JP4977819B2 - Alkaline degreasing cleaner for aluminum or aluminum alloy and pretreatment method of aluminum or aluminum alloy using the same - Google Patents
Alkaline degreasing cleaner for aluminum or aluminum alloy and pretreatment method of aluminum or aluminum alloy using the same Download PDFInfo
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- JP4977819B2 JP4977819B2 JP2007077116A JP2007077116A JP4977819B2 JP 4977819 B2 JP4977819 B2 JP 4977819B2 JP 2007077116 A JP2007077116 A JP 2007077116A JP 2007077116 A JP2007077116 A JP 2007077116A JP 4977819 B2 JP4977819 B2 JP 4977819B2
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- 229910052782 aluminium Inorganic materials 0.000 title claims description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 44
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 22
- 238000005238 degreasing Methods 0.000 title claims description 10
- 238000002203 pretreatment Methods 0.000 title claims description 8
- 238000011282 treatment Methods 0.000 claims description 22
- -1 aluminum compound Chemical class 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 13
- 238000004381 surface treatment Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 239000003599 detergent Substances 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000013527 degreasing agent Substances 0.000 claims description 3
- 238000005237 degreasing agent Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000012459 cleaning agent Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 239000003921 oil Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000003002 pH adjusting agent Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 235000019832 sodium triphosphate Nutrition 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 3
- 235000019801 trisodium phosphate Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical group [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical group [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- IHGSAQHSAGRWNI-UHFFFAOYSA-N 1-(4-bromophenyl)-2,2,2-trifluoroethanone Chemical compound FC(F)(F)C(=O)C1=CC=C(Br)C=C1 IHGSAQHSAGRWNI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011591 potassium Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- ZOEVNLTZXXOQCI-UHFFFAOYSA-K trisodium;[[hydroxy(oxido)phosphoryl]oxy-oxidophosphoryl] hydrogen phosphate Chemical compound [Na+].[Na+].[Na+].OP([O-])(=O)OP(O)(=O)OP([O-])([O-])=O ZOEVNLTZXXOQCI-UHFFFAOYSA-K 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Landscapes
- Chemical Treatment Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
本発明は、アルミニウム又はアルミニウム合金表面に強固に付着した汚れや油、酸化皮膜を除去するための前処理液（アルカリ脱脂洗浄剤）及び前処理方法（清浄化処理）に関するものである。 The present invention relates to a pretreatment liquid (alkaline degreasing cleaner) and a pretreatment method (cleaning treatment) for removing dirt, oil, and oxide film firmly adhered to the surface of aluminum or an aluminum alloy.
アルミニウムやアルミニウム合金は、航空機、自動車などの軽量化対策の素材として注目されているが、防食性を向上させるための表面処理が必須のものとなっている。一般的には化成処理、陽極酸化や塗装などの表面処理が施されている。これらの表面処理を行なう前の前処理としては、次のような前処理剤で洗浄されている：
１）中又は強アルカリ性の脱脂剤、及び
２）中性又は弱アルカリ性の脱脂剤。
しかしながら、上記１）の前処理剤での洗浄では、油は取れるが、アルミニウムやアルミニウム合金の表層を侵食するため電触が生じやすくなり、著しく耐食性を損なうという問題点がある。２）の前処理剤での洗浄では、アルミニウムやアルミニウム合金の表層を侵食することはないが、中性又は弱アルカリ性のため洗浄力が弱く、強固に付着した油をとることが出来ない。
アルミ腐食を抑制しつつ洗浄性を向上しようとする試みとしては、例えば、電子部品のアルミ配線等を洗浄するための洗浄剤として、有機アルカリ成分と水酸基含有化合物よりなる耐アルミ腐食性に優れたアルカリ洗浄剤が開示されている（特許文献１）が、このような洗浄剤は、本願の課題であるアルミニウムの溶解を抑制し、前処理としての脱脂洗浄化能力に優れ、かつその後行なう表面処理の外観や耐食性を改善する事ができる脱脂洗浄剤とは異なるものである。
Aluminum and aluminum alloys are attracting attention as materials for weight reduction measures for aircraft, automobiles, and the like, but surface treatment for improving corrosion resistance is essential. In general, surface treatments such as chemical conversion treatment, anodization and painting are performed. As a pretreatment before performing these surface treatments, the following pretreatment agent is used for cleaning.
1) a neutral or strong alkaline degreasing agent, and 2) a neutral or weak alkaline degreasing agent.
However, in the cleaning with the pretreatment agent of 1), oil can be removed, but since the surface layer of aluminum or aluminum alloy is eroded, electric contact is likely to occur and there is a problem that the corrosion resistance is remarkably impaired. In the cleaning with the pretreatment agent of 2), the surface layer of aluminum or aluminum alloy is not eroded, but the neutrality or weak alkalinity makes the cleaning power weak, and it is not possible to remove the strongly adhered oil.
As an attempt to improve cleanability while suppressing aluminum corrosion, for example, as a cleaning agent for cleaning aluminum wiring of electronic parts, etc., it was excellent in aluminum corrosion resistance consisting of an organic alkali component and a hydroxyl group-containing compound An alkaline cleaning agent is disclosed (Patent Document 1). However, such a cleaning agent suppresses dissolution of aluminum, which is the subject of the present application, has excellent degreasing performance as a pretreatment, and is a surface treatment performed thereafter. It is different from a degreasing detergent that can improve the appearance and corrosion resistance of the shampoo.
本発明は、強力な脱脂能力があり、かつアルミニウムの溶解を抑えることができるアルミニウム又はその合金表面の前処理方法を提供することを目的とする。また、本発明は、さらに前処理後に行なう表面処理、特に前処理による表面状態の影響を受け易い３価クロム化成処理の外観や耐食性を改善することができるアルミニウム又はアルミニウム合金表面の前処理方法を提供することを目的とする。 An object of the present invention is to provide a pretreatment method for the surface of aluminum or an alloy thereof, which has a strong degreasing ability and can suppress dissolution of aluminum. Furthermore, the present invention provides a pretreatment method for an aluminum or aluminum alloy surface that can improve the appearance and corrosion resistance of a surface treatment performed after pretreatment, in particular, trivalent chromium chemical conversion treatment that is easily affected by the surface condition of the pretreatment. The purpose is to provide.
本発明は、アルミニウム又はアルミニウム合金を、アルミニウムの溶解を抑制する作用があるアルミニウム化合物を添加含有させた、特定のアルカリ度（ＰＨ濃度)範囲の洗浄剤で処理することによって上記課題を効率的に達成できるとの知見に基づいてなされたのである。すなわち、本発明によると、アルミニウム化合物を０．１〜１０ｇ／Ｌ含有し、ＰＨが８〜１２であるアルミニウム又はアルミニウム合金用アルカリ脱脂洗浄剤が提供される。また、当該アルカリ脱脂洗浄剤を用いたアルミニウム又はアルミニウム合金の前処理方法が提供される。 The present invention efficiently treats the above problems by treating aluminum or an aluminum alloy with a cleaning agent having a specific alkalinity (PH concentration) range in which an aluminum compound having an action of suppressing dissolution of aluminum is added. It was based on the knowledge that it could be achieved. That is, according to the present invention, an alkaline degreasing detergent for aluminum or aluminum alloy containing 0.1 to 10 g / L of an aluminum compound and having a pH of 8 to 12 is provided. Moreover, the pre-processing method of aluminum or aluminum alloy using the said alkaline degreasing detergent is provided.
本発明によれば、前処理としての表面洗浄化能力に優れ、しかもアルミニウムの溶解を抑制できる。そのため、その後行なう表面処理、特に３価クロム化成処理の外観や耐食性を改善する事ができる。さらに、３価クロム化成処理後の塗装密着性も向上するといった利点も得られ、特に、化成皮膜処理の前処理剤として適している。本発明の洗浄液でアルミニウム又はアルミニウム合金を前処理した後に行なわれた表面処理皮膜は、外観、耐食性等の諸機能に優れるため、航空機部品、自動車部品等の表面処理工程の前処理工程に適している。 According to the present invention, the surface cleaning ability as a pretreatment is excellent, and dissolution of aluminum can be suppressed. Therefore, it is possible to improve the appearance and corrosion resistance of the subsequent surface treatment, particularly trivalent chromium chemical conversion treatment. Furthermore, the advantage that the paint adhesion after the trivalent chromium chemical conversion treatment is improved is obtained, and it is particularly suitable as a pretreatment agent for chemical conversion coating treatment. Since the surface treatment film performed after pretreating aluminum or aluminum alloy with the cleaning liquid of the present invention is excellent in various functions such as appearance and corrosion resistance, it is suitable for the pretreatment step of the surface treatment step of aircraft parts, automobile parts, etc. Yes.
本発明で対象とする表面前処理材料はアルミニウム及びアルミニウム合金である。アルミニウム合金としては、例えばＡ２０１７、ＡＤＣ１２等、アルミニウムとＭｇ、Ｍｎ、Ｚｎ、Ｓｉ、Ｃｕ、Ｎｉなどの合金が挙げられる。また、アルミニウム及びアルミニウム合金の形状は、ダイカスト材、鋳造品、射出成形品など、任意の形状であってもよい。
本発明の洗浄剤に含まれるアルミニウム化合物は、水溶性のアルミニウム化合物であり、例えば塩化アルミニウム、硫酸アルミニウム、硫化アルミニウム、リン化アルミニウム、硝酸アルミニウム、アルミン酸塩、アルミニウムカリウムミョウバンなどが挙げられる。また、金属アルミニウムを強酸又は強アルカリに溶解して実質的にアルミニウム化合物水溶液としたものであってもよい。前記アルミニウム化合物は、単独で、又は２種類以上混合して使用できる。前記アルミニウム化合物の含有量は、好ましくは０．１〜１０ｇ／Ｌの範囲であり、より好ましくは０．５〜１ｇ／Ｌの範囲である。
本発明の洗浄剤のｐＨは、好ましくは８〜１２の範囲であり、より好ましくはｐＨ８〜１０の範囲である。本発明の洗浄剤のｐＨをこのような範囲とすることにより、脱脂洗浄性に優れ、アルミニウム及びアルミニウム合金の溶解を効果的に抑制することができる。ｐＨを調整するためのアルカリ又は酸としては、水酸化アルカリ、炭酸アルカリ、塩酸、硫酸などが使用できる。
The surface pretreatment materials targeted in the present invention are aluminum and aluminum alloys. Examples of the aluminum alloy include aluminum and alloys such as Mg, Mn, Zn, Si, Cu, and Ni, such as A2017 and ADC12. The shape of aluminum and aluminum alloy may be any shape such as a die-cast material, a cast product, and an injection molded product.
The aluminum compound contained in the cleaning agent of the present invention is a water-soluble aluminum compound, and examples thereof include aluminum chloride, aluminum sulfate, aluminum sulfide, aluminum phosphide, aluminum nitrate, aluminate, and aluminum potassium alum. Moreover, what melt | dissolved metallic aluminum in the strong acid or the strong alkali, and was substantially made into the aluminum compound aqueous solution may be used. The said aluminum compound can be used individually or in mixture of 2 or more types. The content of the aluminum compound is preferably in the range of 0.1 to 10 g / L, more preferably in the range of 0.5 to 1 g / L.
The pH of the cleaning agent of the present invention is preferably in the range of 8-12, more preferably in the range of pH 8-10. By setting the pH of the cleaning agent of the present invention in such a range, it is excellent in degreasing cleaning properties, and dissolution of aluminum and aluminum alloy can be effectively suppressed. As the alkali or acid for adjusting the pH, alkali hydroxide, alkali carbonate, hydrochloric acid, sulfuric acid and the like can be used.
本発明の洗浄剤には、さらにアルカリビルダーを含有させてもよい。前記アルカリビルダーとしては、リン酸塩、硫酸塩等の無機ビルダーが挙げられる。リン酸塩としては、第３リン酸ナトリウム、ピロリン酸ナトリウム、トリポリリン酸ナトリウム、第３リン酸カリウム、ピロリン酸カリウム、トリポリリン酸カリウムなどが挙げられる。硫酸塩としては、硫酸ナトリウム、硫酸カリウムなどが挙げられる。前記アルカリビルダーは、単独で、又は２種類以上混合して使用できる。前記アルカリビルダーの含有量は、好ましくは５〜１００ｇ／Ｌの範囲であり、より好ましくは５〜５０ｇ／Ｌの範囲である。ただし、前記アルカリビルダーがケイ酸塩を含む場合には、洗浄後の表面にケイ素が付着する場合があり、後の表面処理に悪影響を及ぼす場合があるため、ケイ酸塩は含まないほうが好ましい。また、前記アルカリビルダーがホウ酸塩を含む場合には、ホウ素が水質汚濁防止法の規制物質であり、安価で効果的に排水を処理することが困難であるという排水処理上の問題点があることから、ホウ酸塩は含まないほうが好ましい。
本発明の洗浄剤には、さらに界面活性剤を含有させてもよい。前記界面活性剤としては、ノニオン系の界面活性剤が好ましい。また、前記ノニオン系の界面活性剤に、使用する界面活性剤の全重量の最大２０重量％までのアニオン系界面活性剤を混合してもよい。前記ノニオン系の界面活性剤としては、ポリオキシエチレンノニルフェニルエーテル、エチレンオキサイドープロピレンオキサイド共重合体等が挙げられる。前記アニオン系界面活性剤としては、アルキルベンゼンスルホン酸等が挙げられる。前記界面活性剤の含有量は、好ましくは０．１〜１０ｇ／Ｌの範囲であり、より好ましくは０．５〜５ｇ／Ｌの範囲である。
The cleaning agent of the present invention may further contain an alkali builder. Examples of the alkali builder include inorganic builders such as phosphates and sulfates. Examples of the phosphate include tribasic sodium phosphate, sodium pyrophosphate, sodium tripolyphosphate, tertiary potassium phosphate, potassium pyrophosphate, potassium tripolyphosphate, and the like. Examples of the sulfate include sodium sulfate and potassium sulfate. The alkali builder can be used alone or in combination of two or more. The content of the alkali builder is preferably in the range of 5 to 100 g / L, more preferably in the range of 5 to 50 g / L. However, when the alkali builder contains a silicate, silicon may adhere to the surface after washing, which may adversely affect the subsequent surface treatment. Therefore, it is preferable not to contain a silicate. Further, when the alkali builder contains borate, boron is a regulated substance of the Water Pollution Control Law, and there is a problem in wastewater treatment that it is difficult to treat wastewater at low cost effectively. Therefore, it is preferable not to contain borate.
The cleaning agent of the present invention may further contain a surfactant. As the surfactant, a nonionic surfactant is preferable. The nonionic surfactant may be mixed with an anionic surfactant up to a maximum of 20% by weight of the total weight of the surfactant to be used. Examples of the nonionic surfactant include polyoxyethylene nonylphenyl ether, ethylene oxide-propylene oxide copolymer, and the like. Examples of the anionic surfactant include alkylbenzene sulfonic acid. The content of the surfactant is preferably in the range of 0.1 to 10 g / L, more preferably in the range of 0.5 to 5 g / L.
本発明における洗浄処理方法としては、特に制限はなく、公知の各種アルカリ洗浄方法を適用することができるが、通常、アルミニウム及びアルミニウム合金を本発明のアルカリ脱脂洗浄剤に浸漬処理することにより行なう。浸漬処理温度は、好ましくは２０〜１００℃の範囲であり、より好ましくは３０〜８０℃の範囲である。浸漬処理時間は、好ましくは１０秒〜１時間であり、より好ましくは１〜３０分間である。ポンプによる洗浄剤の攪拌を行なうか、処理品を遥動させることが好ましい。 There is no restriction | limiting in particular as a washing | cleaning processing method in this invention, Although various well-known alkali washing | cleaning methods can be applied, Usually, it carries out by immersing aluminum and an aluminum alloy in the alkaline degreasing detergent of this invention. The immersion treatment temperature is preferably in the range of 20 to 100 ° C, more preferably in the range of 30 to 80 ° C. The immersion treatment time is preferably 10 seconds to 1 hour, more preferably 1 to 30 minutes. It is preferable to stir the cleaning agent with a pump or to swing the treated product.
（実施例１）
水に第３リン酸ナトリウム２５ｇ／Ｌ、ポリオキシエチレンノニルフェニルエーテル（ミヨシ油脂（株）製 ペレテックス１２２４）４ｇ／Ｌ及びアルキルベンゼンスルホン酸１ｇ／Ｌを溶解し、得られた水溶液に塩化アルミニウム４ｇ／Ｌを添加し、さらにｐＨ調整剤として水酸化ナトリウムを添加してｐＨを９に調整して洗浄剤を得た。アルミダイカスト材（ＡＤＣ−１２）を６０℃、処理時間５分の条件で前記洗浄剤に浸漬させた。
Example 1
3 g of sodium triphosphate 25 g / L, 4 g / L of polyoxyethylene nonylphenyl ether (Peletex 1224 manufactured by Miyoshi Oil & Fats Co., Ltd.) and 1 g / L of alkylbenzene sulfonic acid were dissolved in water, and 4 g of aluminum chloride was dissolved in the resulting aqueous solution. L was added, and sodium hydroxide was added as a pH adjuster to adjust the pH to 9 to obtain a cleaning agent. An aluminum die-cast material (ADC-12) was immersed in the cleaning agent under conditions of 60 ° C. and a treatment time of 5 minutes.
ここで、参考として実施例１の処理液でｐＨを９で一定にした時の塩化アルミニウム塩の添加量とエッチング量との関係を表１に示す。なお、アルミダイカスト材（ＡＤＣ−１２）の浸漬時間は６０℃−３０分とした。
（実施例２）
水に第３リン酸ナトリウム２５ｇ／Ｌ及びエチレンオキサイド−プロピレンオキサイド共重合体（第一工業薬品（株）製 エパン６８０）５ｇ／Ｌを溶解し、得られた水溶液に硫酸アルミニウム５ｇ／Ｌを添加し、さらにｐＨ調整剤として水酸化ナトリウムを添加してｐＨを９に調整して洗浄剤を得た。アルミダイカスト材（ＡＤＣ−１２）を４０℃、処理時間５分の条件で前記洗浄剤に浸漬させた。
(Example 2)
Dissolve 3 g of trisodium phosphate in water and 5 g / L of ethylene oxide-propylene oxide copolymer (Epan 680 manufactured by Daiichi Kogyo Kagaku Co., Ltd.), and add 5 g / L of aluminum sulfate to the resulting aqueous solution. Further, sodium hydroxide was added as a pH adjuster to adjust the pH to 9 to obtain a cleaning agent. An aluminum die-cast material (ADC-12) was immersed in the cleaning agent under conditions of 40 ° C. and a treatment time of 5 minutes.
（実施例３）
水にトリポリリン酸ナトリウム３０ｇ／Ｌ及びポリオキシエチレンノニルフェニルエーテル（ミヨシ油脂（株）製 ペレテックス１２２４）５ｇ／Ｌを溶解し、得られた水溶液に酢酸アルミニウム３ｇ／Ｌを添加し、さらにｐＨ調整剤として水酸化ナトリウムを添加してｐＨを９に調整して洗浄剤を得た。アルミダイカスト材（ＡＤＣ−１２）を６０℃、処理時間５分の条件で前記洗浄剤に浸漬させた。
Example 3
30 g / L of sodium tripolyphosphate and 5 g / L of polyoxyethylene nonylphenyl ether (Peletex 1224 manufactured by Miyoshi Oil & Fats Co., Ltd.) are dissolved in water, and 3 g / L of aluminum acetate is added to the resulting aqueous solution. As a result, sodium hydroxide was added to adjust the pH to 9 to obtain a cleaning agent. An aluminum die-cast material (ADC-12) was immersed in the cleaning agent under conditions of 60 ° C. and a treatment time of 5 minutes.
（実施例４）
水にピロリン酸ナトリウム２０ｇ／Ｌ、硫酸ナトリウム２３ｇ／Ｌ及びポリオキシエチレンノニルフェニルエーテル（ミヨシ油脂（株）製 ペレテックス１２２４）５ｇ／Ｌを溶解し、得られた水溶液にカリウム−アルミニウムミョウバン７ｇ／Ｌを添加し、さらにｐＨ調整剤として水酸化ナトリウムを添加してｐＨを９に調整して洗浄剤を得た。アルミダイカスト材（ＡＤＣ−１２）を６０℃、処理時間５分の条件で前記洗浄剤に浸漬させた。
Example 4
Sodium pyrophosphate 20 g / L, sodium sulfate 23 g / L, and polyoxyethylene nonylphenyl ether (Peletex 1224 manufactured by Miyoshi Oil & Fats Co., Ltd.) 5 g / L were dissolved in water, and potassium-aluminum alum 7 g / L was dissolved in the resulting aqueous solution. Further, sodium hydroxide was added as a pH adjuster to adjust the pH to 9 to obtain a cleaning agent. An aluminum die-cast material (ADC-12) was immersed in the cleaning agent under conditions of 60 ° C. and a treatment time of 5 minutes.
（実施例５）
水にピロリン酸カリウム２０ｇ／Ｌ、硫酸ナトリウム５ｇ／Ｌ、ポリオキシエチレンノニルフェニルエーテル（ミヨシ油脂（株）製 ペレテックス１２２４）１ｇ／Ｌ及びエチレンオキサイド−プロピレンオキサイド共重合体（第一工業薬品（株）製 エパン６８０）４ｇ／Ｌを溶解し、得られた水溶液に硫酸アルミニウム５ｇ／Ｌを添加し、さらにｐＨ調整剤として水酸化ナトリウムを添加してｐＨを９に調整して洗浄剤を得た。アルミダイカスト材（ＡＤＣ−１２）を４０℃、処理時間５分の条件で前記洗浄剤に浸漬させた。
(Example 5)
In water, potassium pyrophosphate 20 g / L, sodium sulfate 5 g / L, polyoxyethylene nonylphenyl ether (Peletex 1224 manufactured by Miyoshi Oil & Fats Co., Ltd.) 1 g / L and ethylene oxide-propylene oxide copolymer (Daiichi Kogyo Chemical Co., Ltd.) Epan 680) 4 g / L was dissolved, aluminum sulfate 5 g / L was added to the resulting aqueous solution, and sodium hydroxide was added as a pH adjuster to adjust the pH to 9 to obtain a cleaning agent. . An aluminum die-cast material (ADC-12) was immersed in the cleaning agent under conditions of 40 ° C. and a treatment time of 5 minutes.
（比較例１）
水に第３リン酸ナトリウム２５ｇ／Ｌ、ポリオキシエチレンノニルフェニルエーテル（ミヨシ油脂（株）製 ペレテックス１２２４）４ｇ／Ｌ及びアルキルベンゼンスルホン酸１ｇ／Ｌを溶解し、得られた水溶液にｐＨ調整剤として硫酸を添加してｐＨを９に調整して洗浄剤を得た。アルミダイカスト材（ＡＤＣ−１２）を６０℃、処理時間５分の条件で前記洗浄剤に浸漬させた。
(Comparative Example 1)
Dissolve trisodium triphosphate 25 g / L, polyoxyethylene nonylphenyl ether (Peletex 1224 manufactured by Miyoshi Oil & Fats Co., Ltd.) 4 g / L and alkylbenzene sulfonic acid 1 g / L in water, and use the resulting aqueous solution as a pH adjuster. Sulfuric acid was added to adjust the pH to 9 to obtain a cleaning agent. An aluminum die-cast material (ADC-12) was immersed in the cleaning agent under conditions of 60 ° C. and a treatment time of 5 minutes.
（比較例２）
水に第３リン酸ナトリウム２５ｇ／Ｌ、ポリオキシエチレンノニルフェニルエーテル（ミヨシ油脂（株）製 ペレテックス１２２４）４ｇ／Ｌ及びアルキルベンゼンスルホン酸１ｇ／Ｌを溶解し、得られた水溶液に塩化アルミニウム４ｇ／Ｌを添加し、さらにｐＨ調整剤として水酸化ナトリウムを添加してｐＨを１３に調整して洗浄剤を得た。アルミダイカスト材（ＡＤＣ−１２）を６０℃、処理時間５分の条件で前記洗浄剤に浸漬させた。
(Comparative Example 2)
3 g of sodium triphosphate 25 g / L, 4 g / L of polyoxyethylene nonylphenyl ether (Peletex 1224 manufactured by Miyoshi Oil & Fats Co., Ltd.) and 1 g / L of alkylbenzene sulfonic acid were dissolved in water, and 4 g of aluminum chloride was dissolved in the resulting aqueous solution. L was added, and sodium hydroxide was further added as a pH adjuster to adjust the pH to 13 to obtain a cleaning agent. An aluminum die-cast material (ADC-12) was immersed in the cleaning agent under conditions of 60 ° C. and a treatment time of 5 minutes.
（比較例３）
水にオルトケイ酸ナトリウム１０ｇ／Ｌ、第３リン酸ナトリウム１５ｇ／Ｌ、ポリオキシエチレンノニルフェニルエーテル（ミヨシ油脂（株）製 ペレテックス１２２４）４ｇ／Ｌ及びアルキルベンゼンスルホン酸１ｇ／Ｌを溶解し、得られた水溶液にｐＨ調整剤として硫酸を添加してｐＨを９に調整して洗浄剤を得た。アルミダイカスト材（ＡＤＣ−１２）を６０℃、処理時間５分の条件で前記洗浄剤に浸漬させた。
(Comparative Example 3)
It is obtained by dissolving 10 g / L of sodium orthosilicate, 15 g / L of trisodium phosphate, 4 g / L of polyoxyethylene nonylphenyl ether (Peretex 1224 manufactured by Miyoshi Oil & Fats Co., Ltd.) and 1 g / L of alkylbenzenesulfonic acid in water. Then, sulfuric acid was added to the aqueous solution as a pH adjuster to adjust the pH to 9 to obtain a cleaning agent. An aluminum die-cast material (ADC-12) was immersed in the cleaning agent under conditions of 60 ° C. and a treatment time of 5 minutes.
（比較例４）
水に第３リン酸ナトリウム２０ｇ／Ｌ、ホウ酸ナトリウム７ｇ／Ｌ及びポリオキシエチレンノニルフェニルエーテル（ミヨシ油脂（株）製 ペレテックス１２２４）３ｇ／Ｌを溶解し、得られた水溶液にｐＨ調整剤として硫酸を添加してｐＨを９に調整して洗浄剤を得た。アルミダイカスト材（ＡＤＣ−１２）を６０℃、処理時間５分の条件で前記洗浄剤に浸漬させた。
(Comparative Example 4)
Dissolve trisodium phosphate 20 g / L, sodium borate 7 g / L, and polyoxyethylene nonylphenyl ether (Peretex 1224 manufactured by Miyoshi Oil & Fats Co., Ltd.) 3 g / L in water, and use the resulting aqueous solution as a pH adjuster. Sulfuric acid was added to adjust the pH to 9 to obtain a cleaning agent. An aluminum die-cast material (ADC-12) was immersed in the cleaning agent under conditions of 60 ° C. and a treatment time of 5 minutes.
（評価１：洗浄力の評価）
実施例１〜５及び比較例１〜４の前処理を完了した各アルミニウムダイカスト材の洗浄力を次の外観基準により評価した。なお、この評価で用いたアルミニウムダイカスト材は、アルミニウム用切削油を表面に塗布して３日放置したものを、実施例１〜５及び比較例１〜４において前処理した。
◎：汚れ、油が充分に除去されており、白銀色の外観を表す。
○：汚れ、油が充分に除去されている。
△：汚れ、油が充分に除去されているが外観が黒い。
×：表面積の５％以上の汚れ、油が残存し、その後の表面処理の耐食性に問題がある。
(Evaluation 1: Evaluation of cleaning power)
The detergency of each aluminum die cast material for which the pretreatments of Examples 1 to 5 and Comparative Examples 1 to 4 were completed was evaluated according to the following appearance criteria. In addition, the aluminum die-cast material used in this evaluation was pretreated in Examples 1 to 5 and Comparative Examples 1 to 4 by applying aluminum cutting oil to the surface and leaving it for 3 days.
A: Dirt and oil are sufficiently removed, and a white silver appearance is exhibited.
○: Dirt and oil are sufficiently removed.
Δ: Dirt and oil are sufficiently removed, but the appearance is black.
X: Dirt and oil of 5% or more of the surface area remain, and there is a problem in the corrosion resistance of the subsequent surface treatment.
（評価２：塩水噴霧試験による耐食性評価）
実施例１〜５及び比較例１〜４の前処理を完了した各アルミニウムダイカスト材に、ディップソール株式会社製アルミニウム用３価クロム化成処理剤ＡＬＴ−６１０を用いて、３価クロム化成処理した（Ａ剤濃度１００ｇ／ＬとＢ剤濃度２０ｇ／Ｌを混合した処理液に、温度４０℃で時間６０秒浸漬した）。ＪＩＳＺ２３１７に規定される塩水噴霧による試験を実施し、下記の基準で耐塩水噴霧耐食性を評価した。
○：試験結果２４時間での腐食面積が５％以内。
△：試験結果２４時間での腐食面積が５％以上。
×：試験結果１２時間での腐食面積が５％以上。
(Evaluation 2: Corrosion resistance evaluation by salt spray test)
Trivalent chromium chemical conversion treatment was performed on each aluminum die-cast material for which the pretreatments of Examples 1 to 5 and Comparative Examples 1 to 4 were completed using a trivalent chromium chemical conversion treatment agent ALT-610 manufactured by Dipsol Co., Ltd. ( It was immersed for 60 seconds at a temperature of 40 ° C. in a treatment liquid in which the concentration of Agent A was 100 g / L and the concentration of Agent B was 20 g / L). The test by salt spray prescribed in JISZ2317 was carried out, and the salt spray corrosion resistance was evaluated according to the following criteria.
○: Corrosion area within 5% within 24 hours of test results.
(Triangle | delta): The corrosion area in 24 hours of a test result is 5% or more.
X: Corrosion area in test result 12 hours is 5% or more.
（評価３：塗膜密着性試験による塗膜密着性評価）
実施例１〜５及び比較例１〜４の前処理を完了した各マグネシウムダイカスト材に塗装を行い（下塗り：エポキシ／ポリエステル樹脂系（久保高ペイント ＡＲＢｔ・１００プライマー）、１６０℃、２０分焼付け；上塗り：アクリル樹脂系（久保高ペイント アクリオンホワイト５００・１００）、１６０℃、２０分焼き付け）、ＪＩＳＫ５４００に規定される碁盤目テープ法による密着性を下記の基準で評価した。
◎：切り傷１本ごとが、細く滑らかで、切り傷の交点と正方形の１目１目にはがれが無い。
○：切り傷の交点にわずかなはがれがあって、正方形の１目１目にはがれが無く欠損部の面積は全正方形の５％以内。
△：切り傷の両側と交点とにはがれがあって、欠損部の面積は全正方形の５〜１５％。
×：切り傷によるはがれの幅が広く、欠損部の面積は全正方形の１５％以上。
以上の評価結果を表２に示す。
(Evaluation 3: Evaluation of coating film adhesion by coating film adhesion test)
Each magnesium die-cast material which completed the pretreatment of Examples 1 to 5 and Comparative Examples 1 to 4 was coated (undercoat: epoxy / polyester resin system (Kubo High Paint ARBt • 100 primer), and baked at 160 ° C. for 20 minutes; Top coating: Acrylic resin-based (Kubo High Paint Acryon White 500/100), 160 ° C., baked for 20 minutes), adhesiveness according to the cross-cut tape method defined in JISK5400 was evaluated according to the following criteria.
A: Each cut is thin and smooth, and there is no peeling between the intersection of the cut and the square.
○: There is a slight peeling at the intersection of the cuts, there is no peeling at the first square, and the area of the defect is within 5% of the total square.
(Triangle | delta): There exists peeling in the both sides and intersection of a cut, and the area of a defect | deletion part is 5 to 15% of all the squares.
X: The width of the peeling due to the cut is wide, and the area of the defect is 15% or more of the total square.
The above evaluation results are shown in Table 2.
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| JPS5921956B2 (en) * | 1976-10-07 | 1984-05-23 | 日産自動車株式会社 | Metal surface cleaning composition |
| JPS54148141A (en) * | 1978-05-12 | 1979-11-20 | Showa Keikinzoku Kk | Formation of anodized layer on aluminum surface |
| JP3333611B2 (en) * | 1993-11-09 | 2002-10-15 | 日本パーカライジング株式会社 | Hexavalent chromium-free chemical conversion surface treatment agent for aluminum and aluminum alloys |
| JP3490021B2 (en) * | 1998-09-08 | 2004-01-26 | 日本パーカライジング株式会社 | Alkaline degreasing solution for metal material and method of using the same |
| JP5051679B2 (en) * | 2003-08-29 | 2012-10-17 | 日本パーカライジング株式会社 | Alkali cleaning method for aluminum or aluminum alloy DI can |
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