JP5549871B2 - Aqueous solution for film formation - Google Patents
Aqueous solution for film formation Download PDFInfo
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- JP5549871B2 JP5549871B2 JP2010169541A JP2010169541A JP5549871B2 JP 5549871 B2 JP5549871 B2 JP 5549871B2 JP 2010169541 A JP2010169541 A JP 2010169541A JP 2010169541 A JP2010169541 A JP 2010169541A JP 5549871 B2 JP5549871 B2 JP 5549871B2
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- film
- aqueous solution
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- 239000007864 aqueous solution Substances 0.000 title claims description 28
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 239000010408 film Substances 0.000 claims description 77
- 239000000126 substance Substances 0.000 claims description 39
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 33
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 29
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 23
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 23
- 229920002554 vinyl polymer Polymers 0.000 claims description 23
- 229910052804 chromium Inorganic materials 0.000 claims description 22
- 239000011651 chromium Substances 0.000 claims description 22
- 229920000620 organic polymer Polymers 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000008119 colloidal silica Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- -1 silicate compound Chemical class 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- 229910001430 chromium ion Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000011282 treatment Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 150000004760 silicates Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 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 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Landscapes
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
Description
本発明は金属および非金属の部材の表面保護用の水溶液ならびに表面保護方法を提供するものである。 The present invention provides an aqueous solution and a surface protection method for protecting the surface of metallic and nonmetallic members.
金属あるいは非金属の基材を表面処理液に浸漬させて表面保護を行う手法は塗布、焼き付け、スプレーなどの表面処理と同様、幅広く行われている。これはめっき皮膜上、化成皮膜上にあっても同様であり、防錆効果、装飾効果、保護膜的な効果などを付加することを目的として行われる。 Techniques for surface protection by immersing a metal or non-metal substrate in a surface treatment solution are widely used, as are surface treatments such as coating, baking, and spraying. This is the same even on the plating film and the chemical conversion film, and is performed for the purpose of adding a rust prevention effect, a decoration effect, a protective film effect, and the like.
これらの表面処理液には各種効果の付与を目的として塗料やケイ酸塩、リン酸塩等、並びにアクリル酸系ポリマー等有機樹脂が用いられ、浸漬した部位に塗膜、ケイ酸塩皮膜、リン酸塩皮膜など無機皮膜、そしてアクリル酸系などの有機樹脂皮膜を形成する。例えば特開２００５−１２６７９６号には三価クロム化成皮膜上に各種オーバーコートを施すことが記載されている。また、特許第３３３２３７３号には、三価クロムを用いた化成皮膜に行うトップコート処理について記載されている。特に三価クロム黒色化成皮膜処理後に三価クロム、リンの酸素酸、亜鉛、有機酸からなる群から選択した一種以上を含有する液に浸漬する仕上げ処理を行うことは一般的に行われている手法であり、仕上げ処理液に有機樹脂を添加して性能を向上させることも行われている。例えばＷＯ２００７／１００１３５号には上記の仕上げ処理液にメタクリル酸系樹脂を添加して用いている実施例が存在する。 These surface treatment liquids use paints, silicates, phosphates, etc., and organic resins such as acrylic polymers for the purpose of imparting various effects. An inorganic film such as an acid film and an organic resin film such as an acrylic acid film are formed. For example, Japanese Patent Application Laid-Open No. 2005-126696 describes that various overcoats are applied on a trivalent chromium chemical conversion film. Japanese Patent No. 3332373 describes a top coat treatment performed on a chemical conversion film using trivalent chromium. In particular, after the trivalent chromium black chemical conversion film treatment, it is generally performed to perform a finishing treatment soaking in a liquid containing at least one selected from the group consisting of trivalent chromium, phosphorus oxygen acid, zinc, and organic acid. This is a technique for improving performance by adding an organic resin to a finishing solution. For example, WO2007 / 100135 includes an example in which a methacrylic acid resin is added to the above-described finishing treatment liquid.
また、塗料による塗装を化成皮膜上に施して各種性能を得ることも一般的に行われている。例えば特開２００３−１６６３０５号にはアルミニウム部材上に化成皮膜を形成し、その上に太陽熱遮蔽塗料を電着塗装する方法が開示されている。 It is also common practice to obtain various performances by applying paint on the chemical conversion film. For example, Japanese Patent Application Laid-Open No. 2003-166305 discloses a method of forming a chemical conversion film on an aluminum member and electrodepositing a solar heat shielding paint thereon.
しかし、塗料を用いた表面処理ではその膜厚の厚さに欠点がある。塗膜厚は一般的には数十μｍ程度であり、寸法の精密さを要求される部材に用いることが出来ない。例えばボルトやナットの締結部位に塗料を用いた場合、ボルトが締結できないなどの問題が発生することが知られている。 However, the surface treatment using a paint has a drawback in the thickness of the film. The coating thickness is generally about several tens of μm, and cannot be used for members that require dimensional precision. For example, it is known that when a paint is used for a bolt or nut fastening site, a problem such as the bolt cannot be fastened occurs.
無機皮膜および有機樹脂皮膜のトップコートに関しては塗料と比べれば膜厚の問題は少ないものの、前記引用文献の実施例を実際に実施した場合には塗料と比較して耐傷性が不足する傾向があり、塗料やトップコートの優れた性能を維持しつつ耐傷性に優れ、かつ保護膜厚の薄い表面保護方法が望まれている。 Although the film thickness problem is less with respect to the top coat of the inorganic film and the organic resin film than the paint, when the examples of the cited references are actually carried out, the scratch resistance tends to be insufficient as compared with the paint. Therefore, a surface protection method having excellent scratch resistance and a thin protective film while maintaining the excellent performance of paints and top coats is desired.
三価クロム黒色化成皮膜処理後の仕上げ処理皮膜については有機樹脂を添加しないと撥水性、耐食性、耐傷性などの機能が不足する。アクリル酸・メタクリル酸系有機樹脂を添加した場合、撥水性、耐食性は向上するが耐傷性については十分に向上しない問題がある。さらに三価クロム黒色化成皮膜に有機樹脂系トップコートを施した場合には水で膨潤することにより白化し不良発生の原因となることがある。また、これらの有機樹脂の代わりにケイ酸塩やコロイダルシリカなどケイ酸化合物を添加して耐食性を向上させる発明が特開２００５−３２０５７３号に開示されている。しかし、実際に実施した場合、皮膜の干渉色が強くなり、望まれる黒色外観が得られにくい問題がある。 If the organic resin is not added to the finish-treated film after the trivalent chromium black chemical conversion film treatment, functions such as water repellency, corrosion resistance, and scratch resistance are insufficient. When an acrylic acid / methacrylic acid organic resin is added, water repellency and corrosion resistance are improved, but scratch resistance is not sufficiently improved. Furthermore, when an organic resin-based topcoat is applied to the trivalent chromium black chemical conversion film, it may swell with water and cause whitening and cause defects. Japanese Patent Laid-Open No. 2005-320573 discloses an invention that improves the corrosion resistance by adding a silicate compound such as silicate or colloidal silica instead of these organic resins. However, when actually carried out, there is a problem that the interference color of the film becomes strong and it is difficult to obtain a desired black appearance.
本発明者が鋭意研究した結果、水酸基を含有する水溶性有機ポリマーを無機皮膜及び有機樹脂皮膜のトップコート並びに化成皮膜処理後の仕上げ処理液、特に三価クロム黒色化成皮膜処理後の仕上げ処理液といった、添加剤と成りうる物質を含有する水溶液に添加することによりトップコート並びに仕上げ皮膜の性能、撥水性、耐傷性を高めることを見出した。特に耐傷性を十分に高めることはアクリル酸系・メタクリル酸系などの有機樹脂を用いた場合には達成出来なかったことである。撥水性、耐傷性を高める原理は不明だが水酸基含有ポリマー、特にポリビニルアルコールまたはポリビニルアセタールを用いたときに大幅に向上する。また、三価クロム黒色化成皮膜後の仕上げ処理に用いた場合、上記有機樹脂を添加したときと異なり、水で膨潤しづらい特徴があるため白化現象は見られない。 As a result of diligent research by the present inventors, a water-soluble organic polymer containing a hydroxyl group is subjected to a top treatment of an inorganic film and an organic resin film, and a finishing treatment liquid after a chemical conversion film treatment, particularly a finishing treatment liquid after a trivalent chromium black chemical conversion film treatment. It has been found that the performance, water repellency and scratch resistance of the top coat and the finished film are improved by adding to an aqueous solution containing a substance that can be an additive. In particular, sufficiently improving the scratch resistance cannot be achieved when an organic resin such as acrylic acid or methacrylic acid is used. Although the principle of improving water repellency and scratch resistance is unknown, it is greatly improved when a hydroxyl group-containing polymer, particularly polyvinyl alcohol or polyvinyl acetal is used. Further, when used for the finishing treatment after the trivalent chromium black chemical conversion film, unlike the case where the organic resin is added, the whitening phenomenon is not seen because it is difficult to swell with water.
水溶性有機ポリマーについては特に制限はないが、ポリビニルアセタール及びポリビニルアルコールにおいて特にトップコート並びに仕上げ処理液の性能を向上させる効果が高い。 Although there is no restriction | limiting in particular about water-soluble organic polymer, The effect which improves the performance of a topcoat and a finishing process liquid especially in polyvinyl acetal and polyvinyl alcohol is high.
しかし、これらの水溶性有機ポリマーのみの水溶液においては上記の保護効果は非常に小さく、主たる成分としての金属、リンの酸素酸、珪酸化合物などのうち１種以上と水溶液中に共存させることによって保護効果を発揮することが分かる。 However, in the aqueous solution containing only these water-soluble organic polymers, the above-mentioned protective effect is very small, and it is protected by coexisting in the aqueous solution with one or more of the main components such as metal, phosphorus oxyacid, and silicate compounds. It turns out that an effect is demonstrated.
以下の説明では発明の範囲を限定することを企図しないが、本発明における有機樹脂保護皮膜形成としては図１のモデルが考えられる。また、図１のモデルはポリビニルアルコール、ポリビニルアセタール単独では有効な皮膜を形成しないが添加剤と共存させることで皮膜を形成することが出来ることを提示することを目的としており、各種機能発現原理を提示することを目的としていない。以下、説明のために三価クロム化成皮膜（これは酸化クロム又は水酸化クロムを骨格としている）をポリビニルアルコールと三価クロムの混合水溶液に浸漬させるモデルで説明するが、例えば前記化成皮膜の代わりに他の基材並びにホウ酸塩、ケイ酸塩、リン酸塩皮膜等、そしてポリビニルアルコールの代わりに各種水溶性有機ポリマー、仕上げ剤中のクロムの代わりにその他の金属イオン、珪酸化合物、リンの酸素酸等に置き換えても同様の議論が成立する。浸漬処理を行うと三価クロム化成皮膜上にポリビニルアルコールと三価クロムの水溶液が均一に広がることになる。ここから乾燥で水を飛ばした場合、水の量が減るにつれてポリビニルアルコールの酸素と三価クロムイオンの配位結合が強くなり、酸化クロム又は水酸化クロムを含有したポリマーが析出する。クロムイオンは例えば水分子に由来する下地の酸素原子又は金属原子と配位結合して骨格を伸ばし皮膜を厚くするとともに、ポリビニルアルコールの疎水基が表面に現れる。これにより、撥水性を発揮ならしめると考える。いわば、ポリビニルアルコールと共存させる金属イオン、リンの酸素酸、珪酸化合物など添加物が下地の金属並びに化成皮膜とポリビニルアルコールのバインダーの役割を果たしているといえる。 Although the following description does not intend to limit the scope of the invention, the model of FIG. 1 can be considered as the organic resin protective film formation in the present invention. In addition, the model in FIG. 1 is intended to show that polyvinyl alcohol and polyvinyl acetal alone do not form an effective film, but can form a film by coexisting with an additive. It is not intended to be presented. Hereinafter, for the purpose of explanation, a model in which a trivalent chromium conversion coating (which has chromium oxide or chromium hydroxide as a skeleton) is immersed in a mixed aqueous solution of polyvinyl alcohol and trivalent chromium will be described. In addition to other substrates and borate, silicate, phosphate coating, etc., various water-soluble organic polymers instead of polyvinyl alcohol, other metal ions, silicate compounds, phosphorus instead of chromium in the finish The same argument holds even if it is replaced with oxygen acid or the like. When the immersion treatment is performed, an aqueous solution of polyvinyl alcohol and trivalent chromium spreads uniformly on the trivalent chromium chemical conversion film. When water is blown off from here, as the amount of water decreases, the coordination bond between oxygen of polyvinyl alcohol and trivalent chromium ions becomes stronger, and a polymer containing chromium oxide or chromium hydroxide is precipitated. Chromium ions, for example, coordinate with a base oxygen atom or metal atom derived from water molecules to stretch the skeleton and thicken the film, and the hydrophobic group of polyvinyl alcohol appears on the surface. This is considered to make water repellency effective. In other words, it can be said that additives such as metal ions coexisting with polyvinyl alcohol, phosphorus oxyacid, and silicic acid compounds serve as a base metal and a binder for the conversion coating and polyvinyl alcohol.
ポリビニルアルコールおよびポリビニルアセタール単独の水溶液では性能を発揮しない理由は以下の通りであると考えられる。ポリビニルアルコールだけではポリビニルアルコールの水酸基が下地の金属並びに化成皮膜と直接、引きつけあうことになるが、バインダー層的なものがないためこの結合が弱く、ポリビニルアルコールの皮膜を形成しづらいために性能を発揮しないと考えられる。さらに、ポリビニルアルコールの場合は繰り返し単位中の水酸基が多く、水溶性が高いため、形成した皮膜も水に溶解し耐水性が低いと考える。 The reason why the performance of the aqueous solution of polyvinyl alcohol and polyvinyl acetal alone is not as follows. With polyvinyl alcohol alone, the hydroxyl group of polyvinyl alcohol is directly attracted to the underlying metal and chemical conversion film, but since there is no binder layer, this bond is weak, and it is difficult to form a film of polyvinyl alcohol. It is thought that it does not demonstrate. Furthermore, in the case of polyvinyl alcohol, since there are many hydroxyl groups in a repeating unit and water solubility is high, it is thought that the formed film | membrane melt | dissolves in water and water resistance is low.
ポリビニルアルコール及びポリビニルアセタールの代わりにポリアクリル酸、ポリメタクリル酸等を用いた場合も同様の議論が成立するが、生成した皮膜の耐キズ性が、ポリビニルアルコール及びポリビニルアセタールを用いた場合より低い。 The same argument holds when polyacrylic acid, polymethacrylic acid, or the like is used instead of polyvinyl alcohol and polyvinyl acetal, but the scratch resistance of the formed film is lower than when polyvinyl alcohol and polyvinyl acetal are used.
以上の知見を基礎として、本発明は水酸基を含有する水溶性有機ポリマーと１種以上の添加剤を含んだ、浸漬により基材表面に皮膜を形成する水溶液であって、該水溶性有機ポリマーが以下の式Ａの単位を６０モル％以上の割合で含有するポリマーであり、
該添加剤がＣｒ、Ｃｏ、Ｆｅ、Ｎｉ、Ｚｎ、Ｙ、Ｌａ、Ｍｏ、Ｗ、Ｔｉ、Ａｌ、Ｚｒ、Ｍｎ、Ｖより選択される１種以上の金属のイオン、リンの酸素酸、珪酸化合物より選択される１種以上含む添加剤である水溶液である。
Based on the above knowledge, the present invention is an aqueous solution containing a water-soluble organic polymer containing a hydroxyl group and one or more additives, which forms a film on the surface of the substrate by dipping. It is a polymer containing a unit of the following formula A in a proportion of 60 mol% or more,
The additive is one or more metal ions selected from Cr, Co, Fe, Ni, Zn, Y, La, Mo, W, Ti, Al, Zr, Mn, and V, phosphorus oxyacid, and silicate compound It is the aqueous solution which is an additive containing 1 or more types selected from more.
さらに本発明は、一実施形態において前記基材は金属または金属の酸化物及び水酸化物、ホウ酸塩、ケイ酸塩、リン酸塩より選択される１種以上を含む化成皮膜である水溶液である。 Furthermore, in one embodiment of the present invention, the substrate is an aqueous solution which is a chemical conversion film containing at least one selected from metals or metal oxides and hydroxides, borates, silicates, and phosphates. is there.
さらに本発明は、一実施形態において前記水溶性有機ポリマーがさらに以下の式Ｂ及び／又は式Ｃの単位を含む、水溶液である。
さらに本発明は、一実施形態において前記水溶性有機ポリマーがポリビニルアルコール、又はポリビニルアセタールから選択される１種以上を含む前記の水溶液である。 Furthermore, this invention is the said aqueous solution containing 1 or more types as which the said water-soluble organic polymer is selected from polyvinyl alcohol or polyvinyl acetal in one Embodiment.
さらに本発明は、一実施形態において前記添加剤において、前記金属イオンが三価クロムイオンである前記の水溶液である。 Furthermore, this invention is the said aqueous solution whose said metal ion is a trivalent chromium ion in the said additive in one Embodiment.
さらに本発明は、一実施形態において前記添加剤において、前記珪酸化合物がコロイダルシリカである前記の水溶液である。 Furthermore, the present invention is the aqueous solution according to one embodiment, wherein the silicic acid compound is colloidal silica in the additive.
さらに本発明は、一実施形態において前記化成皮膜が三価クロムを含む化成皮膜である前記の水溶液である。 Furthermore, the present invention is the aqueous solution according to one embodiment, wherein the chemical conversion film is a chemical conversion film containing trivalent chromium.
さらに本発明は、一実施形態において前記基材を前記の水溶液に浸漬し、厚さ５μｍ以下の薄膜を形成することを特徴とする皮膜形成方法である。 Furthermore, the present invention is a film forming method characterized in that in one embodiment, the substrate is immersed in the aqueous solution to form a thin film having a thickness of 5 μm or less.
さらに本発明は、一実施形態において前記の方法により皮膜を形成した部材である。 Furthermore, this invention is the member which formed the membrane | film | coat by said method in one Embodiment.
本発明に係る処理液は水溶性有機ポリマーと金属イオン、リンの酸素酸、珪酸化合物などより選択される１種以上の物質の水溶液によって与えられる。 The treatment liquid according to the present invention is provided by an aqueous solution of one or more substances selected from water-soluble organic polymers and metal ions, phosphorus oxyacids, silicic acid compounds and the like.
本発明に用いる水溶性有機ポリマーは特にポリビニルアセタール、ポリビニルアルコールが有効であるがこれに限定されるものではなく、式Ａのサブユニットを６０モル％以上含有するものであれば適用可能である。化合物の種類、構造、分子量並びに１種以上の物質の種類や濃度はその目的や共存物質により最適な条件が変化すると考える。 As the water-soluble organic polymer used in the present invention, polyvinyl acetal and polyvinyl alcohol are particularly effective. However, the present invention is not limited thereto, and any water-soluble organic polymer may be used as long as it contains 60 mol% or more of the subunit of formula A. It is thought that the optimum conditions vary depending on the purpose and coexisting substances of the type, structure, molecular weight, and type and concentration of one or more substances.
添加剤としての金属イオンは例えば、Ｃｒ、Ｃｏ、Ｆｅ、Ｎｉ、Ｚｎ、Ｙ、Ｌａ、Ｍｏ、Ｗ、Ｔｉ、Ａｌ、Ｚｒ、Ｍｎ、Ｖより選択される１種以上を使用することができる。リンの酸素酸としてはリン酸、亜リン酸、次亜リン酸、ピロリン酸及びこれらの塩等が挙げられるがこれらに限定されるものではない。ケイ酸化合物としては各種水溶性ケイ酸塩の他、水分散性コロイダルシリカが使用できる。コロイダルシリカとしては、例えば、スノーテックス（商標）シリーズ（日産化学工業（株））、アデライト（商標）ＡＴシリーズ、（（株）ＡＤＥＫＡ）、シリカドール（商標）シリーズ（日本化学工業（株））、カタロイド（商標）シリーズ（日揮触媒化成（株））、等が挙げられる。以上に例示した添加剤は本発明を限定するものではなく、他の原子あるいは分子と配位結合するものであれば何でも良い。添加剤濃度は金属、リンの酸素酸、ケイ素化合物の総和が１０〜３００ｇ／Ｌ、より好ましくは２０〜１００ｇ／Ｌである。 As the metal ion as the additive, for example, one or more selected from Cr, Co, Fe, Ni, Zn, Y, La, Mo, W, Ti, Al, Zr, Mn, and V can be used. Examples of the oxygen acid of phosphorus include, but are not limited to, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, and salts thereof. As the silicate compound, water-dispersible colloidal silica can be used in addition to various water-soluble silicates. Examples of colloidal silica include Snowtex (trademark) series (Nissan Chemical Industry Co., Ltd.), Adelite (trademark) AT series, (ADEKA Corporation), and Silica Doll (trademark) series (Nippon Chemical Industry Co., Ltd.). , Cataloid (trademark) series (JGC Catalysts & Chemicals Co., Ltd.), and the like. The additive exemplified above is not intended to limit the present invention, and any additive may be used as long as it is coordinated with another atom or molecule. The additive concentration is 10 to 300 g / L, more preferably 20 to 100 g / L of the sum of the metal, phosphorus oxyacid, and silicon compound.
例えば三価クロム黒色化成皮膜の仕上げ液への使用では現在使用されている仕上げ液に０．１〜２ｇ／Ｌのポリビニルアルコール、ポリビニルアセタールなどを添加することで効果を発揮する。０．１ｇ／Ｌ以下では十分な効果を発揮せず、２ｇ／Ｌ以上添加しても効果は頭打ちであり、経済性を損なう。 For example, when the trivalent chromium black chemical conversion film is used as a finishing solution, the effect is exhibited by adding 0.1 to 2 g / L polyvinyl alcohol, polyvinyl acetal, or the like to the currently used finishing solution. If it is 0.1 g / L or less, a sufficient effect is not exhibited, and even if 2 g / L or more is added, the effect reaches a peak and the economic efficiency is impaired.
本願発明の処理液の対象となる基材は表面処理、オーバーコートの対象となるものであれば特に限定は存在しないが、好適に用いられるものは、化成皮膜である。ここで化成皮膜とは基材と何らかの物質が化学反応することにより生成する保護皮膜のことをいう。そして、前記化成皮膜は、金属を含み、例えば、Ｃｒ、Ｃｏ、Ｆｅ、Ｎｉ、Ｚｎ、Ｙ、Ｌａ、Ｍｏ、Ｗ、Ｔｉ、Ａｌ、Ｚｒ、Ｍｎ、Ｖより選択される一種以上が含まれる。前記金属は本発明を限定するものではなく、他の原子と配位結合するものであれば何でも良い。また前記金属は例えば、酸化物及び水酸化物、ホウ酸塩、ケイ酸塩、リン酸塩より選択される１種以上の形態で化成皮膜に含まれる。 The base material that is the target of the treatment liquid of the present invention is not particularly limited as long as it is the target of surface treatment and overcoat, but the chemical film is preferably used. Here, the chemical conversion film refers to a protective film formed by a chemical reaction between a substrate and some substance. The chemical conversion film contains a metal, for example, one or more selected from Cr, Co, Fe, Ni, Zn, Y, La, Mo, W, Ti, Al, Zr, Mn, and V. The metal is not intended to limit the present invention, and any metal can be used as long as it is coordinated with another atom. The metal is contained in the chemical conversion film in one or more forms selected from oxides and hydroxides, borates, silicates, and phosphates.
本願発明の処理液によって処理される部材は前記、表面処理、オーバーコートの対象となる部位を含むものであれば何ら限定は存在しない。その部材は自動車をはじめ電気製品、船舶、建築材からコンピュータに至るまで、各種工業製品の部品として用いられるものが主である。例えば、金属板、ボルト、ナット、パイプ、ビス、プリント基板、ダクト、エンジン部品、ホイール、ギヤ、ネジ、バネ、各種複合部品、切削加工品、ワッシャー、工具、等が挙げられるがこれに限定されない。 The member to be treated by the treatment liquid of the present invention is not limited as long as it includes the portion to be surface-treated and overcoated. The members are mainly used as parts of various industrial products from automobiles, electrical products, ships, building materials to computers. Examples include, but are not limited to, metal plates, bolts, nuts, pipes, screws, printed boards, ducts, engine parts, wheels, gears, screws, springs, various composite parts, cutting products, washers, tools, etc. .
また、本願発明の処理液を用いて、部材表面に形成される皮膜の厚さは、５μｍ以下であり、好ましくは、２μｍ以下である。 Moreover, the thickness of the film | membrane formed on the member surface using the process liquid of this invention is 5 micrometers or less, Preferably, it is 2 micrometers or less.
以下、実施例及び比較例により本発明を説明する。実施例で用いためっきの種類、化成処理の組成及び処理条件、並びに仕上げの組成及び処理条件については表１の通りである。
ここで、ポリビニルアセタールは、式Ａに記載のサブユニットを６０〜９５モル％の割合で含み、式Ｂに記載のサブユニットを５〜４０モル％含み、式Ｃに記載のサブユニットを含まず、式Ａと式Ｂの含有率の合計が１００モル％になる化合物である。ポリビニルアルコール（ＰＶＡ）は、式Ａに記載のサブユニットを７０〜１００モル％の割合で含み、式Ｂに記載のサブユニットを含まず、式Ｃに記載のサブユニットを０〜３０モル％含み、式Ａと式Ｃの含有率の合計が１００モル％になる化合物である。またポリアクリル酸ナトリウムは、式Ａ〜式Ｃのサブユニットを含まない。以下の実験では特に断りのない限り、ポリビニルアセタールは式Ａに記載のサブユニットを９０モル％、式Ｂに記載のサブユニットを１０モル％（式Ａ中のＲ1は水素であり、式Ｂ中のＲ2はプロピル、Ｒ3は水素）含むものを、ＰＶＡは式Ａに記載のサブユニットを９０モル％含み、式Ｃに記載のサブユニットを１０モル％含むものを用いた（式Ａ中のＲ1は水素であり、式Ｃ中のＲ4は水素である）。また、実施例で用いたコロイダルシリカは、スノーテックス（商標）（（日産化学工業（株））製である。
Hereinafter, the present invention will be described with reference to examples and comparative examples. Table 1 shows the type of plating, chemical conversion treatment composition and treatment conditions, and finishing composition and treatment conditions used in the examples.
Here, the polyvinyl acetal contains 60 to 95 mol% of the subunit described in Formula A, 5 to 40 mol% of the subunit described in Formula B, and does not include the subunit described in Formula C. A compound in which the total content of Formula A and Formula B is 100 mol%. Polyvinyl alcohol (PVA) contains 70 to 100 mol% of the subunit described in Formula A, does not include the subunit described in Formula B, and includes 0 to 30 mol% of the subunit described in Formula C. A compound in which the total content of Formula A and Formula C is 100 mol%. Moreover, sodium polyacrylate does not contain the subunit of Formula A-Formula C. In the following experiments, unless otherwise specified, polyvinyl acetal contains 90 mol% of the subunit described in Formula A and 10 mol% of the subunit described in Formula B (R 1 in Formula A is hydrogen, In which R 2 is propyl and R 3 is hydrogen), PVA was used containing 90 mol% of the subunit described in Formula A and 10 mol% of the subunit described in Formula C (Formula A) In which R 1 is hydrogen and R 4 in formula C is hydrogen). Moreover, the colloidal silica used in the Examples is manufactured by Snowtex (trademark) ((Nissan Chemical Industry Co., Ltd.).
試験は亜鉛又は亜鉛合金めっきを行ったボルトおよびナットあるいは鉄板（以下に示す耐キズ（２）の試験のみ）を用いて行った。めっき皮膜上に化成皮膜処理を行い、次いで仕上げ処理を行った後の耐キズ性、耐食性、撥水性、外観、ボルトとナットの双方を表面処理した場合の締結について評価した。耐キズ性は（１）ＪＩＳ Ｋ ５６００−５−４に従う鉛筆硬度試験を行った。さらには（１）と別に、（２）振とう機を利用した耐キズ性試験を行った。容器の底面に仕上げ処理をした鉄板を貼り付け、上に長さ１ｃｍ前後のビスを厚さ５ｃｍ程度敷き詰め、２００ｒｐｍで５分振とうさせて、鉄板に付いたキズの量を評価した。以下に示す実施例２と比較例４を標準とし、キズの量が実施例２と同等以下なら○、実施例２と比較例４の中間なら△、比較例４と同等以上なら×の評価とした。耐食性はＪＩＳ Ｚ ２３７１に従う塩水噴霧試験を行い、亜鉛めっきについては白錆５％発生した時間が２４０時間を基準に、それ以上で○、それ未満で×とした。亜鉛鉄合金、亜鉛ニッケル合金めっきではそれぞれ３６０時間、４８０時間を基準とした。撥水性については仕上げ処理後の皮膜表面に水滴を滴下して接触角を測定した。６０度以上を○、３０度以上〜６０度未満を△、３０度未満を×とした。外観はツヤ、黒味、干渉色などを目視にて総合的に判断した。経時変化は仕上げ後の乾燥を自然乾燥のみとし、膨潤しやすい状況下で一日置いた後の変色（白化）の有無を評価した。締結は仕上げ処理後のボルトとナットを締結して、処理前のボルト、ナットと同様に締結できれば○、人力では締結できない、若しくは過度に力を入れないと締結できない状況に陥ったら×とした。膜厚測定は仕上げ皮膜の膜厚をグロー放電発光表面分析（ＧＤＳ）により測定した。 The test was carried out using bolts and nuts plated with zinc or zinc alloy, or iron plates (only scratch resistance test (2) shown below). After the chemical conversion film treatment was performed on the plating film, and then the finishing treatment was performed, scratch resistance, corrosion resistance, water repellency, appearance, and fastening when both the bolt and nut were surface-treated were evaluated. Scratch resistance was (1) a pencil hardness test according to JIS K 5600-5-4. In addition to (1), (2) a scratch resistance test using a shaker was conducted. A finished iron plate was affixed to the bottom of the container, and a screw having a thickness of about 1 cm was spread on top of the vessel, and the plate was shaken at 200 rpm for 5 minutes to evaluate the amount of scratches attached to the iron plate. Example 2 and Comparative Example 4 shown below are standard, and if the amount of scratches is equal to or less than that of Example 2, it is evaluated as ◯ if it is intermediate between Example 2 and Comparative Example 4, and if it is equal to or greater than that of Comparative Example 4, it is evaluated as x. did. Corrosion resistance was evaluated by performing a salt spray test in accordance with JIS Z 2371. For galvanization, the time when white rust was 5% generated was evaluated as ◯ when the time was 240 hours or more and × when it was less. In the case of zinc-iron alloy and zinc-nickel alloy plating, 360 hours and 480 hours were used as references. For water repellency, a water drop was dropped on the surface of the film after the finishing treatment, and the contact angle was measured. 60 degree or more was set as (circle), 30 degree or more-less than 60 degree | times as (triangle | delta), and less than 30 degree | times was set as x. Appearance was comprehensively judged visually for gloss, blackness and interference color. With respect to the change with time, the drying after finishing was only natural drying, and the presence or absence of discoloration (whitening) after standing for one day under the condition of easily swelling was evaluated. For fastening, bolts and nuts after finishing treatment were fastened, and if the bolts and nuts before the treatment could be fastened, it was evaluated as “◯”, and if it could not be fastened by human power, or if it could not be fastened without excessive force, it was marked “X”. In the film thickness measurement, the film thickness of the finished film was measured by glow discharge luminescent surface analysis (GDS).
比較例１、２
ポリビニルアセタール（比較例１）、ポリビニルアルコール（比較例２）の水溶液を作成し、実施例１、２と同条件で仕上げ処理したところ、艶もそれほどなく、耐傷性、耐食性も向上しなかった。
Comparative Examples 1 and 2
When aqueous solutions of polyvinyl acetal (Comparative Example 1) and polyvinyl alcohol (Comparative Example 2) were prepared and finished under the same conditions as in Examples 1 and 2, the gloss was not so much, and scratch resistance and corrosion resistance were not improved.
比較例３
実施例１で仕上げ処理の代わりにウレタン樹脂をエアスプレー塗布し、平均２０μｍの塗膜を形成したところ、艶もよく、耐キズ性においても向上した。しかし、処理したボルトをナットに締結させようとしたところ、締結することができなかった。
Comparative Example 3
In Example 1, a urethane resin was applied by air spraying instead of the finishing treatment to form a coating film having an average of 20 μm. As a result, gloss was good and scratch resistance was improved. However, when the treated bolt was fastened to the nut, it could not be fastened.
比較例４
ポリビニルアセタール、ポリビニルアルコールを添加しない以外は実施例１、２と同条件で後処理を行ったところ、耐食性は実施例と同等レベルまで向上したものの外観に艶がなく、耐傷性も劣る結果となった。
Comparative Example 4
When post-treatment was performed under the same conditions as in Examples 1 and 2 except that polyvinyl acetal and polyvinyl alcohol were not added, the corrosion resistance was improved to the same level as in Examples, but the appearance was not glossy and the scratch resistance was poor. It was.
比較例５
アクリル酸系ポリマーをポリビニルアセタール、ポリビニルアルコールの代わりに添加し、処理したところ、実施例１、２と同等につやのある外観が得られたが耐傷性が劣る結果となった。また、経時で白化する現象が見られた。
Comparative Example 5
When an acrylic acid polymer was added in place of polyvinyl acetal and polyvinyl alcohol and processed, a glossy appearance equivalent to that of Examples 1 and 2 was obtained, but the scratch resistance was poor. Moreover, the phenomenon which whitens with time was seen.
比較例６、７
比較例１、２では皮膜がほとんど形成されなかったので、ポリマーの量を２００倍にして同様の実験を行った。結果、わずかに皮膜が形成されたものの、性能は実施例より大きく劣る。
Comparative Examples 6 and 7
In Comparative Examples 1 and 2, since almost no film was formed, the same experiment was performed with the amount of polymer 200 times. As a result, although a film was slightly formed, the performance was greatly inferior to the examples.
比較例８
ポリビニルアセタール、ポリビニルアルコールを添加しない以外は実施例４と同条件で後処理を行ったところ、耐食性は実施例と同等レベルだが撥水性、耐傷性が大きく劣る。
Comparative Example 8
When post-treatment was performed under the same conditions as in Example 4 except that polyvinyl acetal and polyvinyl alcohol were not added, the corrosion resistance was the same level as in the examples, but the water repellency and scratch resistance were greatly inferior.
ポリビニルアセタール、ＰＶＡの式Ａのサブユニットの割合を変化させて実施例１、実施例２を行い、実施例１４〜１８とした（下記表中の式Ａ〜式Ｃにおいて、Ｒ1は水素、Ｒ2はプロピル、Ｒ3は水素、Ｒ4は水素である）。また、式Ａが５５モル％、式Ｂが４５モル％のポリビニルアセタールを用いて試験を行おうとしたところ、ポリビニルアセタールが処理液に溶解しなかった（比較例９） Example 1 and Example 2 were performed by changing the proportion of the subunit of the formula A of polyvinyl acetal and PVA to obtain Examples 14 to 18 (in the formulas A to C in the table below, R 1 is hydrogen, R 2 is propyl, R 3 is hydrogen, and R 4 is hydrogen). Moreover, when it tried to test using the polyvinyl acetal whose Formula A is 55 mol% and Formula B is 45 mol%, polyvinyl acetal did not melt | dissolve in a process liquid (comparative example 9).
実施例１で仕上げ剤のリン酸クロム（ＩＩＩ）をリン酸コバルト、リン酸亜鉛、リン酸アルミニウムに変更して試験を行った。 In Example 1, the finish was changed to chromium (III) phosphate as cobalt phosphate, zinc phosphate, and aluminum phosphate.
実施例１の仕上げ剤条件で、処理対象となる化成皮膜を変化させて耐キズ性、撥水性試験、締結試験を行った。なお、バナジウム化成皮膜はメタバナジン酸カリウム２ｇ／Ｌ、硫酸セリウム１０ｇ／Ｌ、硝酸リチウム２０ｇ／Ｌの水溶液に４０℃、ｐＨ３．０で６０秒浸漬させて形成した。リン酸塩皮膜は市販のプレパレンＺ（日本パーカライジング（株））にて表面調整後、７０℃に加温した市販のリン酸塩皮膜処理液（パルボンド３３００：日本パーカライジング（株））に１５秒間浸漬し皮膜生成を行った。また、実施例２２〜２５の評価は実施例１の仕上げ剤から水溶性ポリマーを除いた比較例４の仕上げ剤を用いた場合との相対評価である。 Under the finishing agent conditions of Example 1, the chemical conversion film to be treated was changed to perform scratch resistance, water repellency test, and fastening test. The vanadium chemical conversion film was formed by immersing in an aqueous solution of potassium metavanadate 2 g / L, cerium sulfate 10 g / L, and lithium nitrate 20 g / L at 40 ° C. and pH 3.0 for 60 seconds. The phosphate film was immersed in a commercially available phosphate film treatment solution (Palbond 3300: Nippon Parkerizing Co., Ltd.) heated to 70 ° C. after surface adjustment with a commercially available Preparene Z (Nihon Parkerizing Co., Ltd.). A film was formed. Moreover, evaluation of Examples 22-25 is relative evaluation with the case where the finishing agent of the comparative example 4 remove | excluding the water-soluble polymer from the finishing agent of Example 1 was used.
実施例１、２と比較例１、２の比較により、ポリビニルアセタール及びポリビニルアルコールは仕上げ剤に添加することで仕上げ剤の性能を向上させるが、単独で使用しても何の効果ももたらさないことが分かる。 According to the comparison between Examples 1 and 2 and Comparative Examples 1 and 2, polyvinyl acetal and polyvinyl alcohol improve the performance of the finish by adding them to the finish, but they do not have any effect when used alone. I understand.
実施例３、４により、ポリビニルアセタール及びポリビニルアルコールの効果は下地のめっきおよび仕上げ剤の種類にかかわらないことが分かる。 From Examples 3 and 4, it can be seen that the effects of polyvinyl acetal and polyvinyl alcohol do not depend on the type of base plating and finish.
実施例１、２と比較例３の比較により、塗料は精密さを要求される部材においては膜厚の問題で使用できないことが分かる。 From the comparison between Examples 1 and 2 and Comparative Example 3, it can be seen that the paint cannot be used in a member requiring precision because of the problem of film thickness.
実施例１、２と比較例４の比較により、ポリビニルアセタール及びポリビニルアルコールを添加しない場合、添加した場合より耐傷性、外観などが劣ることが分かる。 From the comparison between Examples 1 and 2 and Comparative Example 4, it can be seen that when polyvinyl acetal and polyvinyl alcohol are not added, scratch resistance, appearance, and the like are inferior to those when added.
実施例１、２と比較例５の比較により、従来のアクリル酸系ポリマーとポリビニルアセタール及びポリビニルアルコールを比較した場合に耐傷性、経時変化の面で問題があることが分かる。 Comparison between Examples 1 and 2 and Comparative Example 5 shows that there is a problem in terms of scratch resistance and change with time when a conventional acrylic acid polymer is compared with polyvinyl acetal and polyvinyl alcohol.
実施例１、２と比較例６、７の比較により、水溶性有機ポリマー単独の皮膜を水溶性有機ポリマー高濃度の仕上げ液を用いることで形成しようとした場合、わずかに皮膜が形成し、耐傷性が向上するが、それ以外の機能は向上しないことが分かる。 According to a comparison between Examples 1 and 2 and Comparative Examples 6 and 7, when a film of a water-soluble organic polymer alone was to be formed by using a high-concentration water-soluble organic polymer finishing solution, a film was slightly formed and scratch resistance was obtained. It can be seen that the other functions are not improved.
実施例４と比較例８の比較により、無機系トップコートにおいても水溶性有機ポリマーの添加で耐傷性が向上していることが分かる。 Comparison between Example 4 and Comparative Example 8 shows that the scratch resistance is improved by adding a water-soluble organic polymer even in an inorganic topcoat.
実施例５〜１３は仕上げ剤の組成変化である。添加剤並びに水溶性有機ポリマーが好ましい濃度範囲内であれば、いずれも水溶性有機ポリマーの効果が発揮されていることが分かる。 Examples 5 to 13 are composition changes of the finishing agent. It can be seen that the effects of the water-soluble organic polymer are exhibited as long as the additive and the water-soluble organic polymer are in the preferred concentration range.
実施例１４〜１８は、水溶性ポリマー中の式Ａのサブユニットの割合を変化させている。前記割合が好ましい範囲内であれば、いずれも水溶性有機ポリマーの効果が発揮されていることが分かる。 Examples 14-18 vary the proportion of subunits of formula A in the water-soluble polymer. If the said ratio is in a preferable range, it turns out that the effect of a water-soluble organic polymer is exhibited in any case.
実施例１９〜２１では、仕上げ剤の金属を変更した実施例である。仕上げ剤に添加する金属が、クロムに限らず、他の金属であっても同様の効果が得られることが分かる。 Examples 19 to 21 are examples in which the metal of the finishing agent was changed. It turns out that the same effect is acquired even if the metal added to a finishing agent is not restricted to chromium but another metal.
実施例２２〜２５では、化成皮膜の組成を変更した実施例である。三価クロム化成皮膜に限らず他の基材や皮膜であっても同様の効果が得られることが分かる。 Examples 22 to 25 are examples in which the composition of the chemical conversion film was changed. It turns out that the same effect is acquired even if it is not only a trivalent chromium chemical conversion film but other base materials and films.
Claims (8)
前記水溶性有機ポリマーがさらに以下の式Ｂ及び／又は式Ｃの単位を含むポリマーであり、
該添加剤がＣｒ、Ｃｏ、Ｆｅ、Ｎｉ、Ｚｎ、Ｙ、Ｌａ、Ｍｏ、Ｗ、Ｔｉ、Ａｌ、Ｚｒ、Ｍｎ、Ｖより選択される１種以上の金属のイオン、リンの酸素酸、珪酸化合物より選択される１種以上含む添加剤である水溶液。 An aqueous solution containing a water-soluble organic polymer containing a hydroxyl group and one or more additives, and forming a film on the surface of the substrate by dipping, wherein the water-soluble organic polymer contains 60 mol% of the following unit of formula A: It is a polymer contained in the above proportion,
The water-soluble organic polymer is a polymer further comprising units of the following formula B and / or formula C:
The additive is one or more metal ions selected from Cr, Co, Fe, Ni, Zn, Y, La, Mo, W, Ti, Al, Zr, Mn, and V, phosphorus oxyacid, and silicate compound An aqueous solution which is an additive containing one or more selected from the above.
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