JP6855063B2 - White aluminum molded product, its manufacturing method, and white coloring composition - Google Patents
White aluminum molded product, its manufacturing method, and white coloring composition Download PDFInfo
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- JP6855063B2 JP6855063B2 JP2017117936A JP2017117936A JP6855063B2 JP 6855063 B2 JP6855063 B2 JP 6855063B2 JP 2017117936 A JP2017117936 A JP 2017117936A JP 2017117936 A JP2017117936 A JP 2017117936A JP 6855063 B2 JP6855063 B2 JP 6855063B2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 81
- 229910052782 aluminium Inorganic materials 0.000 title claims description 80
- 238000004040 coloring Methods 0.000 title claims description 43
- 239000000203 mixture Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000011148 porous material Substances 0.000 claims description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 42
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- 238000007743 anodising Methods 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 125000000129 anionic group Chemical group 0.000 claims description 10
- AIABEETXTKSDLE-UHFFFAOYSA-J 2,3-dihydroxybutanedioate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O AIABEETXTKSDLE-UHFFFAOYSA-J 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- -1 amino compound Chemical class 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZWNZGTHTOBNSDL-UHFFFAOYSA-N N.[Ti+4] Chemical compound N.[Ti+4] ZWNZGTHTOBNSDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- ZFXIRKKWRLMMNA-UHFFFAOYSA-L O=[Ti+2].C(C(=O)[O-])(=O)[O-].C(C(=O)O)(=O)[O-].[NH4+] Chemical group O=[Ti+2].C(C(=O)[O-])(=O)[O-].C(C(=O)O)(=O)[O-].[NH4+] ZFXIRKKWRLMMNA-UHFFFAOYSA-L 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FOUZISDNESEYLX-UHFFFAOYSA-N 2-(2-hydroxyethylazaniumyl)acetate Chemical compound OCCNCC(O)=O FOUZISDNESEYLX-UHFFFAOYSA-N 0.000 claims description 3
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 claims description 3
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 claims description 3
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims description 3
- MSYNCHLYGJCFFY-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;titanium(4+) Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O MSYNCHLYGJCFFY-UHFFFAOYSA-B 0.000 claims description 3
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 claims description 3
- ASMBPKXBMUUOFX-UHFFFAOYSA-L CC(C([O-])=O)O.CC(C([O-])=O)O.N.[Ti+4] Chemical compound CC(C([O-])=O)O.CC(C([O-])=O)O.N.[Ti+4] ASMBPKXBMUUOFX-UHFFFAOYSA-L 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical group OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 claims description 3
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004473 Threonine Substances 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 125000002349 hydroxyamino group Chemical group [H]ON([H])[*] 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 229940049920 malate Drugs 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- CYZVXAGZWYPHNJ-UHFFFAOYSA-J tetrapotassium oxalate Chemical compound C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].[K+].[K+].[K+].[K+] CYZVXAGZWYPHNJ-UHFFFAOYSA-J 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- GVQVOUBMSBBCNX-UHFFFAOYSA-N [Na+].[Ti+4] Chemical compound [Na+].[Ti+4] GVQVOUBMSBBCNX-UHFFFAOYSA-N 0.000 claims description 2
- UIEPWBNVIDPGBV-UHFFFAOYSA-N potassium titanium(4+) Chemical compound [K+].[Ti+4] UIEPWBNVIDPGBV-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 239000000049 pigment Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 15
- 239000004408 titanium dioxide Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 239000010407 anodic oxide Substances 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000001962 electrophoresis Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002048 anodisation reaction Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018131 Al-Mn Inorganic materials 0.000 description 1
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- 229910018464 Al—Mg—Si Inorganic materials 0.000 description 1
- 229910018461 Al—Mn Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- ISMLDHVWKDAZAH-UHFFFAOYSA-J azanium 2-hydroxypropanoate titanium(4+) Chemical compound [NH4+].[Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O ISMLDHVWKDAZAH-UHFFFAOYSA-J 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Description
本発明は白色アルミニウム成形体、その製造方法、及び白色着色用組成物に関する。 The present invention relates to a white aluminum molded product, a method for producing the same, and a composition for coloring white.
アルミニウム成形体自体は、金属アルミニウムに由来する金属光沢を有しており、このような成形体を着色された用途に使用する際には、必要により周知の表面処理を行った上で、黒、赤、白等の目的とする任意の色の着色塗料を用いて塗装していた。
上記の塗装とは別に、アルミニウム成形体表面を例えば硫酸法やシュウ酸法によって陽極酸化処理したのち、表面に形成された微細な細孔に任意の染料を含浸させたり、顔料を充填したり、あるいはニッケル等を電解析出させて、電解着色させる方法も広く知られている。しかしながら、これらの方法、特に電解着色法によれば、限定された色彩のものしか得られない。
また電気泳動によって、アルミニウム成形体表面に形成された細孔中に顔料を入れて着色する方法によれば、細孔の径を顔料が入る程度に大きくする必要があり、かつ顔料の径を小さくすることが必要であった。しかし、この方法によっても安定して均一に着色させることが困難であり、かつ細孔に入れることができる顔料の量にも限界があったので濃色に着色させることも困難であった。
The aluminum molded body itself has a metallic luster derived from metallic aluminum, and when such a molded body is used for a colored application, it is required to be subjected to a well-known surface treatment and then black. It was painted with a colored paint of any color of interest such as red and white.
Apart from the above coating, the surface of the aluminum molded body is anodized by, for example, a sulfuric acid method or an oxalic acid method, and then the fine pores formed on the surface are impregnated with an arbitrary dye or filled with a pigment. Alternatively, a method of electrolytically precipitating nickel or the like to electrocolor it is also widely known. However, according to these methods, especially the electrolytic coloring method, only limited colors can be obtained.
Further, according to the method of coloring by putting a pigment in the pores formed on the surface of the aluminum molded product by electrophoresis, it is necessary to increase the diameter of the pores to the extent that the pigment can enter, and to reduce the diameter of the pigment. It was necessary to do. However, even with this method, it is difficult to color the pigment stably and uniformly, and since there is a limit to the amount of pigment that can be put into the pores, it is also difficult to color the color deeply.
また、着色方法ではないが、特許文献１に記載されているように、アルミニウム成形体表面を予め陽極酸化皮膜処理した後、硫酸チタニル等と、陽イオンを形成する錯化剤とを含む混合液中で、電解処理して、陽極酸化皮膜の表面及び孔内面に二酸化チタンを析出させて二酸化チタン含有皮膜を形成するチタニル電解処理工程と、二酸化チタン皮膜を焼成して光触媒能を有する二酸化チタンからなる光触媒皮膜に変化させる焼成処理工程とを有する、陽極酸化皮膜の表面及び孔内面に二酸化チタンからなる光触媒皮膜を形成させる方法が知られている。 Further, although it is not a coloring method, as described in Patent Document 1, a mixed solution containing titanium sulfate or the like and a complexing agent for forming cations after the surface of the aluminum molded body is treated with an anodic oxide film in advance. In the titanyl electrolysis step of electrolyzing to form a titanium dioxide-containing film by precipitating titanium dioxide on the surface and inner surface of the pores of the anodized film, and from titanium dioxide having photocatalytic activity by firing the titanium dioxide film. There is known a method of forming a photocatalyst film made of titanium dioxide on the surface of the anodized film and the inner surface of the pores, which has a firing treatment step of changing the photocatalyst film.
さらに特許文献２には、アルミニウム又はアルミニウム合金からなり、細孔内ではない基材表面に形成した陽極酸化皮膜上に、光触媒作用を有する平均粒径１ｎｍ〜１０００ｎｍの酸化チタン等の半導体微粒子が凝集して堆積してなる光触媒膜がコーティングされてなることを特徴とするアルミニウム又はアルミニウム合金材であり、陽極酸化皮膜に形成された細孔内に酸化チタン等が吸着されない皮膜が記載されている。 Further, in Patent Document 2, semiconductor fine particles such as titanium oxide having an average particle size of 1 nm to 1000 nm having a photocatalytic action are aggregated on an anodized film made of aluminum or an aluminum alloy and formed on the surface of a base material which is not in the pores. It is an aluminum or aluminum alloy material characterized by being coated with a photocatalyst film formed by depositing the photocatalyst film, and describes a film in which titanium oxide or the like is not adsorbed in the pores formed in the anodized film.
特許文献３には、高電圧で陽極酸化したアルミニウム材に対し、金属塩溶液中にて交流電圧を印加して電解着色を行うこと、特許文献４には、陽極酸化皮膜を形成したアルミニウム材を希アルカリ水溶液によりエッチング処理して陽極酸化皮膜の細孔底部のバリヤ層の露出部表面を化学的に溶解した後、顔料粒子又は金属塩を含む電解着色浴中で電解着色、電気泳動して着色することが記載されている。
さらに特許文献５及び６は、アルミニウム等の部材表面を陽極酸化処理して表面に細孔を形成させた後に、チタン錯体溶液中の存在下において、該部材を浸漬し、さらに電解プロセスにて電解処理することによって、該細孔内にて酸化チタン粒子を形成させることが記載されている。
In Patent Document 3, an aluminum material anodized at a high voltage is electrolytically colored by applying an AC voltage in a metal salt solution, and in Patent Document 4, an aluminum material having an anodized film formed is used. After etching with a dilute alkaline aqueous solution to chemically dissolve the exposed surface of the barrier layer at the bottom of the pores of the anodic oxide film, it is electrolytically colored in an electrolytic coloring bath containing pigment particles or metal salts, and then electrolyzed and colored. It is stated that it should be done.
Further, in Patent Documents 5 and 6, after the surface of a member such as aluminum is anodized to form pores on the surface, the member is immersed in the presence of a titanium complex solution and further electrolyzed by an electrolysis process. It is described that the treatment causes titanium oxide particles to be formed in the pores.
従来技術においては、アルミニウム成形体表面を着色するために塗料を塗布していたので、アルミニウム成形体の使用を継続するにつれて、その白色塗膜が剥がれる等して、美観を損ねることがあった。
また陽極酸化皮膜の細孔に電気泳動によって顔料を充填させる方法によると、該顔料が着色力を発揮できる程度の量が充填されるように、該細孔の径を大きくしなければならない。そうするとアルミニウム成形体の表面に粗さが生じ、美観を損ねかねない可能性があった。
さらに、このようにして得られた着色皮膜は緻密な皮膜ではなく、細孔の径が大きいことにより、酸化チタンを充填する以前において、既に細孔による光の反射によってアルミニウム成形体はある程度の光干渉性を有し、透明性のある白色を呈している。そのため、不透明な白色皮膜は得られない。
また、電気泳動により安定した濃色の着色を行うときには、電気泳動時の浴電流が小さいので、顔料が細孔内ではなく細孔外の表面に過剰に析出する傾向があった。また、電析により白色皮膜による着色を行う際には、その条件を正確に制御しないとスポーリングという白色皮膜の破壊が発生する恐れがあった。また、そのために電析時に印加する電圧を高くすることができず、目的とする色にまで濃くすることができなかった。
In the prior art, since the paint was applied to color the surface of the aluminum molded product, the white coating film may be peeled off as the use of the aluminum molded product is continued, which may spoil the aesthetic appearance.
Further, according to the method of filling the pores of the anodized film with a pigment by electrophoresis, the diameter of the pores must be increased so that the pigment is filled in an amount sufficient to exhibit coloring power. Then, the surface of the aluminum molded product becomes rough, which may spoil the aesthetic appearance.
Further, the colored film thus obtained is not a dense film, and the diameter of the pores is large, so that the aluminum molded body has a certain amount of light due to the reflection of light by the pores before the titanium oxide is filled. It has coherence and has a transparent white color. Therefore, an opaque white film cannot be obtained.
Further, when stable dark coloring is performed by electrophoresis, the bath current during electrophoresis tends to be small, so that the pigment tends to be excessively deposited on the surface outside the pores instead of inside the pores. Further, when coloring with a white film by electrodeposition, if the conditions are not accurately controlled, there is a risk that the white film may be destroyed called spalling. Further, for that reason, the voltage applied at the time of electrodeposition could not be increased, and the desired color could not be darkened.
また上記特許文献１に記載されたような、陽極酸化皮膜の表面及び孔内面に二酸化チタンを析出させて二酸化チタン皮膜を形成するチタニル電解処理工程と、その二酸化チタン皮膜を焼成する工程を有する方法によると、十分な量の光触媒用二酸化チタンを析出させることが困難であると共に、比較的耐熱性に劣るアルミニウム成形体を高温に加熱するので、その成形体が変形、または物性が変質する可能性があった。
特許文献２に記載の方法は、陽極酸化処理済みのアルミニウム板を酸化チタンゾル中に浸漬し、電気泳動を行うことによって、アルミニウム板表面に形成された細孔内ではなく、表面上に酸化チタン粒子を析出させることにより、光触媒を担持させる方法であるが、担持される酸化チタンは光触媒用であり、かつ細孔内ではなく、かつ細孔内における担持量も少ないものであった。
特許文献３に記載の方法は陽極酸化皮膜を設けたアルミニウム材表面を、金属塩溶液中にて交流電圧を印加して着色させる方法ではあるが、陽極酸化処理は１回のみであるし、かつ細孔内に金属化合物を析出させることまでを示唆していない。
さらに特許文献４には陽極酸化処理皮膜により形成された細孔内に顔料を充填させる方法が記載されているものの、顔料の充填に先立ち、陽極酸化処理皮膜をエッチングして、バリヤ層を溶解させる工程を備えるのであり、このエッチング工程は当然ながら細孔内のバリヤ層のみを溶解させることはできず、陽極酸化処理皮膜全体をもエッチングさせることが明らかである。その結果、陽極酸化処理皮膜全体に対して凹凸表面を形成させることになり、仮に着色できたとしても、アルミニウム板としては凹凸のある不均一な表面を形成させるに留まる。
加えて、一旦形成した陽極酸化処理皮膜をエッチングすることにより、この陽極酸化処理皮膜が消失する。そのため、細孔は存在するものの、細孔内は陽極酸化処理皮膜によって保護されない状態となり、アルミニウム材を使用するにつれて細孔内やアルミニウム材表面が腐食することになる。
また電析処理の条件によっては、より大電流を発生させる電源装置を必要とするので、必要とする設備がより大規模のものとなる。
よって本発明は陽極酸化により形成された細孔に、スポーリングを起こすことなく、二酸化チタン等の顔料粒子を充填して、不透明で十分な着色皮膜を有しながら、当初の形状を維持し、陽極酸化処理皮膜による本来の物性を備えたアルミニウム成形体を得ること、及びそのために必要な電源設備をより小さいものとすることにある。
Further, a method having a titanyl electrolysis step of forming a titanium dioxide film by precipitating titanium dioxide on the surface and the inner surface of the pores of the anodized film and a step of firing the titanium dioxide film as described in Patent Document 1. According to the report, it is difficult to deposit a sufficient amount of titanium dioxide for photocatalyst, and an aluminum molded product having relatively inferior heat resistance is heated to a high temperature, so that the molded product may be deformed or its physical properties may be altered. was there.
In the method described in Patent Document 2, an anodized aluminum plate is immersed in a titanium oxide sol and electrophoresed, so that titanium oxide particles are formed on the surface of the aluminum plate, not in the pores. This is a method of supporting a photocatalyst by precipitating the above, but the titanium oxide to be supported is for a photocatalyst, and the amount of titanium oxide supported is small not in the pores and in the pores.
The method described in Patent Document 3 is a method of coloring the surface of an aluminum material provided with an anodic oxide film by applying an AC voltage in a metal salt solution, but the anodic oxidation treatment is performed only once and It does not suggest that a metal compound is precipitated in the pores.
Further, although Patent Document 4 describes a method of filling the pores formed by the anodized film with a pigment, the anodized film is etched to dissolve the barrier layer prior to filling the pigment. It is clear that this etching step cannot dissolve only the barrier layer in the pores, and also etches the entire anodized film. As a result, an uneven surface is formed on the entire anodized film, and even if coloring is possible, the aluminum plate only forms an uneven and non-uniform surface.
In addition, the anodized film disappears by etching the once formed anodized film. Therefore, although the pores are present, the inside of the pores is not protected by the anodizing film, and the inside of the pores and the surface of the aluminum material are corroded as the aluminum material is used.
Further, depending on the conditions of the electrodeposition treatment, a power supply device that generates a larger current is required, so that the required equipment becomes larger.
Therefore, in the present invention, the pores formed by anodization are filled with pigment particles such as titanium dioxide without causing spalling, and the original shape is maintained while having an opaque and sufficient colored film. The purpose is to obtain an aluminum molded body having the original physical properties of the anodized film, and to make the power supply equipment required for that purpose smaller.
さらに特許文献５及び６に記載の発明は、細孔内の底部にまで多くの酸化チタン粒子を析出させることを目的としており、そのために電解処理を必要とする。
しかしながら、実際には、細孔内の底部にまで酸化チタン粒子を析出させなくても、十分な白色を得ることができる。しかも電解処理をするための装置等を必要とし、その電解時においてアルミニウム成形体表面の荷電状態が均一ではなく、例えば成形体の縁や角等がより荷電されて、結果的に白色の着色にムラが生じる恐れがある。
Further, the inventions described in Patent Documents 5 and 6 aim to deposit a large number of titanium oxide particles up to the bottom of the pores, and therefore require an electrolytic treatment.
However, in reality, sufficient white color can be obtained without precipitating titanium oxide particles to the bottom of the pores. Moreover, a device or the like for electrolyzing is required, and the charged state of the surface of the aluminum molded body is not uniform at the time of electrolysis, for example, the edges and corners of the molded body are more charged, resulting in white coloring. There is a risk of unevenness.
本発明者らは、上記課題を解決すべく鋭意検討を行った結果、下記の白色アルミニウム成形体、その製造方法、及び白色着色用組成物を発明した。
１．アルミニウム成形体表面に陽極酸化処理により形成された細孔中に酸化チタン粒子を付着させてなる白色アルミニウム成形体。
２．ａ．アルミニウム成形体を陽極酸化処理する工程、
ｂ．陽極酸化処理されたアルミニウム成形体をチタン（IV）錯体を含有する白色着色用組成物中に浸漬する工程。
のａ及びｂ工程を有する白色アルミニウム成形体の製造方法。
３．陰イオン性のチタン（IV）錯体を含有する、陽極酸化処理により表面に細孔が形成されたアルミニウム成形体の該細孔内に酸化チタン粒子を付着させるためのアルミニウム成形体の白色着色用組成物。
４．陰イオン性のチタン（IV）錯体の配位子が、カルボン酸、ヒドロキシカルボン酸、硫酸根、ヒドロキシアミノ酸、アミノ酸及びアミノ系化合物から選ばれた１種以上である３に記載の白色着色用組成物。
５．カルボン酸がしゅう酸であり、ヒドロキシカルボン酸が乳酸、クエン酸、グリコール酸、サリチル酸、酒石酸及びリンゴ酸である４に記載の白色着色用組成物。
６．陰イオン性のチタン（IV）錯体が、ビス（オキサラト）オキソチタン（IV）酸アンモニウム、ビス（オキサラト）オキソチタン（IV）酸カリウム、ビス（オキサラト）ペルオキソチタン（IV）酸カリウム、ビス（オキサラト）ペルオキソチタン（IV）酸アンモニウム、チタン（IV）ラクテート、チタン（IV）ビスラクテートアンモニウム、クエン酸チタン（IV）錯体、ペルオキソクエン酸チタン（IV）アンモニウム、ペルオキソグリコール酸チタン（IV）アンモニウム、トリス（サリチラト）チタン（IV）酸ナトリウム、トリス（サリチラト）チタン（IV）酸アンモニウム、酒石酸チタン（IV）錯体、リンゴ酸チタン（IV）錯体、ペルオキソビス（スルファト）チタン（IV）酸カリウム、ペルオキソビス（スルファト）チタン（IV）酸アンモニウム、オキソビス（スルファト）チタン（IV）酸ナトリウム、オキソビス（スルファト）チタン（IV）酸カリウム、オキソビス（スルファト）チタン（IV）酸アンモニウム、から選ばれた１種以上である４に記載の白色着色用組成物。
７．セリン及び／又はトレオニンを配位子とする４に記載の白色着色用組成物。
８．陰イオン性のチタン（IV）錯体が、（２−ヒドロキシエチル）イミノ二酢酸、ジ（２−ヒドロキシエチル）グリシン、ジアミン系の１，３−プロパンジアミン四酢酸、（２−ヒドロキシエチル）エチレンジアミン三酢酸、１，２−ジアミノプロパン四酢酸、trans−１，２−シクロヘキサンジアミン四酢酸、から選ばれた１種以上である４に記載の白色着色用組成物。
As a result of diligent studies to solve the above problems, the present inventors have invented the following white aluminum molded product, a method for producing the same, and a composition for white coloring.
1. 1. A white aluminum molded body formed by adhering titanium oxide particles into pores formed by anodizing the surface of the aluminum molded body.
2. a. The process of anodizing an aluminum molded product,
b. A step of immersing an anodized aluminum molded article in a white coloring composition containing a titanium (IV) complex.
A method for producing a white aluminum molded product having the steps a and b.
3. 3. Composition for white coloring of an aluminum molded body containing anionic titanium (IV) complex and having pores formed on the surface by anodization treatment for adhering titanium oxide particles into the pores. Stuff.
4. 3. The composition for white coloring according to 3, wherein the ligand of the anionic titanium (IV) complex is at least one selected from carboxylic acid, hydroxycarboxylic acid, sulfate root, hydroxyamino acid, amino acid and amino compound. Stuff.
5. 4. The composition for white coloring according to 4, wherein the carboxylic acid is oxalic acid and the hydroxycarboxylic acid is lactic acid, citric acid, glycolic acid, salicylic acid, tartaric acid and malic acid.
6. The anionic titanium (IV) complex is ammonium bis (oxalate) oxotitanium (IV) acid, potassium bis (oxalate) oxotitanium (IV) acid, potassium bis (oxalate) peroxotitanium (IV) acid, bis (oxalate) peroxo. Ammonium Titanium (IV), Titanium (IV) Lactate, Titanium (IV) Bislactate Ammonium, Titanium Citrate (IV) Complex, Titanium Peroxocitrate (IV) Ammonium, Titanium Peroxoglycolate (IV) Ammonium, Tris (Salichirato) ) Sodium titanium (IV) acid, Tris (salicyrat) titanium (IV) ammonium acid, Titanium tartrate (IV) complex, Titanium malate (IV) complex, Peroxobis (sulfato) Titanium (IV) potassium, Peroxobis (sulfato) ) Ammonium (IV) Titanium (IV), Sodium Oxobis (Sulfato) Titanium (IV), Potassium Oxobis (Sulfato) Titanium (IV), Ammonium Oxobis (Sulfato) Titanium (IV) The white coloring composition according to 4.
7. 4. The composition for white coloring according to 4, wherein serine and / or threonine is used as a ligand.
8. The anionic titanium (IV) complex is (2-hydroxyethyl) iminodiacetic acid, di (2-hydroxyethyl) glycine, diamine-based 1,3-propanediaminetetraacetic acid, (2-hydroxyethyl) ethylenediaminetria. The white coloring composition according to 4, which is at least one selected from acetic acid, 1,2-diaminopropanetetraacetic acid, and trans-1,2-cyclohexanediaminetetraacetic acid.
従来の塗装方法によるものと比較して、本発明によれば陽極酸化皮膜が剥離しない限り、着色皮膜が脱落することがない。加えて陽極酸化皮膜の細孔内に酸化チタン粒子を入れてなる着色されたアルミニウム成形体において、電解処理をせずに酸化チタンを析出させるので、電解処理の条件を設定させる必要がない。電解処理によりアルミニウム成形体表面の荷電状態のムラを考慮する必要がなく、着色ムラの発生を防止できる。 According to the present invention, the colored film does not come off unless the anodized film is peeled off, as compared with the conventional coating method. In addition, in a colored aluminum molded body in which titanium oxide particles are placed in the pores of the anodized film, titanium oxide is precipitated without electrolytic treatment, so that it is not necessary to set the conditions for electrolytic treatment. By the electrolytic treatment, it is not necessary to consider the unevenness of the charged state on the surface of the aluminum molded body, and the occurrence of uneven coloring can be prevented.
本発明は、アルミニウム成形体表面の陽極酸化皮膜に形成された細孔内の特に細孔の開口部付近から中程にかけて、顔料粒子を付着させてなる白色アルミニウム成形体である。また、その白色アルミニウム成形体を得る方法、及びその方法に使用する白色着色用組成物である。そして、より粒子径が小さい、例えば本来は一次粒子が小さいために白色を呈さない酸化チタン等の粒子であっても、その白色着色用組成物を使用して、かつ電解処理を併用することなく、細孔内でこの溶液から顔料を析出させることにより、外部から入射した光がその凝集粒子を構成する酸化チタン粒子間にて乱反射するなどして不透明性が高くなることで、凝集した酸化チタン粒子が白色を呈して、結果的に陽極酸化皮膜が白色を呈することができる。
本発明における白色アルミニウム成形体の白色とは、Ｌ＊値が７０．００以上であり、好ましくは７５．００以上、より好ましくは、８０．００以上である。７０．００未満であると表面の色が白色とはいえない。
また、好ましくはａ＊及び／又はｂ＊を、−５．０〜＋５．０、さらに好ましくは−２．５〜＋２．５、より好ましくは−１．０〜＋１．０の範囲内であると良い。
The present invention is a white aluminum molded product in which pigment particles are adhered to the pores formed on the anodized film on the surface of the aluminum molded product, particularly from the vicinity of the opening of the pores to the middle. Further, it is a method for obtaining the white aluminum molded product, and a white coloring composition used in the method. Then, even if the particles have a smaller particle size, for example, titanium oxide or the like that does not exhibit white because the primary particles are originally small, the white coloring composition is used and the electrolytic treatment is not used in combination. By precipitating the pigment from this solution in the pores, the light incident from the outside is diffusely reflected between the titanium oxide particles constituting the aggregated particles, and the opacity becomes high, so that the aggregated titanium oxide The particles can be white, and as a result, the anodic oxide film can be white.
The white color of the white aluminum molded product in the present invention has an L * value of 70.00 or more, preferably 75.00 or more, and more preferably 80.00 or more. If it is less than 70.00, the surface color cannot be said to be white.
Further, a * and / or b * are preferably in the range of −5.0 to +5.0, more preferably −2.5 to +2.5, and more preferably −1.0 to +1.0. Is good.
本発明における陽極酸化処理は、下記のアルミニウム材料からなる成形体に対してなされる。
（白色アルミニウム成形体のアルミニウム材料）
本発明の白色アルミニウム成形体を構成するアルミニウム材料は、アルミニウムのみからなる材料でも良いが、一般にアルミニウム合金といわれる材料（例えば、Ａｌ−Ｍｎ系合金、Ａｌ−Ｍｇ系合金、Ａｌ-Ｃｕ系合金、Ａｌ−Ｍｇ−Ｓｉ系合金等）であっても良く、陽極酸化処理されて細孔が形成される材料であればよい。またアルミニウム材料自体が他の金属と合金とされることにより、すでに着色された材料であっても良い。
どのようなアルミニウム材料を採用するかは、本発明のアルミニウム成形体の用途によって決められるものである。
なお、陽極酸化処理を行う前に、必要に応じてアルミニウム成形体を１０％程度の硝酸水溶液（室温）に浸漬、水洗、６．５％水酸化ナトリウム水溶液（３０〜５０℃程度）に浸漬、水洗、１０％硝酸水溶液（室温）に浸漬、水洗を順に行って表面を清浄化させておくこともできる。
The anodizing treatment in the present invention is performed on a molded product made of the following aluminum material.
(Aluminum material of white aluminum molded product)
The aluminum material constituting the white aluminum molded body of the present invention may be a material consisting only of aluminum, but a material generally called an aluminum alloy (for example, Al-Mn-based alloy, Al-Mg-based alloy, Al-Cu-based alloy, etc. It may be an Al-Mg-Si based alloy or the like), and may be any material as long as it is anodized to form pores. Further, the aluminum material itself may be an already colored material by being alloyed with another metal.
What kind of aluminum material is adopted is determined by the use of the aluminum molded product of the present invention.
Before performing the anodization treatment, if necessary, the aluminum molded body is immersed in a nitric acid aqueous solution (room temperature) of about 10%, washed with water, and immersed in a 6.5% aqueous sodium hydroxide solution (about 30 to 50 ° C.). The surface can be cleaned by washing with water, immersing in a 10% aqueous nitric acid solution (room temperature), and washing with water in order.
[アルミニウム成形体を陽極酸化処理する工程]
本発明のアルミニウム成形体を得るために行う陽極酸化処理は、一般にアルミニウム成形体表面に形成されて表面に耐食性及び装飾性を付与するために行う処理と同様であり、陽極酸化皮膜に細孔を形成できる処理であることが必要である。
アルミニウム成形体を、陽極酸化処理装置のアノードに電気的に接触させて該アノードおよびカソードとともに電解液中に浸漬させ、前記アノードとカソードとの間で通電させることにより前記アルミニウム成形体に陽極酸化皮膜を形成する。
このときに使用される電解液としては、硫酸、マレイン酸、マロン酸、シュウ酸などからなる電解液が用いられるが、汎用性のある硫酸が特に好ましい。しかし、これらに限定されるものではない。
陽極酸化は、その条件として、上記酸の濃度を５〜２０重量％とした浴中にアルミニウム成形体を浸漬し、電流密度を一定に維持して処理を行う。このときの電流密度としては０．５〜３．０Ａ／ｄｍ２の定電流とすることが好ましく、このような処理を２０〜５０分間行うことが好ましい。しかし、これらの条件も限定されるものではなく、皮膜生成が可能な条件であればよい。
生成する細孔は、アルミニウム成形体の表面に形成された陽極酸化皮膜の深さ方向に延びた長い柱状の空間である細孔として形成される。ただし、アルミニウム成形体表面に対して、直角に形成されるとは限らず、実際には屈曲、枝分かれなど不規則な形状を示す。その開口部の径は、陽極酸化条件により任意に調整することが可能であるが、本発明においてこの工程により生成する陽極酸化皮膜の細孔は、その開口部の径が５〜３００ｎｍであり、好ましくは５〜５０ｎｍであり、より好ましくは８〜５０ｎｍである。３００ｎｍよりも大きいと陽極酸化皮膜を均一な皮膜とすることが困難であり、５ｎｍ未満の多孔質皮膜は得られにくい。
また細孔の長さ、及び陽極酸化皮膜の膜厚は、特に限定されないが、顔料により十分に着色されるに必要な量の顔料を析出させるためには、アルミニウム表面から厚さ方向に向けて５〜５０μｍであり、好ましくは８〜３０μｍである。
陽極酸化処理の後には、アルミニウム成形体を十分に水洗しておく。
[Process of anodizing aluminum molded product]
The anodizing treatment performed to obtain the aluminum molded product of the present invention is generally the same as the treatment performed to impart corrosion resistance and decorativeness to the surface of the aluminum molded product, and pores are formed in the anodized film. It needs to be a process that can be formed.
The aluminum molded body is electrically contacted with the anode of the anodic oxidation treatment apparatus, immersed in the electrolytic solution together with the anode and the cathode, and energized between the anode and the cathode to form an anodic oxide film on the aluminum molded body. To form.
As the electrolytic solution used at this time, an electrolytic solution composed of sulfuric acid, maleic acid, malonic acid, oxalic acid and the like is used, but general-purpose sulfuric acid is particularly preferable. However, it is not limited to these.
As a condition for the anodic oxidation, the aluminum molded product is immersed in a bath having an acid concentration of 5 to 20% by weight to maintain a constant current density. The current density at this time is preferably a constant current of 0.5 to 3.0 A / dm 2 , and such processing is preferably performed for 20 to 50 minutes. However, these conditions are not limited as long as they can form a film.
The generated pores are formed as pores that are long columnar spaces extending in the depth direction of the anodized film formed on the surface of the aluminum molded body. However, it is not always formed at a right angle to the surface of the aluminum molded body, and actually shows an irregular shape such as bending and branching. The diameter of the opening can be arbitrarily adjusted depending on the anodizing conditions, but in the present invention, the pores of the anodized film produced by this step have an opening diameter of 5 to 300 nm. It is preferably 5 to 50 nm, and more preferably 8 to 50 nm. If it is larger than 300 nm, it is difficult to make the anodic oxide film a uniform film, and it is difficult to obtain a porous film of less than 5 nm.
The length of the pores and the film thickness of the anodized film are not particularly limited, but in order to precipitate an amount of pigment necessary for being sufficiently colored by the pigment, the pigment is directed from the aluminum surface toward the thickness direction. It is 5 to 50 μm, preferably 8 to 30 μm.
After the anodizing treatment, the aluminum molded product is thoroughly washed with water.
[陽極酸化処理されたアルミニウム成形体をチタン（IV）錯体を含有する白色着色用組成物中に浸漬する工程]
本発明の方法における陽極酸化皮膜の細孔内に顔料を析出させる工程は、上記の陽極酸化処理後のアルミニウム成形体を、陰イオン性のチタン（IV）錯体を含有する白色着色用組成物中に浸漬する工程である。
（チタン（IV）錯体を含有する白色着色用組成物）
本発明にて使用されるチタン（IV）錯体を含有する白色着色用組成物に含有されるチタン（IV）錯体としては、白色の表面を得る上で陰イオン性のチタン（IV）錯体（チタン錯体自体が負電荷を有する）であることが好ましく、そのチタン（IV）錯体の配位子が、カルボン酸、ヒドロキシカルボン酸、硫酸根、ヒドロキシアミノ酸、アミノ酸及びアミノ系化合物から選ばれた１種以上のものであり、詳しくはカルボン酸がシュウ酸のものであり、ヒドロキシカルボン酸が乳酸、クエン酸、グリコール酸、サリチル酸、酒石酸及びリンゴ酸のものである。
そしてこれらのチタン（IV）錯体としてさらに詳しくは、ビス（オキサラト）オキソチタン（IV）酸アンモニウム、ビス（オキサラト）オキソチタン（IV）酸カリウム、ビス（オキサラト）ペルオキソチタン（IV）酸カリウム、ビス（オキサラト）ペルオキソチタン（IV）酸アンモニウム、チタン（IV）ラクテート、チタン（IV）ラクテートアンモニウム、チタン（IV）ビスラクテートアンモニウム、クエン酸チタン（IV）錯体、ペルオキソクエン酸チタン（IV）アンモニウム、ペルオキソグリコール酸チタン（IV）アンモニウム、トリス（サリチラト）チタン（IV）酸ナトリウム、トリス（サリチラト）チタン（IV）酸アンモニウム、酒石酸チタン（IV）錯体、リンゴ酸チタン（IV）錯体、ペルオキソビス（スルファト）チタン（IV）酸カリウム、ペルオキソビス（スルファト）チタン（IV）酸アンモニウム、オキソビス（スルファト）チタン（IV）酸ナトリウム、オキソビス（スルファト）チタン（IV）酸カリウム、オキソビス（スルファト）チタン（IV）酸アンモニウム、（２−ヒドロキシエチル）イミノ二酢酸、ジ（２−ヒドロキシエチル）グリシン、ジアミン系の１，３−プロパンジアミン四酢酸、（２−ヒドロキシエチル）エチレンジアミン三酢酸、１，２−ジアミノプロパン四酢酸、trans−１，２−シクロヘキサンジアミン四酢酸、あるいは配位子をセリン及び／又はトレオニンとしたものから選択して使用できる。
[Step of immersing the anodized aluminum molded product in a white coloring composition containing a titanium (IV) complex]
In the step of precipitating the pigment in the pores of the anodized film in the method of the present invention, the aluminum molded product after the anodizing treatment is subjected to a white coloring composition containing an anionic titanium (IV) complex. It is a step of immersing in.
(Composition for white coloring containing a titanium (IV) complex)
The titanium (IV) complex contained in the white coloring composition containing the titanium (IV) complex used in the present invention is an anionic titanium (IV) complex (titanium) for obtaining a white surface. The complex itself has a negative charge), and the ligand of the titanium (IV) complex is one selected from carboxylic acid, hydroxycarboxylic acid, sulfate root, hydroxyamino acid, amino acid and amino compound. More specifically, the carboxylic acid is that of oxalic acid, and the hydroxycarboxylic acid is that of lactic acid, citric acid, glycolic acid, salicylic acid, tartaric acid and malic acid.
More specifically, these titanium (IV) complexes include ammonium bis (oxalate) oxotitanium (IV) acid, potassium bis (oxalate) oxotitanium (IV) acid, potassium bis (oxalate) peroxotitanium (IV) acid, and bis (oxalate). ) Ammonium peroxotitanium (IV), titanium (IV) lactate, titanium (IV) lactate ammonium, titanium (IV) bislactate ammonium, titanium citrate (IV) complex, titanium peroxocitrate (IV) ammonium, peroxoglycolic acid Titanium (IV) ammonium, tris (salicyrat) sodium (IV) acid sodium, tris (salicyrat) titanium (IV) ammonium tartrate (IV) complex, titanium malate (IV) complex, peroxobis (sulfato) titanium ( Potassium oxobis (sulfato), ammonium peroxobis (sulfato) (IV), sodium oxobis (sulfato) titanium (IV), potassium oxobis (sulfato) titanium (IV), ammonium oxobis (sulfato) titanium (IV), (2-Hydroxyethyl) iminodiacetic acid, di (2-hydroxyethyl) glycine, diamine-based 1,3-propanediaminetetraacetic acid, (2-hydroxyethyl) ethylenediaminetriacetic acid, 1,2-diaminopropanetetraacetic acid, Trans-1,2-cyclohexanediaminetetraacetic acid or those in which the ligand is serine and / or threonine can be selected and used.
本発明におけるチタン（IV）錯体は、上記の他に、金属錯体自体ではなくても、例えば酸化硫酸チタン（IV）等のチタン源に、シュウ酸とアンモニア、あるいはシュウ酸アンモニウム等の配位子となり得る物質を加えたものから得られる錯体を包含する。また、この時加える配位子は、異なるチタン（IV）錯体を形成する２種類またはそれ以上の混合配位子であってもよい。
白色着色用組成物は、上記のチタン（IV）錯体を溶解するために溶媒として水を使用し、必要に応じて水溶性有機溶媒を併用できる。
さらに上記のチタン（IV）錯体の他にｐＨを調整するための酸、アンモニア等のアルカリ、シュウ酸アンモニウム、酢酸ナトリウム、ギ酸ナトリウム等の塩等も含有させることができる。また、必要に応じてさらに公知の添加剤を併用することができる。
In addition to the above, the titanium (IV) complex in the present invention is not a metal complex itself, but a ligand such as oxalic acid and ammonia or ammonium oxalate to a titanium source such as titanium oxide sulfate (IV). Includes complexes obtained from the addition of potential substances. Further, the ligand added at this time may be two or more kinds of mixed ligands forming different titanium (IV) complexes.
In the white coloring composition, water is used as a solvent for dissolving the above-mentioned titanium (IV) complex, and a water-soluble organic solvent can be used in combination if necessary.
Further, in addition to the above-mentioned titanium (IV) complex, an acid for adjusting pH, an alkali such as ammonia, a salt such as ammonium oxalate, sodium acetate and sodium formate can be contained. Further, if necessary, a known additive can be used in combination.
この工程において、白色着色用組成物中のチタン（IV）錯体の濃度としては二酸化チタン濃度換算にて０．２〜１０．０重量％、好ましくは０．５〜５．０重量％の範囲であり、０．２〜１０．０重量％の範囲を逸脱すると、顔料の充填が不十分、又は析出時の作業性が悪化する可能性がある。
アルミニウム成形体を浸漬するときの白色着色用組成物のｐＨは、３．００〜８．００、好ましくは４．００〜６．００、温度は３０〜８０℃、好ましくは４０〜７０℃、さらに好ましくは５０〜６０℃である。浸漬している時間としては、５〜３０分、好ましくは５〜２０分である。
これらの範囲から濃度、時間、温度が小であれば、十分に白色とならない可能性があり、逆に大であってもより白色となることはない。
In this step, the concentration of the titanium (IV) complex in the white coloring composition is in the range of 0.2 to 10.0% by weight, preferably 0.5 to 5.0% by weight in terms of titanium dioxide concentration. If it deviates from the range of 0.2 to 10.0% by weight, the filling of the pigment may be insufficient or the workability at the time of precipitation may be deteriorated.
The pH of the white coloring composition when the aluminum molded product is immersed is 3.00 to 8.00, preferably 4.0 to 6.00, the temperature is 30 to 80 ° C, preferably 40 to 70 ° C, and further. It is preferably 50 to 60 ° C. The soaking time is 5 to 30 minutes, preferably 5 to 20 minutes.
If the concentration, time, and temperature are small from these ranges, it may not be sufficiently white, and conversely, if it is large, it will not be whiter.
本発明のアルミニウム成形体は艶消しされていてもいなくてもよい。
本発明のアルミニウム成形体は、これまでアルミニウム成形体が使用されてきた、多くの分野・用途にて使用することができる。例えば情報家電の筐体、家具、食器、容器、家電製品、日用品、産業用材料、建築材料等のあらゆる用途において、表面が白色のアルミニウム成形体を必要とする場合に採用することができる。
The aluminum molded article of the present invention may or may not be matte.
The aluminum molded product of the present invention can be used in many fields and applications in which the aluminum molded product has been used so far. For example, it can be adopted when an aluminum molded body having a white surface is required in all applications such as housings for information appliances, furniture, tableware, containers, home appliances, daily necessities, industrial materials, and building materials.
（アルミニウム板の陽極酸化処理工程）
２０℃の１５重量％の硫酸水溶液を用意し、これにＡ１０５０アルミニウム板を浸漬した。このアルミニウム板に直流電流を１．５Ａ／ｄｍ２となるようにして陽極酸化処理多孔質皮膜を形成した。陽極酸化処理時間、多孔質皮膜厚を表１に示す。
(Aluminum plate anodizing process)
A 15% by weight aqueous sulfuric acid solution at 20 ° C. was prepared, and an A1050 aluminum plate was immersed therein. An anodized porous film was formed on this aluminum plate so that the direct current was 1.5 A / dm 2. Table 1 shows the anodic oxidation treatment time and the thickness of the porous film.
（陽極酸化処理されたアルミニウム成形体をチタン（IV）錯体を含有する白色着色用組成物中に浸漬する工程）
上記の工程により得た陽極酸化処理皮膜形成アルミニウム成形体をチタン（IV）錯体を含有する白色着色用組成物中に浸漬した。チタン（IV）錯体の濃度、白色着色用組成物の温度、ｐＨ、浸漬時間を表に示す。
白色着色用組成物のｐＨ調整には、アンモニア水又は水酸化カリウム水溶液を使用した。
また得られた白色アルミニウム成形体のＬ＊ａ＊ｂ＊の各値を表１に示す。
なお、表中のチタン（IV）錯体の欄のＡ〜Ｃは以下の化合物である。
Ａ：ビス（オキサラト）オキソチタン（IV）酸アンモニウム
Ｂ：チタン（IV）ビスラクテートアンモニウム
Ｃ：ビス（オキサラト）オキソチタン（IV）酸カリウム
(Step of immersing the anodized aluminum molded product in a white coloring composition containing a titanium (IV) complex)
The anodized aluminum molded product obtained by the above step was immersed in a white coloring composition containing a titanium (IV) complex. The concentration of the titanium (IV) complex, the temperature, pH, and immersion time of the white coloring composition are shown in the table.
Ammonia water or an aqueous potassium hydroxide solution was used to adjust the pH of the white coloring composition.
Table 1 shows each value of L * a * b * of the obtained white aluminum molded product.
In addition, A to C in the column of titanium (IV) complex in the table are the following compounds.
A: Ammonium bis (oxalate) oxotitanium (IV) B: Titanium (IV) Bislacate ammonium C: Potassium bis (oxalate) oxotitanium (IV)
（評価）
実施例及び比較例にて得られたアルミニウム成形体の表面の皮膜を、分光測色計（日本電色工業社製ＳＥ２００型）で測色（Ｌ＊ａ＊ｂ＊）した。
(Evaluation)
The surface film of the aluminum molded product obtained in Examples and Comparative Examples was color-measured (L * a * b * ) with a spectrophotometer (SE200 type manufactured by Nippon Denshoku Kogyo Co., Ltd.).
実施例によれば、Ｌ＊値が７０．００以上であり、得られたアルミニウム成形体の表面は、縁や角の部分を含めて、均一に白色を呈することを確認できた。
一方、チタン（IV）錯体を含有する白色着色用組成物に浸漬しなかった比較例１によれば、Ｌ＊値が低く白色を呈していないことがわかり、チタン（IV）錯体を含有する白色着色用組成物に浸漬した場合であっても、その条件によっては、十分に白色となった表面を得ることができなかった。
According to the examples, the L * value was 70.00 or more, and it was confirmed that the surface of the obtained aluminum molded product uniformly exhibited white color including the edges and corners.
On the other hand, according to Comparative Example 1 in which the white coloring composition containing the titanium (IV) complex was not immersed, it was found that the L * value was low and the white color was not exhibited, and the white color containing the titanium (IV) complex was found. Even when immersed in the coloring composition, a sufficiently white surface could not be obtained depending on the conditions.
Claims (8)
ｂ．陽極酸化処理されたアルミニウム成形体をチタン（IV）錯体を含有する白色着色用組成物中に浸漬するとともに、電解処理をせずに酸化チタンを析出させ、Ｌ ＊ 値が７０．００以上の白色アルミニウム成形体とする工程、
のａ及びｂ工程を有する白色アルミニウム成形体の製造方法。 a. The process of anodizing an aluminum molded product,
b. The anodized aluminum molded body is immersed in a white coloring composition containing a titanium (IV) complex, and titanium oxide is precipitated without electrolytic treatment, resulting in a white color having an L * value of 70.00 or more. The process of making an aluminum molded body,
A method for producing a white aluminum molded product having the steps a and b.
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