a hydrazide group and a nitrogen-containing skeleton other than the hydrazide group, and polyoxyalkylene. A modified condensate (C) of an alkoxysilane having a group, and 0.1 to 20 parts by weight of the hydrazide compound (B) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (A). Using a coating in which 1 to 40 parts by weight of the modified silane condensate (C) is converted into SiO 2 , the first coating of the aqueous coating is performed to form a lower coating, After curing and drying, a second coating of the water-based paint is performed to form an upper layer coating film.
本発明によれば、水性塗料を重ね塗りして、耐汚染性を具備する塗膜を得る塗装方法において、相互の塗膜密着性を十分に確保することができ、さらには形成塗膜の耐汚染性を飛躍的に高めることができる。 According to the present invention, in the coating method for obtaining a coating film having stain resistance by recoating with a water-based paint, mutual coating film adhesion can be sufficiently ensured, and further, the formed coating film resistance is improved. Contamination can be dramatically increased.
以下、本発明をその実施の形態に基づき詳細に説明する。 Hereinafter, the present invention will be described in detail based on the embodiments.
本発明において使用する水性塗料は、ヒドラジド基と反応可能な反応性官能基を有する合成樹脂エマルション(A)(以下「(A)成分」ともいう)、ヒドラジド基とヒドラジド基以外の含窒素骨格とを有するヒドラジド化合物(B)(以下「(B)成分」ともいう)、及びポリオキシアルキレン基を有するアルコキシシランの変性縮合物(C)(以下「(C)成分」ともいう)を必須成分として含むものである。 The water-based paint used in the present invention includes a synthetic resin emulsion (A) having a reactive functional group capable of reacting with a hydrazide group (hereinafter also referred to as “component (A)”), a hydrazide group and a nitrogen-containing skeleton other than the hydrazide group. As an essential component, a hydrazide compound (B) having a silane (hereinafter also referred to as “component (B)”) and a modified condensation product (C) of an alkoxysilane having a polyoxyalkylene group (hereinafter also referred to as “component (C)”) Is included.
このうち(A)成分は、ヒドラジド基と反応可能な反応性官能基を有する各種合成樹脂エマルションであり、かかる官能基を有する限り、その樹脂骨格は特に限定されず、例えばアクリル樹脂系エマルション、アクリルシリコン樹脂系エマルション、フッ素樹脂系エマルション、ウレタン樹脂系エマルション等が使用できる。 Among these, the component (A) is various synthetic resin emulsions having a reactive functional group capable of reacting with a hydrazide group, and the resin skeleton is not particularly limited as long as it has such a functional group. For example, an acrylic resin emulsion, an acrylic resin Silicon resin emulsion, fluororesin emulsion, urethane resin emulsion and the like can be used.
具体的に(A)成分としては、ヒドラジド基と反応可能な反応性官能基を有するモノマーと、これと共重合可能なモノマーとの共重合により得られる合成樹脂エマルションが使用できる。ヒドラジド基と反応可能な反応性官能基を有するモノマーとしては、例えば、アクロレイン、ダイアセトン(メタ)アクリルアミド、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン等のカルボニル基含有モノマー;グリシジル(メタ)アクリレート、ジグリシジル(メタ)アクリレート等のエポキシ基含有モノマー等が挙げられる。かかるモノマーのモノマー総重量に対する重量比率は、通常0.1〜40重量%、好ましくは0.5〜20重量%である。本発明では、特にモノマー成分としてエポキシ基含有モノマーを含むエポキシ基含有合成樹脂エマルションが好適である。 Specifically, as the component (A), a synthetic resin emulsion obtained by copolymerization of a monomer having a reactive functional group capable of reacting with a hydrazide group and a monomer copolymerizable therewith can be used. Examples of the monomer having a reactive functional group capable of reacting with a hydrazide group include carbonyl group-containing monomers such as acrolein, diacetone (meth) acrylamide, vinyl methyl ketone, vinyl ethyl ketone, and vinyl butyl ketone; glycidyl (meth) acrylate And epoxy group-containing monomers such as diglycidyl (meth) acrylate. The weight ratio of such monomers to the total monomer weight is usually 0.1 to 40% by weight, preferably 0.5 to 20% by weight. In the present invention, an epoxy group-containing synthetic resin emulsion containing an epoxy group-containing monomer as a monomer component is particularly suitable.
上記モノマーと共重合可能なモノマー成分としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート等の(メタ)アクリル酸エステル;アクリル酸、メタクリル酸、クロトン酸、マレイン酸またはそのモノアルキルエステル等のカルボキシル基含有モノマー;N−メチルアミノエチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジメチルアミノエチルビニルエーテル、N−(2−ジメチルアミノエチル)アクリルアミド等のアミノ基含有モノマー;ビニルピリジン等のピリジン系モノマー;2−ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート等の水酸基含有モノマー;酢酸ビニル、プロピオン酸ビニル等のビニルエステル系モノマー;アクリロニトリル、メタアクリロニトリル等のニトリル基含有モノマー;スチレン、2−メチルスチレン、ビニルトルエン等の芳香族モノマー;アクリルアミド、メタクリルアミド、ジアセトンアクリルアミド等のアミド基含有モノマー;ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−(メタ)アクリロイルオキシプロピルトリメトキシシラン、γ−(メタ)アクリロイルオキシプロピルトリエトキシシラン等のアルコキシシリル基含有モノマー;塩化ビニリデン、フッ化ビニリデン等のハロゲン化ビニリデン系モノマー等が挙げられる。これらは1種または2種以上で使用することができる。 Examples of the monomer component copolymerizable with the above monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylic acid esters such as meth) acrylate and cyclohexyl (meth) acrylate; carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or monoalkyl esters thereof; N-methylaminoethyl (meth) acrylate Amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, dimethylaminoethyl vinyl ether and N- (2-dimethylaminoethyl) acrylamide; pyridine monomers such as vinylpyridine; 2-hydride Hydroxyl-containing monomers such as xylethyl (meth) acrylate and hydroxypropyl (meth) acrylate; vinyl ester monomers such as vinyl acetate and vinyl propionate; nitrile group-containing monomers such as acrylonitrile and methacrylonitrile; styrene, 2-methylstyrene, vinyl Aromatic monomers such as toluene; Amide group-containing monomers such as acrylamide, methacrylamide and diacetone acrylamide; Vinyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyl Examples thereof include alkoxysilyl group-containing monomers such as oxypropyltriethoxysilane; vinylidene halide monomers such as vinylidene chloride and vinylidene fluoride. These can be used alone or in combination of two or more.
(A)成分のガラス転移温度(以下「Tg」という)は、適宜設定することができるが、通常−10〜80℃、好ましくは0〜60℃である。Tgが−10℃よりも低い場合は、耐汚染性において十分な効果が得られ難くなり、80℃よりも高い場合は、塗膜に割れ等が発生しやすくなる。 The glass transition temperature (hereinafter referred to as “Tg”) of the component (A) can be appropriately set, but is usually −10 to 80 ° C., preferably 0 to 60 ° C. When Tg is lower than −10 ° C., it is difficult to obtain a sufficient effect in stain resistance, and when it is higher than 80 ° C., cracks and the like are likely to occur in the coating film.
(A)成分において、カルボキシル基含有モノマーを含有する場合、当該モノマーのモノマー総重量に対する重量比率は5%以下、より好ましくは2%以下、さらには1%以下とする。このような範囲に限定することにより、耐汚染性をいっそう高めることができる。 When the component (A) contains a carboxyl group-containing monomer, the weight ratio of the monomer to the total monomer weight is 5% or less, more preferably 2% or less, and further 1% or less. By limiting to such a range, contamination resistance can be further enhanced.
(A)成分の製造方法はとくに限定されないが、たとえば乳化重合法として、バッチ重合、モノマー滴下重合、乳化モノマー滴下重合等の方法により製造することができる。 Although the manufacturing method of (A) component is not specifically limited, For example, it can manufacture by methods, such as batch polymerization, monomer dripping polymerization, emulsion monomer dripping polymerization, as an emulsion polymerization method.
重合に用いる乳化剤は、(A)成分の攪拌安定性や低温安定性を確保できるものを使用する必要がある。種類としては、アニオン性、カチオン性、ノニオン性、両性、ノニオン−カチオン性、ノニオン−アニオン性のもの、あるいは非反応性のもの、反応性を有するものから適宜選択し、単独あるいは併用して使用する。このうち、不飽和二重結合を有する反応性乳化剤の使用は、耐水性を向上させることができ、好ましい。さらには、ノニオン性反応性乳化剤とアニオン性反応性乳化剤の併用が、耐水性、攪拌安定性や低温安定性を向上させると共に、耐汚染性も向上させることができ、好ましい。 As the emulsifier used for the polymerization, it is necessary to use an emulsifier that can ensure the stirring stability and low-temperature stability of the component (A). The type is appropriately selected from anionic, cationic, nonionic, amphoteric, nonionic-cationic, nonionic-anionic, non-reactive, and reactive, and used alone or in combination. To do. Among these, the use of a reactive emulsifier having an unsaturated double bond is preferable because it can improve water resistance. Furthermore, the combined use of a nonionic reactive emulsifier and an anionic reactive emulsifier is preferable because it can improve water resistance, stirring stability and low temperature stability, and can also improve stain resistance.
本発明では、(B)成分として、ヒドラジド基とヒドラジド基以外の含窒素骨格とを有するヒドラジド化合物を使用する。この(B)成分は、重ね塗り時の塗膜密着性を確保するための必須成分である。このような効果が得られる理由は明確ではないが、概ね以下の如き作用機構が推定される。すなわち、本発明では(C)成分に対する(B)成分の相溶性が高く、塗膜形成過程において(C)成分とともに(B)成分が塗膜表面に配向しやすくなる。その結果、第1層目の塗膜表面にはヒドラジド基が存在することとなり、第2層目を重ね塗りした際には、この第1層目のヒドラジド基と第2層目のエマルション官能基との作用により、密着性向上効果が発現するものと考えられる。このような密着性向上効果に加え、本発明では(B)成分を配合することにより顕著な耐汚染性向上効果を得ることができる。このような効果は、(B)成分が(C)成分の触媒として作用し、(C)成分の反応に寄与するためと推測される。 In the present invention, a hydrazide compound having a hydrazide group and a nitrogen-containing skeleton other than the hydrazide group is used as the component (B). This (B) component is an essential component for ensuring the coating film adhesion at the time of overcoating. The reason why such an effect is obtained is not clear, but the following action mechanism is generally estimated. That is, in this invention, the compatibility of (B) component with respect to (C) component is high, and (B) component with the (C) component becomes easy to orientate on the coating-film surface in a coating-film formation process. As a result, a hydrazide group is present on the surface of the first layer coating film, and when the second layer is overcoated, the first layer hydrazide group and the second layer emulsion functional group. It is considered that the effect of improving the adhesion is expressed by the action. In addition to such an effect of improving adhesion, in the present invention, a remarkable effect of improving stain resistance can be obtained by blending component (B). Such an effect is presumed to be because the component (B) acts as a catalyst for the component (C) and contributes to the reaction of the component (C).
(B)成分における含窒素骨格は、その骨格中に窒素原子を有する鎖状、分岐状または環状の有機基であればよく、例えばヒダントイン骨格、ピペラジン骨格等が挙げられる。特に本発明ではヒダントイン骨格が好適である。ヒドラジド基とヒダントイン骨格とを有するヒドラジド化合物としては、例えば1,3−ビス(ヒドラジノカルボエチル)−5−イソプロピルヒダントイン、1,3−ビス(ヒドラジノカルボエチル)−5−(2−メチルメルカプトエチル)ヒダントイン、1−ヒドラジノカルボエチル−3−ヒドラジノカルボイソプロピル−5−(2−メチルメルカプトエチル)ヒダントイン等が挙げられる。とりわけ本発明では、1,3−ビス(ヒドラジノカルボエチル)−5−イソプロピルヒダントインが好適である。 The nitrogen-containing skeleton in the component (B) may be a chain, branched or cyclic organic group having a nitrogen atom in the skeleton, and examples thereof include a hydantoin skeleton and a piperazine skeleton. In particular, the hydantoin skeleton is preferred in the present invention. Examples of the hydrazide compound having a hydrazide group and a hydrantoin skeleton include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin and 1,3-bis (hydrazinocarboethyl) -5- (2-methylmercapto And ethyl) hydantoin and 1-hydrazinocarboethyl-3-hydrazinocarboisopropyl-5- (2-methylmercaptoethyl) hydantoin. In particular, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin is preferred in the present invention.
一般に、塗料分野におけるヒドラジド化合物としては、シュウ酸ジヒドラジド 、マロン酸ジヒドラジド 、コハク酸ジヒドラジド 、グルタル酸ジヒドラジド 、アジピン酸ジヒドラジド 、セバシン酸ジヒドラジド等の飽和脂肪族カルボン酸のジヒドラジド化合物が汎用的に使用されている。このようなヒドラジド化合物は、−(CH2)n−で表される炭化水素基の両末端にヒドラジド基を有する構造であり、ヒドラジド基以外の含窒素骨格を有するものではなく、このような化合物を使用しても本発明の如き顕著な効果を得ることはできない。 In general, dihydrazide compounds of saturated aliphatic carboxylic acids such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, and sebacic acid dihydrazide are widely used as hydrazide compounds in the paint field. Yes. Such a hydrazide compound has a structure having a hydrazide group at both ends of a hydrocarbon group represented by — (CH 2 ) n —, and does not have a nitrogen-containing skeleton other than the hydrazide group. Even if it uses, the remarkable effect like this invention cannot be acquired.
(B)成分は、(A)成分の固形分100重量部に対し、0.1〜20重量部(好ましくは0.5〜10重量部)の範囲で添加する。(B)成分の混合比率がこのような範囲内であれば、本発明の効果を十分に得ることができる。(B)成分が0.1重量部より少ない場合は、密着性向上効果や耐汚染性向上効果が得られ難くなる。逆に(B)成分が20重量部より多い場合は、形成塗膜の耐水性、耐汚染性等が低下するおそれがあり、グロスエナメルにおいては十分な光沢が得られ難くなる。 The component (B) is added in the range of 0.1 to 20 parts by weight (preferably 0.5 to 10 parts by weight) with respect to 100 parts by weight of the solid content of the component (A). When the mixing ratio of the component (B) is within such a range, the effects of the present invention can be sufficiently obtained. When the amount of the component (B) is less than 0.1 parts by weight, it is difficult to obtain an effect of improving adhesion and an effect of improving stain resistance. On the other hand, when the component (B) is more than 20 parts by weight, the water resistance and stain resistance of the formed coating film may be lowered, and it is difficult to obtain a sufficient gloss in the gloss enamel.
本発明における、ポリオキシアルキレン基を有するアルコキシシランの変性縮合物(C)は、低汚染化剤としてはたらくものであり、本発明の水性塗料に耐汚染性を付与するのに不可欠の成分である。
(C)成分としては、ポリオキシアルキレン基の繰返し単位における炭素数が1〜4のものが好ましく、炭素数2のポリオキシエチレン基がより好ましい。また、ポリオキシエチレン基の平均分子量は150〜2000であることが好ましい。
(C)成分のアルコキシル基としては、炭素数1〜4のものが好ましく、炭素数2のエトキシ基がより好ましい。
The modified condensation product (C) of alkoxysilane having a polyoxyalkylene group in the present invention serves as a low-contamination agent and is an essential component for imparting stain resistance to the water-based paint of the present invention. .
As the component (C), those having 1 to 4 carbon atoms in the repeating unit of the polyoxyalkylene group are preferred, and polyoxyethylene groups having 2 carbon atoms are more preferred. Moreover, it is preferable that the average molecular weights of a polyoxyethylene group are 150-2000.
(C) As an alkoxyl group of a component, a C1-C4 thing is preferable and a C2-ethoxy group is more preferable.
(C)成分は公知の方法により得ることができ、具体的な製造方法としては、例えばアルコキシシランの縮合物の1種以上を、ポリオキシアルキレン基含有物1種以上でエステル交換反応させる方法等が挙げられる。すなわち、一般式
(R1O)4−a−SiR2 a
(式中、R1は炭素数1〜4のアルキル基を示し、R2はアルキル基、アリール基、アラルキル基、炭素数1〜4のアルコキシル基を示し、aは0〜2の整数を示す)で表されるアルコキシシランの縮合物(以下「p成分」という。また、その縮合前の原料を「p成分のモノマー」という。)を、一般式
R3−(OCnH2n)m−R4
(式中、R3は水素原子またはアルキル基、エポキシ基、アシル基を示し、R4は水酸基、アルキル基、アルコキシル基、エポキシ基、アシル基、カルボキシル基を示し、nは1〜4の整数、mは1〜20の整数を示す)で表されるポリオキシアルキレン基含有化合物(以下「q成分」という。)でエステル交換することにより製造する。特に、エステル交換反応においては、末端に少なくとも1つ以上の水酸基を有する必要があるので、末端に水酸基を有するようなq成分を使用する。エステル交換反応を行う際には、必要に応じエステル交換触媒を添加することができる。
Component (C) can be obtained by a known method. Specific production methods include, for example, a method of transesterifying one or more of the alkoxysilane condensates with one or more polyoxyalkylene group-containing products, etc. Is mentioned. That is, the general formula (R 1 O) 4-a -SiR 2 a
(Wherein R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents an alkyl group, an aryl group, an aralkyl group, or an alkoxyl group having 1 to 4 carbon atoms, and a represents an integer of 0 to 2) ) Represented by a general formula R 3 — (OC n H 2n ) m — (hereinafter referred to as “component p”). R 4
(In the formula, R 3 represents a hydrogen atom, an alkyl group, an epoxy group, or an acyl group, R 4 represents a hydroxyl group, an alkyl group, an alkoxyl group, an epoxy group, an acyl group, or a carboxyl group, and n is an integer of 1 to 4. , M represents an integer of 1 to 20) and is produced by transesterification with a polyoxyalkylene group-containing compound (hereinafter referred to as “q component”). Particularly, in the transesterification reaction, since it is necessary to have at least one hydroxyl group at the terminal, a q component having a hydroxyl group at the terminal is used. When performing the transesterification reaction, a transesterification catalyst can be added as necessary.
具体的にp成分のモノマーとしては、例えばテトラメトキシシラン、テトラエトキシシラン、テトラ−n−プロポキシシラン、テトラ−i−プロポキシシラン、テトラ−n−ブトキシシラン、テトラ−i−ブトキシシラン、テトラ−t−ブトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリプロポキシシラン、エチルトリブトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、プロピルトリプロポキシシラン、プロピルトリブトキシシラン、ブチルトリメトキシラン、ブチルトリエトキシシラン、ブチルトリプロポキシシラン、ブチルトリブトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジプロポキシシラン、ジメチルジブトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジエチルジプロポキシシラン、ジエチルジブトキシシランの縮合物等が挙げられる。これらは単独もしくは複数の種類を混合して使用することができる。 Specific examples of the p component monomer include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, and tetra-t. -Butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyl Triethoxysilane, propyltripropoxysilane, propyltributoxysilane, butyltrimethoxylane, butyltriethoxysilane, butyltripropoxysilane, butyltributoxysilane, dimethyl Silane, dimethyl diethoxy silane, dimethyl dipropoxy silane, dimethyl dibutoxy silane, diethyl dimethoxy silane, diethyl diethoxy silane, diethyl di-propoxysilane, and condensate of diethyl dibutoxy silane. These can be used individually or in mixture of several types.
p成分のアルコキシシリル基の炭素数は通常1〜4(好ましくは2)である。また、p成分の平均縮合度は1〜20が好ましい。平均縮合度が20を超えると、取り扱いが不便になるので好ましくない。 Carbon number of the alkoxysilyl group of the p component is usually 1 to 4 (preferably 2). Further, the average condensation degree of the p component is preferably 1-20. When the average degree of condensation exceeds 20, it is not preferable because handling becomes inconvenient.
q成分の具体例として、ポリオキシエチレングリコール、ポリオキシエチレングリコールモノアルキルエーテル、ポリオキシエチレン−プロピレングリコール、ポリオキシエチレン−テトラメチレングリコール、ポリオキシエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ポリオキシエチレンジグリコール酸、ポリオキシエチレングリコールビニルエーテル、ポリオキシエチレングリコールアリルエーテル、ポリオキシエチレングリコールジアリルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンアルキルアミン等が挙げられる。これらの化合物は、1種もしくは2種以上の組み合わせから選択することができる。 Specific examples of the q component include polyoxyethylene glycol, polyoxyethylene glycol monoalkyl ether, polyoxyethylene-propylene glycol, polyoxyethylene-tetramethylene glycol, polyoxyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly Oxyethylene diglycolic acid, polyoxyethylene glycol vinyl ether, polyoxyethylene glycol allyl ether, polyoxyethylene glycol diallyl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine Etc. These compounds can be selected from one or a combination of two or more.
q成分の平均分子量は150〜2000が好ましい。平均分子量が150未満の場合は、p成分とのエステル交換反応によって得られた低汚染化剤を塗料に混合した際の安定性が劣ってくる傾向にあり、グロスペイントでは優れた光沢が得られなくなってくる。逆に、q成分の平均分子量が2000を超えると、硬化塗膜の耐水性や硬度が低下する傾向にある。 The average molecular weight of the q component is preferably 150 to 2000. When the average molecular weight is less than 150, the stability when the low-contaminating agent obtained by the transesterification reaction with the p component is mixed with the paint tends to be inferior. With gloss paint, excellent gloss is obtained. It will disappear. Conversely, if the average molecular weight of the q component exceeds 2000, the water resistance and hardness of the cured coating film tend to decrease.
(C)成分の添加量は、(A)成分の固形分100重量部に対して、SiO2換算で1〜40重量部の範囲内とする。(C)成分が1重量部未満の場合は、低汚染化の効果を発現させることができない。(C)成分が40重量部を超える場合は、水性塗料の粘度安定性が低下してしまう傾向にあり、グロスペイントでは光沢の低下を引き起こすおそれがある。 (C) amount of component, 100 parts by weight of the solid content of the component (A), in the range of 1 to 40 parts by weight in terms of SiO 2. When the component (C) is less than 1 part by weight, the effect of reducing contamination cannot be expressed. When the component (C) exceeds 40 parts by weight, the viscosity stability of the water-based paint tends to decrease, and gloss paint may cause a decrease in gloss.
なお、本発明におけるSiO2換算とは、アルコキシシランやシリケート等のSi−O結合をもつ化合物を、完全に加水分解した後に、900℃で焼成した際にシリカ(SiO2)となって残る重量分にて表したものである。
一般に、アルコキシシランやシリケートは、水と反応して加水分解反応が起こりシラノールとなり、さらにシラノール同士やシラノールとアルコキシにより縮合反応を起こす性質を持っている。この反応を究極まで行うと、シリカ(SiO2)となる。これらの反応は
RO(Si(OR)2O)nR+(n+1)H2O→nSiO2+(2n+2)ROH
(Rはアルキル基を示す。nは整数。)
という反応式で表される。本発明におけるSiO2換算は、この反応式をもとに残るシリカ成分の量を換算したものである。
The SiO 2 conversion in the present invention means the weight remaining as silica (SiO 2 ) when a compound having a Si—O bond such as alkoxysilane or silicate is completely hydrolyzed and then baked at 900 ° C. Expressed in minutes.
In general, alkoxysilanes and silicates have a property of reacting with water to cause a hydrolysis reaction to form silanol, and further causing a condensation reaction between silanols or between silanol and alkoxy. When this reaction is performed to the ultimate, silica (SiO 2 ) is obtained. These reactions are RO (Si (OR) 2 O) n R + (n + 1) H 2 O → nSiO 2 + (2n + 2) ROH
(R represents an alkyl group. N is an integer.)
It is expressed by the reaction formula. The SiO 2 conversion in the present invention is the conversion of the amount of the remaining silica component based on this reaction formula.
本発明において、(C)成分は水と反応するものであるため、あまり長期にわたって水を含む(A)成分と接触させておくことは避けたほうがよい。従って、本発明における水性塗料は、流通段階では2成分以上の多成分タイプの塗料として扱い、使用時に混合する形態であることが望ましい。この際の形態としては、例えば、1成分目として(A)成分、2成分目として(B)成分、(C)成分の混合物、あるいは1成分目として(A)成分、(B)成分の混合物、2成分目として(C)成分の混合物とすることが可能である。 In the present invention, since the component (C) reacts with water, it is better to avoid contact with the component (A) containing water for a long period of time. Accordingly, it is desirable that the water-based paint in the present invention be handled as a multi-component type paint having two or more components at the distribution stage and mixed at the time of use. As a form in this case, for example, (A) component as the first component, (B) component as the second component, (C) component mixture, or (A) component and (B) component mixture as the first component The second component can be a mixture of component (C).
本発明における水性塗料には、上記成分の他に、必要に応じて通常塗料に用いられる有機溶剤、無機系着色顔料、有機系着色顔料、体質顔料、骨材等を配合することができ、本発明に影響しない程度の可塑剤、造膜助剤、防腐剤、防黴剤、消泡剤、増粘剤、レベリング剤、顔料分散剤、カップリング剤、沈降防止剤、たれ防止剤、艶消し剤、紫外線吸収剤、酸化防止剤、光安定剤等の添加剤を単独あるいは併用して配合することもできる。
また、上記(B)成分以外の硬化触媒を添加することもできる。このような硬化触媒としては、たとえば、ジブチル錫ジラウレート、ジブチル錫マレート、ジオクチル錫ジラウレート、ジオクチル錫マレート等の有機錫化合物;リン酸、モノメチルホスフェート、モノエチルホフェート、モノオクチルホスフェート等のリン酸またはリン酸エステル類;プロピレンオキサイド、ブチレンオキサイド、グリシジルメタクリレート、γ−グリシドキシプロピルトリエトキシシラン、エピコート828等のエポキシ化合物とリン酸および/または酸性モノリン酸エステルとの付加物;有機チタネート化合物;有機アルミニウム化合物;有機ジルコニウム化合物;マレイン酸、アジピン酸、アゼライン酸、これらの酸無水物、パラトルエンスルフォン酸等の酸性化合物;ヘキシルアミン、N.N−ジメチルドデシルアミン等のアミン類;水酸化ナトリウム等のアルカリ性化合物等が例示できる。このような硬化触媒の添加量は、(A)成分の固形分100重量部に対して、通常0.1〜20重量部程度である。
In addition to the above-mentioned components, the water-based paint in the present invention can be blended with organic solvents, inorganic color pigments, organic color pigments, extender pigments, aggregates, etc. that are usually used in paints, if necessary. Plasticizers that do not affect the invention, film-forming aids, antiseptics, antifungal agents, antifoaming agents, thickeners, leveling agents, pigment dispersants, coupling agents, anti-settling agents, anti-sagging agents, matte Additives such as an agent, an ultraviolet absorber, an antioxidant, and a light stabilizer can be used alone or in combination.
In addition, a curing catalyst other than the component (B) can be added. Examples of such a curing catalyst include organic tin compounds such as dibutyltin dilaurate, dibutyltin malate, dioctyltin dilaurate, and dioctyltin malate; phosphoric acid such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, monooctyl phosphate; Phosphate esters; Adducts of epoxy compounds such as propylene oxide, butylene oxide, glycidyl methacrylate, γ-glycidoxypropyltriethoxysilane, and Epicoat 828 with phosphoric acid and / or acidic monophosphate esters; organic titanate compounds; organic Aluminum compounds; organic zirconium compounds; acidic compounds such as maleic acid, adipic acid, azelaic acid, acid anhydrides thereof, paratoluenesulfonic acid; hexylamine, N.I. Examples thereof include amines such as N-dimethyldodecylamine; alkaline compounds such as sodium hydroxide. The addition amount of such a curing catalyst is about 0.1-20 weight part normally with respect to 100 weight part of solid content of (A) component.
本発明は、主に建築物、土木構築物等の保護に使用するものであり、例えばコンクリート、モルタル、金属、ガラス、磁器タイル、サイディングボード、押出成形板、プラスチック等の各種基材の表面仕上げに使用することができる。これら基材は、既存塗膜を有するものであってもよい。上記水性塗料の塗装前には、シーラー、サーフェーサー、フィラー等による表面処理を適宜行うこともできる。
本発明における水性塗料は、このような基材の最終の仕上材として使用し、2回以上の重ね塗りによって仕上げを行うものである。通常は、第1回目の塗装を行い下層塗膜を形成させ、その塗膜が乾燥した後に第2回目の塗装を行って上層の塗膜を形成させる。ここで、下層塗膜の乾燥状態は、指触乾燥、半硬化乾燥、硬化乾燥のいずれであってもよいが、本発明では、とりわけ下層塗膜が硬化乾燥した状態である場合に顕著な効果を得ることができる。具体的に、標準状態(気温23℃・相対湿度50%)では3日以上、さらには7日以上の乾燥時間を設けた場合に顕著な効果が得られる。
水性塗料の塗装方法としては、ハケ塗り、スプレー塗装、ローラー塗装等種々の方法を適宜採用することができる。乾式建材に対しては、工場等においてプレコートすることも可能である。
The present invention is mainly used for protection of buildings, civil engineering structures, etc., for example, for surface finishing of various substrates such as concrete, mortar, metal, glass, porcelain tiles, siding boards, extrusion boards, plastics, etc. Can be used. These base materials may have an existing coating film. Prior to the application of the water-based paint, a surface treatment with a sealer, a surfacer, a filler or the like can be appropriately performed.
The water-based paint in the present invention is used as the final finishing material of such a substrate and is finished by two or more overcoats. Usually, the first coating is performed to form a lower layer coating, and after the coating is dried, the second coating is performed to form an upper coating. Here, the dried state of the lower layer coating film may be any of touch drying, semi-cured drying, and cured drying. In the present invention, however, a remarkable effect is obtained particularly when the lower layer coating film is in a cured and dried state. Can be obtained. Specifically, in a standard state (temperature 23 ° C./relative humidity 50%), a remarkable effect can be obtained when a drying time of 3 days or more, further 7 days or more is provided.
As a method for applying the water-based paint, various methods such as brush coating, spray coating, and roller coating can be appropriately employed. Dry building materials can be pre-coated at factories and the like.
以下に実施例及び比較例を示し、本発明の特徴をより明確にする。 Examples and Comparative Examples are shown below to clarify the features of the present invention.
[アルコキシシラン変性縮合物の合成]
テトラエトキシシランの縮合物である平均分子量750のエチルシリケート縮合物(平均分子量750、シリカ残量比率40重量%)100重量部と平均分子量200のポリオキシエチレングリコール#200(和光純薬株式会社製)106.7重量部を混合し、さらに触媒としてジブチル錫ジラウレート0.02重量部を添加後、75℃で8時間脱エタノール反応を行い、アルコキシシラン変性縮合物を合成した。このアルコキシシラン変性縮合物のシリカ残量比率は20.9重量%であった。
[Synthesis of alkoxysilane-modified condensate]
100 parts by weight of an ethyl silicate condensate having an average molecular weight of 750 (average molecular weight 750, residual silica ratio of 40% by weight), which is a condensate of tetraethoxysilane, and polyoxyethylene glycol # 200 having an average molecular weight of 200 (manufactured by Wako Pure Chemical Industries, Ltd.) ) 106.7 parts by weight, and 0.02 part by weight of dibutyltin dilaurate was added as a catalyst, followed by deethanol reaction at 75 ° C. for 8 hours to synthesize an alkoxysilane-modified condensate. The residual silica ratio of the alkoxysilane-modified condensate was 20.9% by weight.
[塗料の作製]
表1の配合に従い、以下に示す原料を常法により混合し、次いで上記アルコキシシラン変性縮合物を混合することにより水性塗料を製造した。
・合成樹脂エマルション1(メチルメタクリレート・2−エチルヘキシルアクリレート・スチレン・グリシジルメタクリレート・メタクリル酸共重合体、固形分50重量%、pH6.2、Tg14℃)
・合成樹脂エマルション2(メチルメタクリレート・2−エチルヘキシルアクリレート・スチレン・メタクリル酸共重合体、固形分50重量%、pH6.1、Tg14℃)
・着色顔料:酸化チタン
・造膜助剤:2,2,4−トリメチル−1,3−ペンタンジオールモノイソブチレート
・触媒:ジブチルスズジラウレート
・増粘剤:ウレタン系増粘剤
・消泡剤:シリコーン系消泡剤
・ヒドラジド化合物1:1,3−ビス(ヒドラジノカルボエチル)−5−イソプロピルヒダントイン
・ヒドラジド化合物2:アジピン酸ジヒドラジド
[Preparation of paint]
In accordance with the formulation shown in Table 1, the following raw materials were mixed by a conventional method, and then the alkoxysilane-modified condensate was mixed to produce an aqueous coating material.
Synthetic resin emulsion 1 (methyl methacrylate, 2-ethylhexyl acrylate, styrene, glycidyl methacrylate, methacrylic acid copolymer, solid content 50% by weight, pH 6.2, Tg 14 ° C.)
Synthetic resin emulsion 2 (methyl methacrylate, 2-ethylhexyl acrylate, styrene, methacrylic acid copolymer, solid content 50% by weight, pH 6.1, Tg 14 ° C.)
-Color pigment: Titanium oxide-Film-forming aid: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate-Catalyst: Dibutyltin dilaurate-Thickener: Urethane thickener-Antifoaming agent: Silicone-based antifoaming agent / hydrazide compound 1: 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin / hydrazide compound 2: adipic acid dihydrazide
[試験方法]
上記方法により得られた水性塗料につき、以下の試験を行った。
[Test method]
The following tests were conducted on the water-based paint obtained by the above method.
・鏡面光沢度
水性塗料を150×120×3mmの透明なガラス板にWET膜厚が150μmとなるようにアプリケーター引きし、標準状態(気温23℃・相対湿度50%)で2日間乾燥養生した後、60度の角度での光沢値を測定した。
-Specular Gloss After applying a water-based paint to a transparent glass plate of 150 x 120 x 3 mm so that the WET film thickness is 150 μm and drying and curing in standard conditions (temperature 23 ° C, relative humidity 50%) for 2 days The gloss value at an angle of 60 degrees was measured.
・耐水性
150×70×3mmのフレキシブル板に、SK#1000プライマー(エポキシ樹脂系プライマー;エスケー化研株式会社製)を乾燥膜厚30μmとなるようにスプレー塗装し、標準状態で8時間乾燥を行った。
次に、作製した塗料組成物を乾燥膜厚が40μmとなるようにスプレー塗装し試験体を作製した。作製した試験体を標準状態で7日間乾燥養生した後、50℃の温水に1時間浸漬した後の光沢保持率を算出した。評価基準は、光沢保持率95%以上を「◎」、90%以上95%未満を「○」、80%以上90%未満を「△」、80%未満を「×」とした。
・ Water resistance Spray coating of SK # 1000 primer (epoxy resin primer; manufactured by SK Kaken Co., Ltd.) on a flexible plate of 150 × 70 × 3 mm to a dry film thickness of 30 μm, followed by drying for 8 hours under standard conditions went.
Next, the prepared coating composition was spray-coated so that the dry film thickness was 40 μm to prepare a test body. The prepared specimen was dried and cured for 7 days in a standard state, and the gloss retention after being immersed in warm water at 50 ° C. for 1 hour was calculated. The evaluation criteria were a gloss retention ratio of 95% or more as “」 ”, 90% or more and less than 95% as“ ◯ ”, 80% or more and less than 90% as“ Δ ”, and less than 80% as“ X ”.
・耐汚染性
150×75×0.8mmのアルミ板に、SK#1000プライマーを乾燥膜厚30μmとなるようにスプレー塗装し、標準状態で8時間乾燥を行った。
次に、作製した塗料組成物を乾燥膜厚が40μmとなるようにスプレー塗装し試験体を作製した。作製した試験体を、標準状態で7日間乾燥養生した後、塗膜面に15重量%カーボンブラック水分散ペースト液を、直径20mm、高さ5mmとなるように滴下し、50℃の恒温室中に2時間放置した。その後流水中にて洗浄し、塗膜表面の汚染の程度を目視により4段階(優:◎>○>△>×:劣)で評価した。
Contamination resistance A 150 × 75 × 0.8 mm aluminum plate was spray-coated with a SK # 1000 primer so as to have a dry film thickness of 30 μm, and dried in a standard state for 8 hours.
Next, the prepared coating composition was spray-coated so that the dry film thickness was 40 μm to prepare a test body. The prepared specimen was dried and cured in a standard state for 7 days, and then a 15 wt% carbon black aqueous dispersion paste solution was dropped onto the coating surface so as to have a diameter of 20 mm and a height of 5 mm in a constant temperature room at 50 ° C. For 2 hours. Thereafter, the film was washed in running water, and the degree of contamination on the coating film surface was visually evaluated in four stages (excellent: ◎>◯>Δ> ×: inferior).
・重ね塗り時密着性
150×75×0.8mmのアルミ板に、SK#1000プライマーを乾燥膜厚30μmとなるようにスプレー塗装し、標準状態で8時間乾燥を行った。
次に、作製した塗料組成物を乾燥膜厚が40μmとなるようにスプレー塗装し、各条件下(標準状態2日、標準状態10日、50℃2日、50℃10日)で養生した後、さらに同一塗料組成物を乾燥膜厚が40μmとなるようにスプレー塗装し、標準状態で3日間養生したものを試験体とした。作製した試験体を、JIS K 5600−5−6に準じた碁盤目テープ法にて密着性を評価した。評価基準は、欠損部面積が5%以内のものを「○」、欠損部面積が5〜35%のものを「△」、欠損部面積が35%以上のものを「×」とした。
-Adhesion at the time of recoating The SK # 1000 primer was spray-coated on a 150 × 75 × 0.8 mm aluminum plate so as to have a dry film thickness of 30 μm, and dried for 8 hours in a standard state.
Next, after spray coating the prepared coating composition so that the dry film thickness becomes 40 μm and curing under each condition (standard state 2 days, standard state 10 days, 50 ° C. 2 days, 50 ° C. 10 days) Further, the same coating composition was spray-coated so as to have a dry film thickness of 40 μm and cured for 3 days in a standard state to obtain a test body. The prepared specimens were evaluated for adhesion by a cross-cut tape method according to JIS K 5600-5-6. Evaluation criteria were “◯” when the defect area was 5% or less, “Δ” when the defect area was 5 to 35%, and “X” when the defect area was 35% or more.
[試験結果]
試験結果を表2に示す。実施例1〜4では、いずれの試験においても良好な結果を得ることができた。
[Test results]
The test results are shown in Table 2. In Examples 1 to 4, good results could be obtained in any test.
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