JPH0320496A - Sealant for aluminum-based metal having oxide film and method for sealing oxide film of aluminum-based metal using the same - Google Patents
Sealant for aluminum-based metal having oxide film and method for sealing oxide film of aluminum-based metal using the sameInfo
- Publication number
- JPH0320496A JPH0320496A JP15419889A JP15419889A JPH0320496A JP H0320496 A JPH0320496 A JP H0320496A JP 15419889 A JP15419889 A JP 15419889A JP 15419889 A JP15419889 A JP 15419889A JP H0320496 A JPH0320496 A JP H0320496A
- Authority
- JP
- Japan
- Prior art keywords
- sealing
- oxide film
- aluminum
- titanium fluoride
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007789 sealing Methods 0.000 title claims abstract description 98
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 46
- 229910052782 aluminium Inorganic materials 0.000 title claims description 42
- 229910052751 metal Inorganic materials 0.000 title claims description 42
- 239000002184 metal Substances 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 31
- 239000000565 sealant Substances 0.000 title abstract 4
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims abstract description 55
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 25
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 17
- 150000002739 metals Chemical class 0.000 claims description 10
- 150000003754 zirconium Chemical class 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 abstract 3
- 229910000838 Al alloy Inorganic materials 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- HLJCWGPUCQTHFY-UHFFFAOYSA-H disodium;hexafluorotitanium(2-) Chemical compound [F-].[F-].[Na+].[Na+].F[Ti](F)(F)F HLJCWGPUCQTHFY-UHFFFAOYSA-H 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 25
- 230000007797 corrosion Effects 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- -1 zirconium potassium fluoride Chemical compound 0.000 description 13
- 239000010407 anodic oxide Substances 0.000 description 10
- 239000000975 dye Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 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 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
(.a)産業上の利用分野
本発明は酸化皮膜を有するアルミニウム系金属の封孔処
理剤及びこれを用いたアルミニウム系金属の酸化皮膜の
封孔処理方法に閃する。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field The present invention relates to a sealing agent for aluminum-based metals having an oxide film and a method for sealing an oxide film of aluminum-based metals using the same. .
(b)従来の技術
アルミニウム又はその合金(以下、アルミニウム系金属
という)の陽極酸化皮膜の封孔処理方法として、以下の
方法が提案されている。(b) Prior Art The following method has been proposed as a method for sealing an anodic oxide film of aluminum or its alloy (hereinafter referred to as aluminum-based metal).
即ち、■陽極酸化皮膜を有するアルミニウム系金属を、
フッ化ジルコニウムカリウムの0.1〜4g/lの水溶
液中で50〜100℃で加熱処理する方法である(特公
昭4 9−2 3 0 8 6号公報).
■陽極酸化皮膜を有するアルミニウム系金属を、フッ化
ジルコニウム塩の水溶液中で低温処理する方法である(
特開昭62−130295号公報).
(c)発明が解決しようとする課題
上記■の方法では、陽極酸化皮膜に優れた耐食性を付与
し得るが、処理皮膜が光線を反射して虹色を呈するので
商品価値が低下するなど、特有の欠点があった。また、
フッ化ジルコニウムカリウムに起因する懸濁物質が生じ
、それが皮膜表面に付着して封孔ムラを生じるなどの課
題もあった.又、上記■の方法では、上記■のような+
amはないが、低温で封孔処理をするために封孔が不充
分で脱色が生じ、このため1日以上の二一シングが必要
となる.
本発明は、フッ化チタン、フッ化チタニウム塩又はこれ
らの塩の少なくとも1種とフッ化ジルコニウム塩の混合
物を含む水溶液中で酸化皮膜を有するアルミニウム系金
属の封孔処理を行うことにより、処理皮膜が虹色を呈さ
ず、又染料の泣き出し、つまり脱色がなく、しかも均一
に封孔しうる上、封孔効果の優れた、アルミニウム系金
属の封孔処理剤及びこれを用いたアルミニウム系金属の
酸化皮膜の封孔処理方法を提供することを目的とする.
(d)課題を解決するための手段
上記巨的を達或するために、本発明のアルミニウム系金
属の封孔処理剤及びこれを用いたアルミニウム系金属の
酸化皮膜の封孔処理方法においては、アルミニウム系金
属の酸化皮膜をフッ化チタン、フッ化チタニウム塩或い
はこれらの塩とフッ化ジルコニウム塩の混合物を含む水
溶液中で封孔処理するとの技術的手段を講じたものであ
る。That is, ■ an aluminum-based metal with an anodic oxide film,
This method involves heat treatment at 50 to 100°C in an aqueous solution of zirconium potassium fluoride at a concentration of 0.1 to 4 g/l (Japanese Patent Publication No. 49-23-086). ■It is a method of low-temperature treatment of aluminum-based metals with anodized oxide films in an aqueous solution of zirconium fluoride salt (
(Japanese Patent Application Laid-Open No. 62-130295). (c) Problems to be Solved by the Invention The above method (■) can impart excellent corrosion resistance to the anodic oxide film, but the treated film reflects light and takes on an iridescent color, reducing its commercial value. There was a drawback. Also,
There were also problems such as suspended solids caused by potassium zirconium fluoride, which adhered to the film surface and caused uneven sealing. In addition, in the method of ■ above, +
Although there is no AM, the sealing process is performed at low temperatures, which results in insufficient sealing and discoloration, which requires 21-day shinging for more than one day. The present invention provides a treatment film by sealing an aluminum metal having an oxide film in an aqueous solution containing titanium fluoride, a titanium fluoride salt, or a mixture of at least one of these salts and a zirconium fluoride salt. A pore-sealing agent for aluminum-based metals that does not exhibit rainbow colors, does not cause dye bleeding or decolorization, can seal pores uniformly, and has an excellent pore-sealing effect, and aluminum-based metals using the same. The purpose of this study is to provide a method for sealing oxide films. (d) Means for Solving the Problems In order to achieve the above-mentioned goals, the sealing agent for aluminum-based metals and the method for sealing oxide films of aluminum-based metals using the same of the present invention include: A technical measure is taken to seal an oxide film of an aluminum metal in an aqueous solution containing titanium fluoride, a titanium fluoride salt, or a mixture of these salts and a zirconium fluoride salt.
即ち、請求項1の酸化皮膜を有するアルミニウム系金属
の封孔処理剤においては、アルミニウム系金属の酸化皮
膜を封孔するための封孔処理剤であって、該封孔処理剤
がフッ化チタン、フッ化チタニウム塩又はこれらの塩の
少なぐとも1種と77化ジルコニウム塩の混合物を含む
水溶液からなるものである.
以下、先ず、この封孔処理剤について詳細に説明する。That is, the sealing agent for an aluminum-based metal having an oxide film according to claim 1 is a pore-sealing agent for sealing an oxide film of an aluminum-based metal, wherein the pore-sealing agent is made of titanium fluoride. , a titanium fluoride salt, or a mixture of at least one of these salts and a zirconium 77ide salt. Hereinafter, first, this pore sealing agent will be explained in detail.
本発明において、酸化皮膜を有するアルミニウム系金属
とは、アルミニウム又はアルミニウム系合金の表面に、
化学的或いは電ス化学的(陽極酸化皮115I)に酸化
皮膜を形威したアルミニウム系金属をいうが、特に陽極
酸化皮膜が特性に優れるので好ましい.
そして、上記アルミニウム系金属に陽極酸化皮膜を形威
する方法としては、公知の陽極酸化法が採用される.
具体的に、たとえば硫酸、リン酸、クロム酸等からなる
無機酸、シュウ酸、パラ7エノールスルホン酸、スルホ
サリチル酸、マロン酸等からなる有機酸又は水酸化ナト
リウム、リン酸三ナトリウム等からなる水溶液中で、直
流、交流、パルス、PR法又は交直重畳法による電解に
よって陽極酸化皮膜が形威される.
ところで、本発明では上記酸化皮膜は染料や金属塩なと
で着色されたものも含む。In the present invention, an aluminum-based metal having an oxide film refers to aluminum or an aluminum-based alloy having
It refers to an aluminum-based metal that has been formed with an oxide film chemically or electrochemically (anodic oxide film 115I), and an anodic oxide film is particularly preferred because of its excellent properties. A known anodic oxidation method is used to form an anodic oxide film on the aluminum metal. Specifically, for example, inorganic acids such as sulfuric acid, phosphoric acid, and chromic acid, organic acids such as oxalic acid, para-7-enolsulfonic acid, sulfosalicylic acid, and malonic acid, or aqueous solutions such as sodium hydroxide and trisodium phosphate. In this process, an anodic oxide film is formed by electrolysis using direct current, alternating current, pulse, PR method, or AC/DC superposition method. Incidentally, in the present invention, the above-mentioned oxide film includes one colored with a dye or a metal salt.
上記酸化皮膜を有するアルミニウム系金属は封孔処理剤
中で封孔処理が為されるが、本発明においてはこの封孔
処理剤がフッ化チタン、フッ化チタニウム塩又はこれら
の塩の少なくとも1種と77化ジルコニウム塩の混合物
を含む水溶液からなる点に最も大きな特徴を有するので
ある。The above-mentioned aluminum-based metal having an oxide film is sealed in a sealing agent, and in the present invention, the sealing agent is titanium fluoride, a titanium fluoride salt, or at least one of these salts. The most significant feature is that it consists of an aqueous solution containing a mixture of zirconium salt and zirconium 77ide salt.
即ち、フッ化チタン、フッ化チタニウム塩又はこれらの
塩の少なくとも1種とフッ化ジルコニウム塩の混合物を
必須戊分とする封孔処理剤ではフッ化ジルコニウム塩の
みを用いた場合のような問題が発生せず、以下に述べる
理由により、優れた封孔効果が得られるのである.
上記フッ化チタニウム塩としてはへキサ7ルオロチタン
(F/ )F!!ナトリウム、ヘキサ7ルオロチタン(
■)l!!カリウム又はヘキサ7ルオロチタン(IV)
酸アンモニウムなどが挙げられる。That is, a pore sealing agent that essentially contains titanium fluoride, a titanium fluoride salt, or a mixture of at least one of these salts and a zirconium fluoride salt does not have the same problems as when only a zirconium fluoride salt is used. This does not occur, and for the reasons described below, an excellent sealing effect can be obtained. As the titanium fluoride salt, hexa7fluorotitanium (F/ )F! ! Sodium, hexa7fluoro titanium (
■) l! ! Potassium or hexa7fluorotitanium (IV)
Examples include ammonium acid.
そしてフッ化チタンと77化チタニウム塩は単独或いは
混合して用いることができる.ところで、本発明ではフ
ッ化ジルコニウム塩は単独で用いると上述の問題が発生
するために単独で用いることはないが、上記のフッ化チ
タン及び/又はフッ化チタニウム塩と77化ジルコニウ
ム塩との混合物は好適に用いることができる。このフッ
化ジルコニウム塩としてはヘキサ7ルオロジルコニウム
(■)酸ナトリウム、ヘキサ7ルオロジルコニウム(I
V)酸カリウム又はヘブタ7ルオロジルコニウム(1”
/)酸アンモニウムなどが挙げられる。Titanium fluoride and titanium 77ide salt can be used alone or in combination. Incidentally, in the present invention, zirconium fluoride salt is not used alone because the above-mentioned problems occur when used alone, but a mixture of titanium fluoride and/or the titanium fluoride salt and zirconium 77ide salt is used. can be suitably used. Examples of the fluoridated zirconium salt include sodium hexa7fluorozirconium (■), hexa7fluorozirconium (I
V) acid potassium or hebuta-7fluorozirconium (1”
/) acid ammonium, etc.
本発明の封孔処理剤において、これらの金属塩の濃度と
しては0.1〜100g/1,特に0.5〜50g/l
の範囲とするのが望ましく、この金属塩の濃度が、0.
1g/f未満では耐食性の充分優れた封孔効果が得られ
ない場合があり、又、100g/1を超えると意味がな
いだけでなく不経済である。In the pore sealing agent of the present invention, the concentration of these metal salts is 0.1 to 100 g/l, particularly 0.5 to 50 g/l.
It is desirable that the concentration of this metal salt be in the range of 0.
If it is less than 1 g/f, a sealing effect with sufficiently excellent corrosion resistance may not be obtained, and if it exceeds 100 g/f, it is not only meaningless but also uneconomical.
又、この封孔処理剤のpHは3.5〜6.5の範囲、特
に4〜6の範囲にするのが望まし<,pHが3.5未満
になると酸性度が高くなり過ぎて皮膜が破壊される恐れ
が有り、又、逆にpHが6.5を超えると上記金属塩が
加水分解されて保存中に変化し、均一な封孔効果が得ら
れない恐れが生じるので好ましくない。The pH of this pore sealing agent is preferably in the range of 3.5 to 6.5, especially in the range of 4 to 6. If the pH is less than 3.5, the acidity will be too high and the film will be damaged. On the other hand, if the pH exceeds 6.5, the metal salts may be hydrolyzed and change during storage, which is not preferable because a uniform sealing effect may not be obtained.
このpH調整剤としては硫酸、リン酸等の無機酸、酢酸
、クエン酸、コハク陵、グルコン酸、グリシン、マロン
酸、しゅう酸、ギ酸等の有機酸、アルカリ金属の水酸化
物、炭酸塩又は重炭酸塩、アンモニア、有機酸のアルカ
リ金属塩、各種アミン類等が挙げられる。これらの塩又
は塩基或いは有W1m更に有機酸のアルカリ金属塩は1
種類を用いても良いし、2種以上を併用しても良く、特
にその併用が有効な場合が有る。Examples of the pH adjusting agent include inorganic acids such as sulfuric acid and phosphoric acid, organic acids such as acetic acid, citric acid, succinic acid, gluconic acid, glycine, malonic acid, oxalic acid, and formic acid, alkali metal hydroxides, carbonates, etc. Examples include bicarbonate, ammonia, alkali metal salts of organic acids, and various amines. These salts or bases or alkali metal salts of organic acids are
One type may be used or two or more types may be used in combination, and there are cases where the combination is particularly effective.
ところで、本発明の封孔処理剤には、所望により、界面
活性剤を0.5〜50g/1の範囲で添加しても良いの
である。Incidentally, a surfactant may be added to the pore sealing agent of the present invention in an amount of 0.5 to 50 g/1, if desired.
このように界面活性剤を添加することにより、酸化皮膜
と封孔処理剤との親和性が良好となり、フッ化チタンや
フッ化チタニウム塩等の金属塩による封孔が円滑に行な
われるのである。By adding a surfactant in this manner, the affinity between the oxide film and the sealing agent becomes good, and the sealing with a metal salt such as titanium fluoride or titanium fluoride salt is performed smoothly.
上記界面活性剤としては、例えば脂肪酸塩、アルキル硫
酸エステル塩、アルキルベンゼンスルホン酸塩、ボリオ
キシエチレンアルキル硫酸エステル酸等の7二オン系界
面活性剤、ポリオキシエチレンRm酸エステル、ボリオ
キシエチレン7ルキルエーテル、ポリオキシエチレンア
ルキルフェノールエーテル等のノニオン系界面活性剤を
挙げることができる。Examples of the above-mentioned surfactants include fatty acid salts, alkyl sulfate salts, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate ester acids, polyoxyethylene Rm acid esters, polyoxyethylene 7-rukyl esters, etc. Examples include nonionic surfactants such as ether and polyoxyethylene alkylphenol ether.
次に、請求項2の発明について詳細に説明する。Next, the invention of claim 2 will be explained in detail.
請求項2の酸化皮膜を有するアルミニウム系金属の封孔
処理剤においては、゛フッ化チタン及び/又はフッ化チ
タニウム塩(A)と77化シルコエウム塩(B)の混合
物が(A)100重量部に対し(B)10〜400重量
部であることを特徴とするものである.
即ち、フッ化ジルコニウム塩を単独で用いると、上述の
欠点が生じるのであるが、このようにフッ化チタン及び
/又はフッ化チタニウム塩とフッ化ジルコニウム塩の混
合物とすることにより、後述する理由より、均一で、し
かも優れた封孔効果が得られるのである。In the sealing agent for aluminum-based metals having an oxide film according to claim 2, ``a mixture of titanium fluoride and/or titanium fluoride salt (A) and silcoium 77ide salt (B) is (A) 100 parts by weight. (B) in an amount of 10 to 400 parts by weight. That is, if zirconium fluoride salt is used alone, the above-mentioned disadvantages will occur, but by using titanium fluoride and/or a mixture of titanium fluoride and zirconium fluoride salt, for the reasons described below. A uniform and excellent sealing effect can be obtained.
つまりフッ化チタンとフッ化ジルコニウム塩との混合物
、フッ化チタニウム塩と77化ノルコニウム塩との混合
物、更にフッ化チタン、フッ化チタニウム塩及びフッ化
ジルコニウム塩との混合物が挙げられる.
そして、この場合、フッ化チタン及び/又はフッ化チタ
ニウム塩(A)とフッ化ジルコニウム塩(B)の混合物
が(A)100重量部に対し(B)10〜400重量部
であることが望まし(、(A)100重量部に対し、(
B)が10重量部未満ではフッ化ジルコニウム塩を加え
たことによる相乗効果が乏しく、これを加えた意味がな
く、一方、(B)が4oO重量部を超えると上述の欠点
、つまりフッ化ジルコニウム塩のみを用いた場合と同様
の欠点が発生する恐れが有るので好ましくないのである
。That is, examples include mixtures of titanium fluoride and zirconium fluoride salts, mixtures of titanium fluoride salts and norconium 77ide salts, and mixtures of titanium fluoride, titanium fluoride salts, and zirconium fluoride salts. In this case, it is desirable that the mixture of titanium fluoride and/or titanium fluoride salt (A) and zirconium fluoride salt (B) be 10 to 400 parts by weight of (B) based on 100 parts by weight of (A). For 100 parts by weight of (A), (
If B) is less than 10 parts by weight, the synergistic effect of adding the zirconium fluoride salt will be poor, and there is no point in adding it. On the other hand, if (B) exceeds 40 parts by weight, the above-mentioned disadvantages will occur, that is, the zirconium fluoride salt will be added. This is not preferable because it may cause the same drawbacks as when using only salt.
この発明においては、フッ化チタン及び/又はフッ化チ
タニウム塩とフッ化ジルコニウム塩の混合物を封孔処理
剤の必須戊分とした点に特徴を有し、その他は請求項1
の封孔処理剤と同様であるので省略する.
更に、請求項3のアルミニウム系金属の酸化皮膜の封孔
処理方法について詳細に説明する.請求項3のアルミニ
ウム系金属の酸化皮膜の封孔処理方法においては、アル
ミニウム系金属の酸化皮膜を77化チタン、フッ化チタ
ニウム塩或いはこれらの塩とフッ化ジルコニウム塩の混
合物を含む水溶液中で予備封孔処理後、本封孔すること
を特徴とするものである。This invention is characterized in that titanium fluoride and/or a mixture of titanium fluoride salt and zirconium fluoride salt is an essential component of the pore sealing agent, and the rest is claimed in claim 1.
This is the same as the pore sealing agent, so it will be omitted. Furthermore, the method for sealing an oxide film of an aluminum-based metal according to claim 3 will be explained in detail. In the method for sealing an oxide film of an aluminum-based metal according to claim 3, the oxide film of an aluminum-based metal is preliminarily prepared in an aqueous solution containing titanium 77ide, titanium fluoride salt, or a mixture of these salts and zirconium fluoride salt. After the sealing treatment, the main sealing is performed.
即ち、この発明においては、請求項1の封孔処理剤を用
いてアルミニウムP.金属の酸化皮膜の封孔処理を行う
方法についてのものである。That is, in this invention, aluminum P. This article concerns a method for sealing a metal oxide film.
従って、フッ化チタン、フッ化チタニウム塩或いはこれ
らの塩とフッ化ゾルコニウム塩の混合物の意味は、a求
項1の場合と同様であるので省略する。Therefore, the meaning of titanium fluoride, titanium fluoride salt, or a mixture of these salts and zorconium fluoride salt is the same as in the case of item a, and will therefore be omitted.
本発明においては、先ずこの封孔処理剤を用いてアルミ
ニウム系金属の酸化皮膜を予air孔処理する第1工程
、を実施する。In the present invention, first, a first step is carried out in which the oxide film of the aluminum-based metal is subjected to a pre-air hole treatment using this sealing agent.
この酸化皮膜は染料や金属塩などで着色されたものも含
む.
この酸化皮膜を有するアルミニウム系金属を予備封孔す
るには、上記封孔処理剤を処理槽に投入し、所望により
、水で77化チタンやフッ化チタニウム塩等の金属塩の
濃度を0.1〜100g/1、特に0.5〜50g/1
の範囲に調整したり、pH調整剤でpHを3.5〜6.
5の範囲、特に4〜6の範囲にllI!!!を行い、こ
の処理液の温度を、通常、室温〜50℃、好ましくは2
0〜40℃に調整し、通常30秒〜20分、好ましくは
1〜10分問酸化皮膜を有するアルミニウム系金属を浸
漬すれば良いのである。This oxide film also includes those colored with dyes or metal salts. To pre-seal the aluminum-based metal having this oxide film, the above-mentioned sealing agent is put into a treatment tank, and if desired, the concentration of metal salt such as titanium 77ide or titanium fluoride is reduced to 0.0 with water. 1-100g/1, especially 0.5-50g/1
or adjust the pH to a range of 3.5 to 6.0 with a pH adjuster.
llI in the range of 5, especially in the range of 4 to 6! ! ! The temperature of this treatment liquid is usually from room temperature to 50°C, preferably 2°C.
The temperature may be adjusted to 0 to 40°C, and the aluminum metal having an oxide film may be immersed for usually 30 seconds to 20 minutes, preferably 1 to 10 minutes.
本発明においては、次に、上記第1工程で予備封孔した
酸化皮膜を有するアルミニウム系金属を、本封孔する第
2工程を実施する。In the present invention, next, a second step is performed in which the aluminum-based metal having the oxide film that has been preliminarily sealed in the first step is subjected to main sealing.
この本封孔の方法としては特に限定されるものではない
。The method of this main hole sealing is not particularly limited.
例えば上記第1工程で予IiIN孔した酸化皮膜を有す
るアルミニウム系金属を、(イ)90゜C以上の熱水中
に5分以上浸漬したり、(ロ)2kg/cm2以上の水
蒸気で5分以上封孔処理したり、(ハ)M孔助剤を含む
水溶液中で80℃以上で5分以上封孔処理するなどの方
法が挙げられる.
本発明においては本封孔が、従来の方法より、水蒸只の
圧力が低くてよく、しかも至極短時間で行う事ができる
が、これは本発明では予a封孔をしているからである。For example, an aluminum-based metal having an oxide film that has been pre-IiIN holed in the first step is (a) immersed in hot water of 90°C or more for 5 minutes or more, or (b) immersed in water vapor of 2 kg/cm2 or more for 5 minutes. Examples of methods include the above-mentioned sealing treatment, and (iii) sealing treatment at 80° C. or higher for 5 minutes or more in an aqueous solution containing an M pore aid. In the present invention, the actual sealing requires a lower pressure of water vapor than the conventional method, and can be performed in an extremely short time. This is because the present invention performs pre-sealing. be.
なお、上記(ハ)の封孔助剤としては特に限定されるも
のではなく公知のものが用いられるが、具体的には例え
ば商品名が、酢酸ニッケル系封孔助剤であるシーリング
ソル}ASL(サンド社製〉、7−コー(古河電工製)
、トップシール(奥野製薬製)等が挙げられるのであり
、又、封孔助剤の濃度はその効果が得られる範囲であれ
ば特に限定されるものではないが、一般に1〜10g/
1、特に4〜7g/lの範囲とするのが望ましい,この
ように封孔処哩を行うことにより、耐食性が優れ、しか
も封孔処理中に染料等の泣き出し、つまり脱色がなく、
更に手で触れても染料等が手に転着せず優れた封孔効果
を実現しうるのである.即ち、従米、染料等で着色した
酸化皮膜を通常の封孔方法で封孔すると、この封孔の際
に、この染料等が封孔液中に泣き出し、つまり脱色が生
じ、色の薄化や色ムラの原因となり実用性に欠ける場合
があった。しかしながら本発明の封孔方法によると、こ
のような脱色がなく、耐食性も優れる上、均一な封孔効
果が得られるのである。Note that the sealing aid in (c) above is not particularly limited and any known one may be used, but specifically, for example, the product name is Sealing Sol}ASL, which is a nickel acetate-based sealing aid. (manufactured by Sandoz Co., Ltd.), 7-Co (manufactured by Furukawa Electric)
, Top Seal (manufactured by Okuno Pharmaceutical Co., Ltd.), etc. The concentration of the sealing aid is not particularly limited as long as the effect can be obtained, but it is generally 1 to 10 g/
1. In particular, it is desirable that the content be in the range of 4 to 7 g/l.By performing the sealing treatment in this way, corrosion resistance is excellent, and there is no bleeding of dyes, etc., or decolorization during the sealing treatment.
Furthermore, even if you touch it with your hands, dyes will not transfer to your hands, and an excellent sealing effect can be achieved. In other words, when an oxide film colored with a dye or the like is sealed using a normal sealing method, the dye, etc. leaks into the sealing solution during sealing, resulting in decolorization and thinning of the color. This may cause color unevenness and may be impractical. However, according to the pore sealing method of the present invention, such discoloration does not occur, corrosion resistance is excellent, and a uniform pore sealing effect can be obtained.
この本封孔処理後、適宜水洗、乾燥することにより、充
分に満足し得る耐食性が付与された封孔処理皮膜が得ら
れるのである。After this main pore-sealing treatment, a pore-sealing film with sufficiently satisfactory corrosion resistance can be obtained by appropriately washing with water and drying.
次に、請求項4の発明について詳細に説明する。Next, the invention of claim 4 will be explained in detail.
請求項4のアルミニウム系金属の酸化皮膜の封孔処理方
法においては、請求項2の封孔処理剤を用いてアルミニ
ウム系金属の酸化皮膜を、開求項3と同様の封孔処理を
行う方法についてのものである。In the method for sealing an oxide film of an aluminum-based metal according to claim 4, the oxide film of an aluminum-based metal is subjected to the same sealing treatment as in claim 3 using the sealing agent of claim 2. It is about.
従って、この封孔処理方法に用いられる封孔処理剤の詳
細な説明、及び封孔処理方法については省略する。Therefore, a detailed explanation of the sealing agent used in this sealing method and the sealing method will be omitted.
即ち、請求項4のアルミニウム系金属の酸化皮膜の封孔
処理方法においては、フッ化チタン及び/又はフッ化チ
タニウム塩(A)とフッ化ジルコニウム塩(B)の混合
物が(A)100重量部に対し(B)10〜400重量
部である封孔処理剤で、請求項3と同様の方法で封孔処
理を行うものである。That is, in the method for sealing an oxide film of an aluminum-based metal according to claim 4, the mixture of titanium fluoride and/or titanium fluoride salt (A) and zirconium fluoride salt (B) is 100 parts by weight of (A). The sealing agent is used in an amount of 10 to 400 parts by weight based on (B), and the sealing treatment is performed in the same manner as in claim 3.
このようにフッ化チタン及び/又はフッ化チタニウム塩
とフッ化ゾルコニウム塩の混合物とすることにより、両
者の相乗作用により、一m均一で、至極優れた耐食性を
発現し、しかも優れた封孔効果が得られるのである。By using a mixture of titanium fluoride and/or titanium fluoride salt and zorconium fluoride salt in this way, the synergistic effect of the two allows for extremely excellent corrosion resistance to be achieved evenly over one meter, and an excellent sealing effect. is obtained.
(e)作用
本発明において、フッ化チタン、フッ化チタニウム塩又
はこれらの塩の少なくとも1種とフッ化ジルコニウム塩
の混合物を用いると、充分な耐食性が付与されるがその
理由は、フッ化チタン等の金属塩からの加水分解物の粒
径がフッ化ジルコニウム塩からの加水分解物の粒径より
小さく、このため該加水分解物が酸化皮膜内に円滑に侵
入し、これが当該酸化皮膜における微細孔を確実に塞ぐ
ためと解される。(e) Effect In the present invention, when titanium fluoride, a titanium fluoride salt, or a mixture of at least one of these salts and a zirconium fluoride salt is used, sufficient corrosion resistance is imparted. The particle size of the hydrolyzate from the metal salt is smaller than the particle size of the hydrolyzate from the zirconium fluoride salt, and therefore the hydrolyzate smoothly penetrates into the oxide film, which causes fine particles in the oxide film to form. It is understood that this is to ensure that the hole is closed.
又、本発明の方法では、予備封孔処理を高温で行っても
処理皮膜が光線を反射して虹色を呈するといった問題は
ないが、予備封孔を高温で行うと着色酸化皮膜からの脱
色が生じるが、予備封孔を比較的低温で行い、これによ
って、脱色を防止する一方、本封孔により完全に封孔す
るため均一に且つ確実に封孔しうるのであり、この結果
酸化皮膜の耐食性が至極優れる作用を有するのである。In addition, in the method of the present invention, even if the pre-sealing treatment is performed at a high temperature, there is no problem that the treated film reflects light and exhibits a rainbow color, but if the pre-sealing treatment is performed at a high temperature, the colored oxide film may be decolored. However, pre-sealing is performed at a relatively low temperature, which prevents discoloration, while the main sealing seals the pores completely, making it possible to seal the pores uniformly and reliably.As a result, the oxide film is It has the effect of extremely excellent corrosion resistance.
ところで、本発明において、フッ化チタン及び/又はフ
ッ化チタニウム塩とフッ化ジルコニウム塩との混合物を
用いると、一層優れた耐食性が得られるが、これは各金
属塩からの加水分解物が均一に混合された状態になり、
粒子同士の反発が解消され、この結果、加水分解物がa
簗じやすくなってその粒径が一層小さくなって酸化皮膜
の微細孔への侵入が一層容易になるためと解される。By the way, in the present invention, even better corrosion resistance can be obtained by using titanium fluoride and/or a mixture of titanium fluoride salt and zirconium fluoride salt, but this is because the hydrolyzate from each metal salt is uniformly distributed. becomes a mixed state,
The repulsion between particles is eliminated, and as a result, the hydrolyzate becomes a
It is understood that this is because the particles become easier to swallow and their particle size becomes smaller, making it easier for them to penetrate into the micropores of the oxide film.
(f)実施例
以下、本発明を実施例に基づき詳細に説明するが、本発
明はこれに限定されるものではない。(f) Examples Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.
実施例1
アルミニウム板(AI 0 5 0P−82 4材、寸
法5 0mmX 1 0 0mmX 1 am)を常法
に従い、アルカリ脱脂、酸洗浄をした。これを1 8
0 g/ lH 2SO,水溶液中で、温度20℃、電
流密度1.5A/dm”の条件下、25分間電解して陽
極酸化皮膜(厚さ12μIII)を形威した。Example 1 An aluminum plate (AI 050P-82 4 material, dimensions 50 mm x 100 mm x 1 am) was degreased with alkaline and washed with acid according to a conventional method. This is 1 8
An anodic oxide film (thickness: 12 μIII) was formed by electrolyzing for 25 minutes in an aqueous solution containing 0 g/lH 2 SO at a temperature of 20° C. and a current density of 1.5 A/dm.
これを水洗後、フッ化チタン5g/l、ドデンルベンゼ
ンスルホン酸ナトリウム2g/1の水溶液に30℃で1
0分間浸漬して予備封孔した。次いで、これを水洗後、
封孔助剤であるシーリングソルトASL−New(サン
ド社製商品名)5g/ffi水溶液中に、温度9゜0゜
Cで5分間浸漬して本封孔した。 次に、これをJIS
H 8601に従ってアルカリ滴下試験による耐
食性試験を行った。After washing with water, it was added to an aqueous solution of 5 g/l of titanium fluoride and 2 g/l of sodium dodenlebenzenesulfonate at 30°C.
The holes were preliminarily sealed by immersion for 0 minutes. Next, after washing it with water,
The pores were immersed in a 5 g/ffi aqueous solution of sealing salt ASL-New (trade name, manufactured by Sandoz Co., Ltd.), which is a pore-sealing agent, at a temperature of 9.degree. Next, convert this to JIS
Corrosion resistance testing by alkaline drop test was carried out according to H 8601.
その結果105秒であった。The result was 105 seconds.
実施例2
アルミニウム板(A60635−T5材、寸法5 0m
mX 1 0 0wmX 1mm)に、実施例1と同様
に20分間電解して陽極酸化皮i(厚さ9μm)を形威
した.
これを水洗後、ヘキサ7ルオロチタン(IV)酸ナトリ
ウムSg/1、ドデシルベンゼンスルホン酸ナトリウム
1g/1の水溶液に40℃で3分間浸漬して予@封孔し
た。次いで、これを水洗後、90℃の熱水中に、温度9
5゜Cで5分間浸漬して本封孔した。Example 2 Aluminum plate (A60635-T5 material, dimension 50m
The anodic oxide film i (thickness: 9 μm) was formed by electrolysis for 20 minutes in the same manner as in Example 1. After washing with water, this was pre-sealed by immersing it in an aqueous solution of sodium hexa7fluorotitanate (IV) Sg/1 and sodium dodecylbenzenesulfonate 1 g/1 at 40° C. for 3 minutes. Next, after washing it with water, it was placed in hot water at a temperature of 90°C.
The hole was finally sealed by immersion at 5°C for 5 minutes.
次に、これをJIS H 8601に従ってアルカ
リ滴下試験による耐食性試験を行った。Next, this was subjected to a corrosion resistance test using an alkali dropping test according to JIS H 8601.
その結果125秒であった。The result was 125 seconds.
実施例3
アルミニウム板(A60635−T5材、寸法50II
I+1×100I×1ffiII1)に、実施例1と同
様に50分間電解して陽極酸化皮膜(厚さ22μII1
)を形戒した。これをA Iua+iniun B l
ue 2 LW(サンド社製青色染料)3g/fの水溶
液中に、温度50℃で5分間浸漬し、青色酸化皮膜を得
た。Example 3 Aluminum plate (A60635-T5 material, size 50II
I + 1 x 100 I
) was admonished. This is A Iua + iniun B l
It was immersed in an aqueous solution of 3 g/f of ue 2 LW (blue dye manufactured by Sandoz Co., Ltd.) at a temperature of 50° C. for 5 minutes to obtain a blue oxide film.
これを水洗後、ヘキサ7ルオ口チタン(R’)酸ナトリ
ウム5g/1とへキサ7ルオロジルコニウム(’IY)
Wlナトリウム2,Sg/1の水溶液に20℃で8分間
浸漬して予備封孔した。次いで、これを水洗後、封孔助
剤であるシーリングソル} ASL−New(サンド社
製商品名)5g/j!水溶液中に、温度90℃で5分間
浸漬して本封孔した。After washing this with water, 5g/1 sodium hexa7fluorotitanium (R') and hexa7fluorozirconium ('IY)
It was preliminarily sealed by immersing it in an aqueous solution of Wl sodium 2, Sg/1 at 20°C for 8 minutes. Next, after washing it with water, sealing sol which is a sealing agent} ASL-New (trade name manufactured by Sandoz Co., Ltd.) 5 g/j! It was immersed in an aqueous solution at a temperature of 90° C. for 5 minutes to perform main sealing.
次に、これをJIS H 8601に従ってアルカ
リ滴下試験による耐食性試験を行った。Next, this was subjected to a corrosion resistance test using an alkali dropping test according to JIS H 8601.
その結果250秒であった。The result was 250 seconds.
本発明法によれば、充分に満足できる耐食性が得られる
ことが認められる。According to the method of the present invention, it is recognized that sufficiently satisfactory corrosion resistance can be obtained.
また、本実施例で得られた処理皮膜は、種々の方向から
光を当てても何ら虹色を呈さず、封孔ムラも全く認めら
れなかった。尚、処理温度を70℃とした場合も、処理
表面は虹色を呈さず、封孔ムラも全くなかった。Further, the treated film obtained in this example did not exhibit any iridescent color even when exposed to light from various directions, and no sealing unevenness was observed at all. Note that even when the treatment temperature was 70° C., the treated surface did not exhibit rainbow color and there was no uneven sealing at all.
更に、このものに手で触れても手に染料が全く転着する
ことがなかった。Furthermore, even when this material was touched with the hands, no dye was transferred to the hands.
比較例1
アルミニウム板(A 1 0 5 0P−82 4材、
寸法50mmX1 00mmX1−一を用い、これを実
施例1と同様の条件で20分間電解して陽極酸化皮膜(
厚さ9μm)を形威させた。これを水洗し、次いで、(
N H .)2Z rF .を1g/l及びアニオン界
面活性剤であるボリオキシエチレンラウリル硫酸ナトリ
ウムを0.25g/1含む水溶液(液温30℃)に30
分間浸漬して封孔処理後、乾燥した。Comparative Example 1 Aluminum plate (A 1 0 5 0P-82 4 material,
Using a size 50mm x 100mm x 1-1, this was electrolyzed for 20 minutes under the same conditions as in Example 1 to form an anodized film (
The thickness was 9 μm). Wash this with water, then (
N.H. )2Z rF. 30% in an aqueous solution (liquid temperature 30°C) containing 1g/l of
After soaking for a minute and sealing, it was dried.
得られた処理皮膜は、虹色を全く呈さなかったが、手で
触れると指紋跡がつき、しかも養生シートを貼ると剥が
れなくなるなどの問題が生じた。Although the obtained treated film did not exhibit any iridescent color, it had problems such as fingerprint marks when touched by hand and difficulty in peeling off when a curing sheet was applied.
ところで、上記陽極酸化皮膜を実施例3と同様に着色し
、これを水洗し、次いで、(NH.).ZrF6を1g
/l及びアニオン界面活性剤であるボリオキシエチレン
ラウリル硫酸ナトリウムを0.25g/1含む水溶液(
液温30℃)に30分間浸漬して封孔処理後、乾燥した
。By the way, the above anodic oxide film was colored in the same manner as in Example 3, washed with water, and then coated with (NH.). 1g of ZrF6
An aqueous solution containing 0.25 g/l and anionic surfactant sodium polyoxyethylene lauryl sulfate (
After pore-sealing treatment by immersing it in a liquid temperature of 30° C. for 30 minutes, it was dried.
このものに手で触れると手に染料が転着することが認め
られた。It was observed that when this material was touched with the hands, the dye was transferred to the hands.
比較例2
アルミニウム板(*施例2で用いたものと同じ)を実施
例2と同様にして陽極酸化処理し、(NH.).ZrF
.1g/f(ジルコニウム金属に換算して0.41g/
J!)の水溶液に70℃で30分間浸漬して封孔処理し
た.実施例1と同様に耐食性を調べたところ約90秒で
あった。この処理皮膜は、種々の方向から光を当てた場
合に着しい虹色を呈し、商品価値が低かった。Comparative Example 2 An aluminum plate (*same as that used in Example 2) was anodized in the same manner as in Example 2, and (NH.). ZrF
.. 1g/f (0.41g/f in terms of zirconium metal)
J! ) for 30 minutes at 70°C to seal the holes. Corrosion resistance was examined in the same manner as in Example 1 and was found to be approximately 90 seconds. This treated film exhibited a dark iridescent color when exposed to light from various directions, and its commercial value was low.
([1>発明の効果
本発明は、以上説明したように構威されているので、以
下に記載されるような効果を奏する。([1> Effects of the Invention Since the present invention is structured as described above, it produces the effects described below.
本発明の封孔処理剤においては、フッ化チタン、フッ化
チタニウム塩又はこれらの塩の少なくとも1種とフッ化
ジルコニウム塩の混合物を用いており、これらの塩から
の加水分解物が酸化皮膜内に円滑に侵入し、これが当該
酸化皮膜における微細孔を確実に塞ぐため優れた封孔効
果を奏するのである。The pore sealing agent of the present invention uses titanium fluoride, a titanium fluoride salt, or a mixture of at least one of these salts and a zirconium fluoride salt, and the hydrolyzate from these salts is released into the oxide film. It penetrates smoothly into the oxide film and reliably closes the micropores in the oxide film, resulting in an excellent pore-sealing effect.
又、本発明の方法では、予{II封孔処理を高温で行っ
ても処理皮膜が光線を反射して虹色を呈するといった問
題はないが、予備封孔を高温で行うと着色酸化皮膜から
の脱色が生じるが、予@封孔を比較的低温で行い、これ
によって、脱色を防止する一方、本封孔により完全に封
孔するため均一に且つ確実に封孔しうるのであり、この
結果酸化皮膜の耐食性が至極優れる効果を有するのであ
る.ところで、本発明において、フッ化チタン及び/又
はフッ化チタニウム塩とフッ化ジルコニウム塩との混合
物を用いると、各金属塩からの加水分解物が均一に混合
されて粒子同士の反発が解?l’fされるのでその粒径
が一層小さくなって酸化皮膜の微細孔への侵入が一N1
容易になり、この結果、層優れた耐食性が得られるので
ある。In addition, in the method of the present invention, even if the pre-sealing treatment is performed at a high temperature, there is no problem that the treated film reflects light and exhibits an iridescent color, but if the pre-sealing treatment is performed at a high temperature, the colored oxide film However, pre-sealing is performed at a relatively low temperature, which prevents discoloration, while main sealing completely seals the pores, making it possible to seal them uniformly and reliably. The corrosion resistance of the oxide film is extremely effective. By the way, in the present invention, when titanium fluoride and/or a mixture of titanium fluoride salt and zirconium fluoride salt is used, the hydrolyzates from each metal salt are uniformly mixed, and the repulsion between particles is eliminated. Since the particle size is further reduced, it is difficult for the particles to penetrate into the micropores of the oxide film by 1 N1.
As a result, excellent corrosion resistance can be obtained.
Claims (4)
封孔処理剤であって、該封孔処理剤がフッ化チタン、フ
ッ化チタニウム塩又はこれらの塩の少なくとも1種とフ
ッ化ジルコニウム塩の混合物を含む水溶液からなる酸化
皮膜を有するアルミニウム系金属の封孔処理剤。(1) A sealing agent for sealing an oxide film of an aluminum-based metal, the sealing agent comprising titanium fluoride, a titanium fluoride salt, or at least one of these salts and a zirconium fluoride salt. A pore sealing agent for aluminum-based metals having an oxide film made of an aqueous solution containing a mixture of.
)とフッ化ジルコニウム塩(B)の混合物が(A)10
0重量部に対し(B)10〜400重量部である請求項
1記載の酸化皮膜を有するアルミニウム系金属の封孔処
理剤。(2) Titanium fluoride and/or titanium fluoride salt (A
) and fluorinated zirconium salt (B) is (A) 10
The sealing agent for aluminum-based metals having an oxide film according to claim 1, wherein the amount of (B) is 10 to 400 parts by weight relative to 0 parts by weight.
フッ化チタニウム塩或いはこれらの塩とフッ化ジルコニ
ウム塩の混合物を含む水溶液中で予備封孔処理後、本封
孔することを特徴とするアルミニウム系金属の酸化皮膜
の封孔処理方法。(3) Titanium fluoride, aluminum-based metal oxide film,
1. A method for sealing an oxide film of an aluminum-based metal, comprising performing preliminary sealing in an aqueous solution containing a titanium fluoride salt or a mixture of these salts and a zirconium fluoride salt.
)とフッ化ジルコニウム塩(B)の混合物が(A)10
0重量部に対し(B)10〜400重量部である請求項
3記載のアルミニウム系金属の酸化皮膜の封孔処理方法
。(4) Titanium fluoride and/or titanium fluoride salt (A
) and fluorinated zirconium salt (B) is (A) 10
4. The method for sealing an oxide film of an aluminum-based metal according to claim 3, wherein the amount of (B) is 10 to 400 parts by weight relative to 0 parts by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15419889A JPH0320496A (en) | 1989-06-15 | 1989-06-15 | Sealant for aluminum-based metal having oxide film and method for sealing oxide film of aluminum-based metal using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15419889A JPH0320496A (en) | 1989-06-15 | 1989-06-15 | Sealant for aluminum-based metal having oxide film and method for sealing oxide film of aluminum-based metal using the same |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0320496A true JPH0320496A (en) | 1991-01-29 |
Family
ID=15578983
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15419889A Pending JPH0320496A (en) | 1989-06-15 | 1989-06-15 | Sealant for aluminum-based metal having oxide film and method for sealing oxide film of aluminum-based metal using the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0320496A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996027698A3 (en) * | 1995-03-08 | 1996-12-05 | Henkel Kgaa | Chromium-free process for improving the adherence of paint applied by thin-film anodic oxidation |
WO2005016849A1 (en) * | 2003-08-13 | 2005-02-24 | Honeywell Specialty Chemicals Seelze Gmbh | Oxidic aluminum compounds with metals and fluorine |
JP2007277597A (en) * | 2006-04-03 | 2007-10-25 | Muramatsu Kagaku Kk | Sealing method of aluminum or aluminum alloy |
CN103590086A (en) * | 2013-11-14 | 2014-02-19 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | Nickel-free hole sealing agent for aluminum alloy and hole sealing treatment process of agent |
CN109056028A (en) * | 2018-07-20 | 2018-12-21 | 江苏飞拓界面工程科技有限公司 | A kind of aluminium and aluminium alloy anode oxide aftertreatment fluid and preparation method thereof |
-
1989
- 1989-06-15 JP JP15419889A patent/JPH0320496A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996027698A3 (en) * | 1995-03-08 | 1996-12-05 | Henkel Kgaa | Chromium-free process for improving the adherence of paint applied by thin-film anodic oxidation |
US5961809A (en) * | 1995-03-08 | 1999-10-05 | Henkel Kommanditgesellschaft Auf Aktien | Chromium-free process for improving paint adhesion after thin-layer anodization |
WO2005016849A1 (en) * | 2003-08-13 | 2005-02-24 | Honeywell Specialty Chemicals Seelze Gmbh | Oxidic aluminum compounds with metals and fluorine |
JP2007277597A (en) * | 2006-04-03 | 2007-10-25 | Muramatsu Kagaku Kk | Sealing method of aluminum or aluminum alloy |
JP4620625B2 (en) * | 2006-04-03 | 2011-01-26 | 村松化学有限会社 | Sealing method for aluminum or aluminum alloy |
CN103590086A (en) * | 2013-11-14 | 2014-02-19 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | Nickel-free hole sealing agent for aluminum alloy and hole sealing treatment process of agent |
CN109056028A (en) * | 2018-07-20 | 2018-12-21 | 江苏飞拓界面工程科技有限公司 | A kind of aluminium and aluminium alloy anode oxide aftertreatment fluid and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH11509579A (en) | Method for sealing metal anodized with a solution containing lithium and fluoride without using heavy metal | |
JPH0320496A (en) | Sealant for aluminum-based metal having oxide film and method for sealing oxide film of aluminum-based metal using the same | |
NO833388L (en) | PROCEDURE FOR SURFACE TREATMENT OF ALUMINUM AND ALUMINUM ALLOYS | |
JPH11236698A (en) | Corrosion resistant magnesium material product having brightness of metallic bare surface and its production | |
JPH03232996A (en) | Improvement of resistance to low temperature corrosion of anodically oxidized aluminum | |
CN110158136A (en) | A kind of aluminium electrolytic coloring titanium color surface treatment method | |
JPH06235091A (en) | Pretreatment of colored titanium material by anodization and production of colored titanium material | |
JP2004018901A (en) | Surface treatment method for magnesium material product | |
KR100400104B1 (en) | aluminum surface treatment method | |
JPS5827997A (en) | Pretreatment of stainless steel for color formation | |
KR20210001331U (en) | Method for surface treatment of aluminum alloy member and member made of anodized aluminum alloy | |
JPH1112762A (en) | Surface-treated aluminum material for two-piece can and production of surface-treated aluminum material for two-piece can | |
EP0015279A1 (en) | Coating system. | |
US3791943A (en) | Process for after treatment of anodic oxide or chemical conversion coatings of aluminum or aluminum alloys | |
JP3933751B2 (en) | Method for producing surface-treated aluminum material for two-piece can lid material with open can tab | |
CN110541168B (en) | Nickel remover and nickel removing method | |
JPH01139798A (en) | Surface treating agent for aluminum-based metal having oxide film | |
JPS62256994A (en) | Surface treating agent for aluminum-base metal having oxide film | |
JPS63206499A (en) | White color treatment of aluminum or aluminum alloy | |
JPH0238680B2 (en) | SANKAHIMAKUOJUSURUARUMINIUMUKEIKINZOKUNOHYOMENSHORIHOHO | |
JPH11209893A (en) | Formation of anode oxidation coating film | |
JPS5938388A (en) | Surface treatment of aluminum alloy casting or aluminum alloy die casting | |
JPS62256995A (en) | Surface treatment of aluminum metal having oxide film | |
CN114959828A (en) | Aluminum alloy anode process | |
JPH0313598A (en) | Chemical method for avoiding rainbow effect on member composed of aluminum or aluminum alloy |