JP2019002049A - White aluminum molding, production method thereof, and white pigmentation composition - Google Patents
White aluminum molding, production method thereof, and white pigmentation composition Download PDFInfo
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- JP2019002049A JP2019002049A JP2017117936A JP2017117936A JP2019002049A JP 2019002049 A JP2019002049 A JP 2019002049A JP 2017117936 A JP2017117936 A JP 2017117936A JP 2017117936 A JP2017117936 A JP 2017117936A JP 2019002049 A JP2019002049 A JP 2019002049A
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000000465 moulding Methods 0.000 title abstract 5
- 230000019612 pigmentation Effects 0.000 title abstract 2
- 239000011148 porous material Substances 0.000 claims abstract description 44
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 20
- 238000004040 coloring Methods 0.000 claims description 45
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 238000007743 anodising Methods 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- ZWNZGTHTOBNSDL-UHFFFAOYSA-N N.[Ti+4] Chemical compound N.[Ti+4] ZWNZGTHTOBNSDL-UHFFFAOYSA-N 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- -1 amino compound Chemical class 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 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
- 239000002253 acid Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 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
- 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 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 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 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
- 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
- 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 3
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound 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
- 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
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 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 2
- RAYRIKMEHHXYJD-UHFFFAOYSA-N [NH4+].[NH4+].[NH4+].Oc1ccccc1C([O-])=O.Oc1ccccc1C([O-])=O.Oc1ccccc1C([O-])=O Chemical compound [NH4+].[NH4+].[NH4+].Oc1ccccc1C([O-])=O.Oc1ccccc1C([O-])=O.Oc1ccccc1C([O-])=O RAYRIKMEHHXYJD-UHFFFAOYSA-N 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- WHGNSQAWNMAUKZ-UHFFFAOYSA-K trisodium;2-carboxyphenolate Chemical compound [Na+].[Na+].[Na+].OC(=O)C1=CC=CC=C1[O-].OC(=O)C1=CC=CC=C1[O-].OC(=O)C1=CC=CC=C1[O-] WHGNSQAWNMAUKZ-UHFFFAOYSA-K 0.000 claims description 2
- 239000000049 pigment Substances 0.000 abstract description 18
- 239000004408 titanium dioxide Substances 0.000 abstract description 12
- 230000000704 physical effect Effects 0.000 abstract description 3
- 238000004901 spalling Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract 3
- 238000007254 oxidation reaction Methods 0.000 abstract 3
- 239000000463 material Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000001962 electrophoresis Methods 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
- 239000000956 alloy Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 229910045601 alloy Inorganic materials 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
- 230000001376 precipitating effect Effects 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
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 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
- 229910021365 Al-Mg-Si alloy 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
- 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
- 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
- GVQVOUBMSBBCNX-UHFFFAOYSA-N [Na+].[Ti+4] Chemical compound [Na+].[Ti+4] GVQVOUBMSBBCNX-UHFFFAOYSA-N 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
- 239000010407 anodic oxide Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 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
- 238000005452 bending Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 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
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- IXNPPKLOBLWSPQ-UHFFFAOYSA-N oxotitanium(2+) Chemical compound [Ti+2]=O IXNPPKLOBLWSPQ-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- UIEPWBNVIDPGBV-UHFFFAOYSA-N potassium titanium(4+) Chemical compound [K+].[Ti+4] UIEPWBNVIDPGBV-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000004065 semiconductor Substances 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
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 229910000349 titanium oxysulfate 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
Abstract
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 body, a production method thereof, and a white coloring composition.
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, after performing a known surface treatment if necessary, black, It was painted with a desired color paint such as red or white.
Apart from the above coating, after anodizing the surface of the aluminum molded body by, for example, sulfuric acid method or oxalic acid method, impregnating fine dyes formed on the surface with arbitrary dyes, filling with pigments, Alternatively, a method of electrolytically depositing nickel or the like and electrolytically coloring is also widely known. However, according to these methods, particularly electrolytic coloring methods, only limited colors can be obtained.
In addition, according to the method of coloring by putting a pigment in the pores formed on the surface of the aluminum molded body by electrophoresis, it is necessary to increase the pore diameter to such an extent that the pigment can enter, and to reduce the pigment diameter. It was necessary to do. However, even with this method, it is difficult to stably and uniformly color, and since there is a limit to the amount of pigment that can be put into the pores, it is also difficult to 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。 Moreover, although it is not a coloring method, as described in Patent Document 1, after the surface of the aluminum molded body is preliminarily treated with an anodized film, a mixed liquid containing titanyl sulfate and the like and a complexing agent that forms a cation is used. Among them, from a titanyl electrolytic treatment process for forming a titanium dioxide-containing film by depositing titanium dioxide on the surface of the anodized film and the inner surface of the hole by electrolytic treatment, and titanium dioxide having a photocatalytic ability by firing the titanium dioxide film There is known a method of forming a photocatalytic film made of titanium dioxide on the surface of the anodized film and the inner surface of the hole, which has a baking treatment step for changing to a photocatalytic 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。 Furthermore, in Patent Document 2, semiconductor fine particles such as titanium oxide having an average particle diameter 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 a substrate surface that is not in pores. A film is described which is an aluminum or aluminum alloy material characterized by being coated with a photocatalyst film deposited in such a manner that 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。
Patent Document 3 discloses that an aluminum material anodized at a high voltage is subjected to electrolytic coloring by applying an AC voltage in a metal salt solution. Patent Document 4 includes an aluminum material on which an anodized film is formed. 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 anodized film, followed by electrolytic coloring and electrophoretic coloring in an electrolytic coloring bath containing pigment particles or metal salts It is described to do.
Furthermore, in Patent Documents 5 and 6, after anodizing the surface of a member such as aluminum to form pores on the surface, the member is immersed in the presence of a titanium complex solution, and further electrolyzed by an electrolytic process. It is described that titanium oxide particles are formed in the pores by treatment.
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 body, as the use of the aluminum molded body was continued, the white coating film was peeled off, and the appearance was sometimes impaired.
Further, according to the method of filling the pores of the anodic oxide film with electrophoresis, the diameter of the pores must be increased so that the pigment can be filled in such an amount that the coloring power can be exerted. Then, the surface of the aluminum molded body becomes rough, and there is a possibility that the aesthetic appearance may be impaired.
Further, the colored film obtained in this way is not a dense film, but has a large pore diameter, so that the aluminum molded body has already had a certain amount of light due to reflection of light by the pores before filling with titanium oxide. It has coherence and has a transparent white color. Therefore, an opaque white film cannot be obtained.
In addition, when performing stable dark coloring by electrophoresis, since the bath current during electrophoresis is small, the pigment tends to be excessively deposited on the surface outside the pores, not in the pores. Further, when coloring with a white film by electrodeposition, the white film called spalling may be destroyed unless the conditions are accurately controlled. For this reason, the voltage applied during electrodeposition cannot be increased, and the target color cannot be increased.
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 comprising a titanyl electrolytic treatment step of forming titanium dioxide film by depositing titanium dioxide on the surface of the anodized film and the inner surface of the hole as described in Patent Document 1, and a step of firing the titanium dioxide film According to the above, it is difficult to deposit a sufficient amount of titanium dioxide for photocatalyst, and an aluminum molded body that is relatively inferior in heat resistance is heated to a high temperature, so that the molded body 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 subjected to electrophoresis, so that titanium oxide particles are not formed in the pores formed on the surface of the aluminum plate but on the surface. In this method, the photocatalyst is supported by precipitating, but the supported titanium oxide is for the photocatalyst and is not in the pores, and the amount carried in the pores is small.
The method described in Patent Document 3 is a method of coloring an aluminum material surface provided with an anodized film by applying an AC voltage in a metal salt solution, but the anodizing treatment is performed only once, and There is no suggestion of depositing a metal compound in the pores.
Further, although Patent Document 4 describes a method of filling a pigment into pores formed by an anodized film, the barrier layer is dissolved by etching the anodized film before filling the pigment. It is obvious that this etching step cannot naturally dissolve only the barrier layer in the pores, but also etches the entire anodized film. As a result, an uneven surface is formed on the entire anodized film, and even if it can be colored, the aluminum plate only forms an uneven and uneven surface.
In addition, this anodized film disappears by etching the once formed anodized film. Therefore, although there are pores, the pores are not protected by the anodized film, and the inside of the pores and the aluminum material surface corrode as the aluminum material is used.
In addition, depending on the conditions of the electrodeposition process, a power supply device that generates a larger current is required, so that the necessary equipment becomes larger.
Therefore, the present invention fills the pores formed by anodization with pigment particles such as titanium dioxide without causing spalling, and maintains the original shape while having an opaque and sufficient colored film, The object is to obtain an aluminum molded body having original physical properties by an anodized film and to make the power supply equipment necessary 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 are intended to deposit a large amount of titanium oxide particles up to the bottom in the pores, and thus require electrolytic treatment.
In practice, however, a sufficient white color can be obtained without precipitating titanium oxide particles to the bottom of the pores. Moreover, an apparatus for performing an electrolysis process is required, and the state of charge on the surface of the aluminum molded body is not uniform during the electrolysis. For example, the edges and corners of the molded body are more charged, resulting in white coloring. There may be 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 intensive studies to solve the above problems, the present inventors have invented the following white aluminum molded body, a method for producing the same, and a white coloring composition.
1. A white aluminum molded body obtained by adhering titanium oxide particles in pores formed by anodizing treatment on the surface of an aluminum molded body.
2. a. A process of anodizing the aluminum molded body,
b. A step of immersing the anodized aluminum molded body in a white coloring composition containing a titanium (IV) complex.
The manufacturing method of the white aluminum molded object which has a and b process of these.
3. A composition for white coloring of an aluminum molded body containing an anionic titanium (IV) complex and having titanium oxide particles adhered to the pores of the aluminum molded body having pores formed on the surface by anodizing treatment object.
4). 4. The white coloring composition according to 3, wherein the ligand of the anionic titanium (IV) complex is at least one selected from carboxylic acids, hydroxycarboxylic acids, sulfate radicals, hydroxyamino acids, amino acids, and amino compounds. object.
5. 5. The white coloring composition 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). Anionic titanium (IV) complexes include ammonium bis (oxalato) oxotitanium (IV), potassium bis (oxalato) oxotitanium (IV), potassium bis (oxalato) peroxotitanium (IV), bis (oxalato) peroxo Titanium (IV) Ammonium, Titanium (IV) Lactate, Titanium (IV) Bislactate Ammonium, Titanium (IV) Citrate Complex, Titanium (IV) Ammonium Peroxocitrate, Titanium (IV) Ammonium Peroxoglycolate, Tris (Salicylate ) Sodium titanate (IV), tris (salicylate) ammonium titanate (IV), titanium tartrate (IV) complex, titanium malate (IV) complex, peroxobis (sulfato) titanium titanate (IV), peroxobis (sulfato) ) Ammonium titanate (IV) 5. The white coloring composition according to 4, which is one or more selected from sodium bis (sulfato) titanium (IV), potassium oxobis (sulfato) titanium (IV), and ammonium oxobis (sulfato) titanium (IV). object.
7). 5. The white coloring composition according to 4, wherein serine and / or threonine is used as a ligand.
8). Anionic titanium (IV) complexes include (2-hydroxyethyl) iminodiacetic acid, di (2-hydroxyethyl) glycine, diamine-based 1,3-propanediaminetetraacetic acid, (2-hydroxyethyl) ethylenediamine 5. The white coloring composition according to 4, which is one or more 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。 Compared with the conventional coating method, according to the present invention, the colored film does not fall off unless the anodized film is peeled off. In addition, in the colored aluminum molded body in which titanium oxide particles are put in the pores of the anodized film, titanium oxide is deposited without electrolytic treatment, so that it is not necessary to set conditions for electrolytic treatment. It is not necessary to consider unevenness of the charged state on the surface of the aluminum molded body by electrolytic treatment, 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 body in which pigment particles are adhered in the pores formed on the anodized film on the surface of the aluminum molded body, particularly from the vicinity of the opening of the pore to the middle. Moreover, it is the method of obtaining the white aluminum molded object, and the composition for white coloring used for the method. And even if the particle diameter is smaller, for example, particles of titanium oxide or the like that originally do not exhibit white color because the primary particles are small, using the white coloring composition and without using electrolytic treatment in combination By depositing 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, resulting in high opacity, and so on. The particles can exhibit a white color, and as a result, the anodized film can exhibit a white color.
The white of the white aluminum molded body in the present invention has an L * value of 70.00 or more, preferably 75.00 or more, more preferably 80.00 or more. If it is less than 70.00, the surface color cannot be said to be white.
Preferably, a * and / or b * is in the range of −5.0 to +5.0, more preferably −2.5 to +2.5, and more preferably −1.0 to +1.0. And 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 body made of the following aluminum material.
(Aluminum material of white aluminum compact)
The aluminum material constituting the white aluminum molded body of the present invention may be a material made of only aluminum, but is generally a material called an aluminum alloy (for example, an Al—Mn alloy, an Al—Mg alloy, an Al—Cu alloy, Al—Mg—Si alloy or the like, and any material that is anodized to form pores may be used. Further, the aluminum material itself may be an already colored material by being alloyed with another metal.
Which aluminum material is used is determined by the use of the aluminum molded body of the present invention.
Before performing the anodizing treatment, if necessary, the aluminum molded body is immersed in a 10% nitric acid aqueous solution (room temperature), washed with water, and immersed in a 6.5% sodium hydroxide aqueous solution (about 30 to 50 ° C.). It is also possible to clean the surface by washing with water and dipping in a 10% nitric acid aqueous solution (room temperature) followed by washing with water.
[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。
[Step of anodizing aluminum compact]
The anodizing treatment performed for obtaining the aluminum molded body of the present invention is generally the same as the treatment performed on the surface of the aluminum molded body for imparting corrosion resistance and decorativeness to the surface. It must be a process that can be formed.
An aluminum molded body is brought into electrical contact with the anode of the anodizing apparatus, immersed in an electrolyte together with the anode and the cathode, and energized between the anode and the cathode, whereby an anodized film is formed on the aluminum molded body. Form.
As the electrolytic solution used at this time, an electrolytic solution composed of sulfuric acid, maleic acid, malonic acid, oxalic acid, or the like is used, and versatile sulfuric acid is particularly preferable. However, it is not limited to these.
Anodizing is performed by immersing the aluminum molded body in a bath having the acid concentration of 5 to 20% by weight and maintaining the current density constant. The current density at this time is preferably a constant current of 0.5 to 3.0 A / dm 2 , and such treatment is preferably performed for 20 to 50 minutes. However, these conditions are not limited as long as the film can be generated.
The generated pores are formed as pores which 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 necessarily formed at a right angle with respect to the surface of the aluminum molded body, and actually shows an irregular shape such as bending or branching. The diameter of the opening can be arbitrarily adjusted according to the anodizing conditions, but the pores of the anodized film produced by this step in the present invention have a diameter of 5 to 300 nm. Preferably it is 5-50 nm, More preferably, it is 8-50 nm. If it is larger than 300 nm, it is difficult to make the anodized film uniform, and a porous film of less than 5 nm is difficult to obtain.
Further, the length of the pores and the thickness of the anodized film are not particularly limited, but in order to deposit an amount of the pigment necessary to be sufficiently colored by the pigment, it is directed from the aluminum surface in the thickness direction. It is 5-50 micrometers, Preferably it is 8-30 micrometers.
After the anodizing treatment, the aluminum molded body is sufficiently 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 anodized aluminum molded body in white coloring composition containing titanium (IV) complex]
In the method of the present invention, the step of precipitating the pigment in the pores of the anodized film comprises the step of depositing the aluminum molded body after the anodizing treatment in a white coloring composition containing an anionic titanium (IV) complex. It is the process of immersing in.
(White coloring composition containing titanium (IV) complex)
The titanium (IV) complex contained in the white coloring composition containing the titanium (IV) complex used in the present invention includes 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 selected from carboxylic acid, hydroxycarboxylic acid, sulfate radical, hydroxyamino acid, amino acid and amino compound More specifically, the carboxylic acid is oxalic acid, and the hydroxycarboxylic acid is lactic acid, citric acid, glycolic acid, salicylic acid, tartaric acid and malic acid.
More specifically, these titanium (IV) complexes are more specifically ammonium bis (oxalato) oxotitanium (IV), potassium bis (oxalato) oxotitanium (IV), potassium bis (oxalato) peroxotitanium (IV), bis (oxalato) ) Ammonium peroxotitanium (IV), Titanium (IV) lactate, Titanium (IV) lactate ammonium, Titanium (IV) ammonium bislactate, Titanium (IV) complex, Titanium (IV) ammonium peroxocitrate, Peroxoglycolic acid Titanium (IV) ammonium, Tris (salicylate) titanium (IV) acid sodium, Tris (salicylate) titanium (IV) acid ammonium, Tartrate (IV) complex, Titanium malate (IV) complex, Peroxobis (sulfato) titanium ( IV) Potassium acid, pe Oxobis (sulfato) titanium (IV) ammonium, oxobis (sulfato) titanium (IV) sodium, oxobis (sulfato) titanium (IV) potassium, oxobis (sulfato) titanium (IV) ammonium, (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 a ligand selected from serine and / or threonine can be 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, for example, a titanium source such as titanium oxide (IV) oxide, a ligand such as oxalic acid and ammonia, or ammonium oxalate Includes complexes obtained from the addition of potential substances. The ligand added at this time may be two or more mixed ligands that form different titanium (IV) complexes.
The white coloring composition uses water as a solvent in order to dissolve the titanium (IV) complex, and a water-soluble organic solvent can be used in combination as necessary.
Further, in addition to the above titanium (IV) complex, an acid for adjusting pH, an alkali such as ammonia, a salt such as ammonium oxalate, sodium acetate, sodium formate and the like can also be contained. Moreover, a well-known additive can be used together as needed.
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 0.2 to 10.0% by weight, preferably 0.5 to 5.0% by weight in terms of titanium dioxide concentration. Yes, if it is out of the range of 0.2 to 10.0% by weight, there is a possibility that the pigment is not sufficiently filled or the workability at the time of precipitation is deteriorated.
The pH of the white coloring composition when the aluminum molded body is immersed is 3.00 to 8.00, preferably 4.00 to 6.00, the temperature is 30 to 80 ° C., preferably 40 to 70 ° C., and Preferably it is 50-60 degreeC. As immersion time, it is 5 to 30 minutes, Preferably it is 5 to 20 minutes.
If the concentration, time, and temperature are small from these ranges, there is a possibility that the color will not be sufficiently white.
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 body of the present invention may or may not be matt.
The aluminum molded body of the present invention can be used in many fields and applications where aluminum molded bodies have been used so far. For example, it can be employed when an aluminum molded body with a white surface is required in all uses such as a housing of 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 sulfuric acid aqueous solution at 20 ° C. was prepared, and an A1050 aluminum plate was immersed therein. An anodized porous film was formed on this aluminum plate with a direct current of 1.5 A / dm 2 . Table 1 shows the anodizing time and the porous film thickness.
（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 body in a white coloring composition containing a titanium (IV) complex)
The anodized film-formed aluminum molded body obtained by the above process 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 potassium hydroxide aqueous solution was used for pH adjustment of the white coloring composition.
Further, Table 1 shows each value of L * a * b * of the obtained white aluminum molded body.
In addition, AC of the column of the titanium (IV) complex in a table | surface is the following compounds.
A: ammonium bis (oxalato) oxotitanium (IV) B: ammonium titanium (IV) bislactate ammonium C: potassium bis (oxalato) 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 film on the surface of the aluminum molded body obtained in Examples and Comparative Examples was measured (L * a * b * ) with a spectrocolorimeter (SE200 model manufactured by Nippon Denshoku Industries 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 Example, L * value is 70.00 or more, It has confirmed that the surface of the obtained aluminum molded object was uniformly white including an edge and a corner | angular part.
On the other hand, according to Comparative Example 1 which was not immersed in the white coloring composition containing the titanium (IV) complex, it was found that the L * value was low and no white color was exhibited, and the white color containing the titanium (IV) complex. 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. A process of anodizing the aluminum molded body,
b. A step of immersing the anodized aluminum molded body in a white coloring composition containing a titanium (IV) complex.
The manufacturing method of the white aluminum molded object which has a and b process of these.
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| JP2016531208A (en) * | 2013-09-27 | 2016-10-06 | アップル インコーポレイテッド | Method for forming white anodic oxide film by injection of metal complex |
| JP2017025384A (en) * | 2015-07-23 | 2017-02-02 | 株式会社サクラクレパス | Colored aluminum molded body and method for producing the same |
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| WO2015129663A1 (en) * | 2014-02-28 | 2015-09-03 | 株式会社サクラクレパス | Colored formed aluminum body and method for manufacturing same |
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