JP2013032554A - Surface treatment liquid for fastening member - Google Patents
Surface treatment liquid for fastening member Download PDFInfo
- Publication number
- JP2013032554A JP2013032554A JP2011167772A JP2011167772A JP2013032554A JP 2013032554 A JP2013032554 A JP 2013032554A JP 2011167772 A JP2011167772 A JP 2011167772A JP 2011167772 A JP2011167772 A JP 2011167772A JP 2013032554 A JP2013032554 A JP 2013032554A
- Authority
- JP
- Japan
- Prior art keywords
- surface treatment
- treatment liquid
- film
- magnesium
- coated
- 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.)
- Granted
Links
- 238000004381 surface treatment Methods 0.000 title claims abstract description 83
- 239000007788 liquid Substances 0.000 title claims abstract description 79
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 239000011701 zinc Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 18
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002738 chelating agent Substances 0.000 claims description 20
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 150000002681 magnesium compounds Chemical class 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical group OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims 2
- 238000005260 corrosion Methods 0.000 abstract description 32
- 230000007797 corrosion Effects 0.000 abstract description 32
- 229910019142 PO4 Inorganic materials 0.000 abstract description 16
- 239000010452 phosphate Substances 0.000 abstract description 16
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000013522 chelant Substances 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- -1 phosphate compound Chemical class 0.000 description 14
- 238000007747 plating Methods 0.000 description 11
- 239000003973 paint Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 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 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- OXAUNDBQHKIUSD-UHFFFAOYSA-N azanium;titanium;fluoride Chemical compound [NH4+].[F-].[Ti] OXAUNDBQHKIUSD-UHFFFAOYSA-N 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- HLJCWGPUCQTHFY-UHFFFAOYSA-H disodium;hexafluorotitanium(2-) Chemical compound [F-].[F-].[Na+].[Na+].F[Ti](F)(F)F HLJCWGPUCQTHFY-UHFFFAOYSA-H 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- UWTJALAXUKLZON-UHFFFAOYSA-I lithium titanium(4+) pentafluoride Chemical compound [Li+].[F-].[F-].[F-].[F-].[F-].[Ti+4] UWTJALAXUKLZON-UHFFFAOYSA-I 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical class [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- SQTLECAKIMBJGK-UHFFFAOYSA-I potassium;titanium(4+);pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[K+].[Ti+4] SQTLECAKIMBJGK-UHFFFAOYSA-I 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
本発明は、締結部品の表面処理に用いる表面処理液に関し、さらに詳しくはクロムを含まない、環境負荷を軽減した耐食性に優れる表面処理皮膜を形成するための表面処理液に関する。 The present invention relates to a surface treatment liquid used for the surface treatment of fastening parts, and more particularly to a surface treatment liquid for forming a surface treatment film that does not contain chromium and has excellent corrosion resistance with reduced environmental load.
従来、耐食性の良好なねじ、ボルト、ナットなどの締結部品を亜鉛めっきされたものが多用されているが、湿潤雰囲気、排ガス雰囲気、海岸近傍の雰囲気等に長期間にわたって曝されると表面に白錆が発生し、外観を劣化させる。また、さらに腐食が進むと、基材が腐食して赤錆が発生し、基材の強度を劣化させる。このような錆の防止には、亜鉛めっきされた締結部品をクロメート処理する方法が採用されていた。しかし、クロメート処理では、クロムイオンを含む廃液の処理に多大な負担がかかる。また、環境負荷物質の削減として、六価クロムの廃止やクロムフリーの要求が強くなっている。 Conventionally, galvanized fastening parts such as screws, bolts and nuts with good corrosion resistance have been used. However, when exposed to humid atmosphere, exhaust gas atmosphere, atmosphere near the coast, etc. for a long time, the surface becomes white. Rust is generated and the appearance is deteriorated. Further, when the corrosion further progresses, the base material corrodes and red rust is generated, and the strength of the base material is deteriorated. In order to prevent such rust, a method of chromating a galvanized fastening part has been adopted. However, the chromate treatment places a great burden on the treatment of the waste liquid containing chromium ions. In addition, the abolition of hexavalent chromium and the demand for chromium-free materials are increasing as a means of reducing environmentally hazardous substances.
亜鉛めっき鋼板に用いるクロムフリーの処理液として、たとえば、特許文献１には、チタン、ジルコニウムなどのフッ素化合物と、コバルト、マンガン、マグネシウム、アルミニウムなどの陽イオンを含む酸性液状組成物を用いて被膜を形成することが示されている。 As a chromium-free treatment liquid used for a galvanized steel sheet, for example, Patent Document 1 discloses a coating using an acidic liquid composition containing a fluorine compound such as titanium or zirconium and a cation such as cobalt, manganese, magnesium, or aluminum. Has been shown to form.
また特許文献２には、亜鉛めっき鋼板の表面処理に用いる表面処理液として、水溶性の多価金属リン酸塩化合物と、ヘキサフルオロチタン酸（またはその塩）と、バナジウム化合物と、キレート剤とを含む表面処理液が示されている。 Patent Document 2 discloses a water-soluble polyvalent metal phosphate compound, hexafluorotitanic acid (or a salt thereof), a vanadium compound, and a chelating agent as a surface treatment liquid used for the surface treatment of a galvanized steel sheet. A surface treatment liquid containing is shown.
しかしながら、前述の処理液を締結部品に適用した場合、耐食性は良好ではない。これは、締結部品は形状の凹凸が激しく、特に突起部に被覆された亜鉛は反応性に富むので、前述の酸性の処理液と反応し、亜鉛被覆が反応により消失してしまうことが原因である。 However, when the above-mentioned processing liquid is applied to a fastening part, the corrosion resistance is not good. This is because the fastening parts have severe irregularities in the shape, especially the zinc coated on the protrusions is highly reactive, so it reacts with the above acidic treatment liquid and the zinc coating disappears due to the reaction. is there.
一方、亜鉛被覆との反応を抑制するために、処理液を中性からアルカリ性にした場合には、密着性が著しく悪くなり、やはり耐食性は良好ではない。 On the other hand, when the treatment liquid is changed from neutral to alkaline in order to suppress the reaction with the zinc coating, the adhesion is remarkably deteriorated and the corrosion resistance is not good.
また、処理液は、強酸性から弱酸性へ酸性度が減るにしたがい、液が不安定になり、不均一な沈澱が生じ易い。このような処理液を締結部品に塗布すると不均一な皮膜が生じやすく、皮膜の密着性低下をきたし、それにより耐食性が劣化しやすい。 Further, as the acidity of the treatment liquid decreases from strong acidity to weak acidity, the liquid becomes unstable and non-uniform precipitation tends to occur. When such a treatment liquid is applied to a fastening part, a non-uniform film is likely to be formed, and the adhesion of the film is lowered, thereby easily deteriorating the corrosion resistance.
本発明の目的は、凹凸のある締結部品の亜鉛または亜鉛合金を含む被覆材に対しても反応性が小さく、また該被覆部と密着性が良く耐食性の良好な皮膜を形成する締結部品用の安定な表面処理液を提供することにある。 It is an object of the present invention to provide a fastening component that has a low reactivity with respect to a coating material containing zinc or a zinc alloy of an uneven fastening component and that forms a film having good adhesion and good corrosion resistance with the coating portion. The object is to provide a stable surface treatment solution.
さらにまた、本発明の目的は、前記表面処理液により皮膜を形成してなる締結部品の表面上にさらに上塗り塗料を被覆する場合において、該上塗り塗料層との密着性の良好な下地材としての機能も併せ持つ皮膜を形成することが可能な表面処理液を提供することにある。 Furthermore, an object of the present invention is to provide a base material having good adhesion to the top coating layer in the case where a top coating is further coated on the surface of the fastening part formed with the surface treatment liquid. An object of the present invention is to provide a surface treatment liquid capable of forming a film having a function.
本発明は、亜鉛または亜鉛合金を含む被覆材で被覆処理を施した締結部品の表面上に皮膜を形成するための表面処理液であって、第一リン酸アルミニウムおよび第一リン酸マグネシウムの少なくとも１種と、ヘキサフルオロチタン酸もしくはその塩と、キレート剤を含み、かつ表面処理液がｐＨ２〜５に調整されてなることを特徴とする締結部品用表面処理液である。 The present invention relates to a surface treatment liquid for forming a film on the surface of a fastening part that has been coated with a coating material containing zinc or a zinc alloy, and includes at least one of primary aluminum phosphate and primary magnesium phosphate. A surface treatment liquid for fastening parts, which comprises one type, hexafluorotitanic acid or a salt thereof, and a chelating agent, and the surface treatment liquid is adjusted to pH 2-5.
また本発明は、亜鉛または亜鉛合金を含む被覆材で被覆された締結部品の表面上に皮膜を形成するための表面処理液であって、第一リン酸アルミニウムおよび第一リン酸マグネシウムの１種または２種と、ヘキサフルオロチタン酸もしくはその塩と、キレート剤と、水酸化マグネシウム、酸化マグネシウムおよび炭酸マグネシウムから選択される１種以上のマグネシウム化合物を含み、ｐＨが２〜５に調整されてなることを特徴とする締結部品用表面処理液である。 The present invention also provides a surface treatment liquid for forming a film on the surface of a fastening part coated with a coating material containing zinc or a zinc alloy, which is one kind of primary aluminum phosphate and primary magnesium phosphate. Or two types, hexafluoro titanic acid or its salt, a chelating agent, and 1 or more types of magnesium compounds selected from magnesium hydroxide, magnesium oxide, and magnesium carbonate, and pH is adjusted to 2-5 This is a surface treatment liquid for fastening parts.
また本発明は、前記表面処理液が、亜鉛または亜鉛合金を含む被覆材で被覆処理を施した締結部品に皮膜を形成するための締結部品用表面処理液である。 Moreover, this invention is a surface treatment liquid for fastening parts for the said surface treatment liquid to form a membrane | film | coat on the fastening part which performed the coating process with the coating material containing zinc or a zinc alloy.
また本発明は、表面処理液が、ｐＨ３〜４に調整されてなる締結部品用表面処理液である。 Moreover, this invention is a surface treatment liquid for fastening components by which surface treatment liquid is adjusted to pH 3-4.
また本発明は、前記キレート剤が、１−ヒドロキシエチリデン−１，１−ジホスホン酸である締結部品用表面処理液である。 Moreover, this invention is a surface treatment liquid for fastening parts whose said chelating agent is 1-hydroxy ethylidene-1, 1- diphosphonic acid.
また本発明は、アンモニア水溶液によってｐＨ調整されてなる締結部品用表面処理液である。 Further, the present invention is a surface treatment liquid for fastening parts, the pH of which is adjusted with an aqueous ammonia solution.
本発明によると、凹凸のある締結部品の亜鉛または亜鉛合金を含む被覆層に対しても反応性が小さく、また該被覆層との密着性が良い、皮膜耐食性が良好な皮膜を形成する表面処理液を提供することができ、これにより、耐食性の良好な被覆締結部品を提供することができる。 According to the present invention, a surface treatment that forms a film with low film corrosion resistance and good reactivity with a coating layer containing zinc or a zinc alloy of an uneven fastening part and having good adhesion to the coating layer. A liquid can be provided, and thereby a coated fastening part having good corrosion resistance can be provided.
また、本発明によると、前記表面処理液による被覆締結部品の表面にさらに上塗り塗料による被覆を行う場合に、前記皮膜は、上塗り塗料との密着性が良好であり、より耐食性が良好な被覆締結部品を提供することができる。 Further, according to the present invention, when the surface of the coated fastening part with the surface treatment liquid is further coated with a top coating, the coating has good adhesion with the top coating and has a better corrosion resistance. Parts can be provided.
本発明において、亜鉛または亜鉛合金を含む被覆材で被覆処理を施した締結部品としては、前記被覆処理を施したねじ、ボルト、ナット、ワッシャー、リベット、ピン、レンチ、止め輪、ビス、スクリュー、座金、スペーサー、シムなど、部材と部材を固定するために使用される締結用部品が挙げられる。 In the present invention, as a fastening part coated with a coating material containing zinc or a zinc alloy, screws, bolts, nuts, washers, rivets, pins, wrench, retaining rings, screws, screws, Examples include fastening parts used for fixing members such as washers, spacers, and shims.
亜鉛または亜鉛合金を含む被覆材による被覆処理としては、亜鉛めっきまたは亜鉛合金めっき、またはジンクリッチ塗料による被覆処理等を挙げることができ、とりわけ、亜鉛めっきによって被覆された締結部品に対して好適に保護皮膜を形成することができる。 Examples of the coating treatment with a coating material containing zinc or zinc alloy include zinc plating, zinc alloy plating, coating treatment with zinc rich paint, etc., and particularly suitable for fastening parts coated with zinc plating. A protective film can be formed.
この亜鉛めっきまたは亜鉛合金めっきとしては、特に制限されないが、溶融亜鉛めっき、溶融Ｚｎ−５質量％Ａｌ合金めっき、溶融Ｚｎ−５５質量％Ａｌ合金めっき、電気亜鉛めっき、電気Ｚｎ−Ｎｉ合金めっき等を挙げることができる。 The zinc plating or zinc alloy plating is not particularly limited, but includes hot dip galvanizing, hot dip Zn-5 mass% Al alloy plating, hot dip Zn-55 mass% Al alloy plating, electrogalvanizing, electric Zn-Ni alloy plating, etc. Can be mentioned.
本発明の表面処理液に含有される第一リン酸アルミニウムおよび第一リン酸マグネシウムは、皮膜を形成する主体(ベース)となる成分である。第一リン酸アルミニウムおよび第一リン酸マグネシウムは、工業的に製造され、市販されているものであれば、いずれも好適に使用することができる。また、第一リン酸アルミニウムとしては、Ａｌ／Ｐのモル比が０．７／３〜１．２／２のものが好ましく、第一リン酸マグネシウムとしては、Ｍｇ／Ｐのモル比が０．７／２〜１．２／２のものが好ましい。 The primary aluminum phosphate and primary magnesium phosphate contained in the surface treatment liquid of the present invention are components that are the main (base) for forming a film. Any of primary aluminum phosphate and primary magnesium phosphate can be suitably used as long as they are industrially manufactured and commercially available. The primary aluminum phosphate preferably has an Al / P molar ratio of 0.7 / 3 to 1.2 / 2, and the primary magnesium phosphate has an Mg / P molar ratio of 0.00. 7/2 to 1.2 / 2 are preferred.
これら第一リン酸アルミニウムおよび第一リン酸マグネシウムは、それぞれの１種を単独で使用することもでき、２種を併用することもできる。 These primary aluminum phosphates and primary magnesium phosphates can be used alone or in combination of two.
表面処理液中の第一リン酸アルミニウムおよび第一リン酸マグネシウム（以下、本発明においては、これらの１種または２種を総称してリン酸塩化合物ということがある）の濃度は、表面処理液全体に対して１重量％以上５０重量％以下となる量を用いることが好ましい。１重量％未満では、加水分解を起こし沈殿を生じることがあり、５０重量％を超えると、このリン酸塩化合物の溶解度を超えてリン酸塩化合物が沈殿し、表面処理液の安定性に問題を生じることがある。 The concentration of primary aluminum phosphate and primary magnesium phosphate (hereinafter, in the present invention, one or two of them may be collectively referred to as a phosphate compound) in the surface treatment liquid is determined by the surface treatment. It is preferable to use an amount of 1% by weight or more and 50% by weight or less with respect to the whole liquid. If the amount is less than 1% by weight, hydrolysis may occur and precipitation may occur. If the amount exceeds 50% by weight, the phosphate compound precipitates exceeding the solubility of the phosphate compound, and the stability of the surface treatment solution is problematic. May occur.
また、本発明の表面処理液に含有されるヘキサフルオロチタン酸(チタンフッ化水素酸)は、遊離のものであっても、またその塩であっても、工業的に製造され、市販されているものであれば、いずれも好適に使用することができる。 Further, the hexafluorotitanic acid (titanium hydrofluoric acid) contained in the surface treatment liquid of the present invention is industrially produced and commercially available, whether it is free or a salt thereof. Any material can be suitably used.
ヘキサフルオロチタン酸の塩としては、リチウム、カリウム、ナトリウムなどのアルカリ金属との塩やアンモニウム塩が挙げられる。 Examples of the salt of hexafluorotitanic acid include salts with alkali metals such as lithium, potassium and sodium, and ammonium salts.
具体的な化合物として、ヘキサフルオロチタン酸ナトリウム(チタンフッ化ナトリウム)、ヘキサフルオロチタン酸カリウム(チタンフッ化カリウム)、ヘキサフルオロチタン酸リチウム(チタンフッ化リチウム)およびヘキサフルオロチタン酸アンモニウム(チタンフッ化アンモニウム)などを挙げることができる。これらのうち、ヘキサフルオロチタン酸塩としては、ヘキサフルオロチタン酸アンモニウムが好ましい。 Specific compounds include sodium hexafluorotitanate (sodium titanium fluoride), potassium hexafluorotitanate (potassium titanium fluoride), lithium hexafluorotitanate (lithium titanium fluoride), and ammonium hexafluorotitanate (ammonium titanium fluoride). Can be mentioned. Of these, the hexafluorotitanate is preferably ammonium hexafluorotitanate.
本発明の表面処理液においては、ヘキサフルオロチタン酸は、遊離のものとその塩を、それぞれ単独で使用することもでき、遊離のものとその塩とを併用することもできる。 In the surface treatment liquid of the present invention, the hexafluorotitanic acid can be used alone or in combination with a free salt thereof, or the free product and salt thereof can be used in combination.
ヘキサフルオロチタン酸（以下、ヘキサフルオロチタン酸塩を含めた意味で、ヘキサフルオロチタン酸ということがある）は、前記リン酸塩化合物１００重童部に対して、１０重量部以上１０００重量部以下含有することが好ましい。１０重量部未満では、優れた耐食性を有する均一で緻密な皮膜を形成することができず、また、形成された皮膜は、機械的強度が低くなってしまう。また、１０００重量部を超えると結合に関与しないチタンが増えすぎて、優れた耐食性を有する均一で緻密な皮膜を形成することができず、形成された皮膜の機械的強度が低くなる。 Hexafluorotitanic acid (hereinafter sometimes referred to as hexafluorotitanate in the meaning including hexafluorotitanate) is 10 parts by weight or more and 1000 parts by weight or less with respect to 100 parts by weight of the phosphate compound. It is preferable to contain. If the amount is less than 10 parts by weight, a uniform and dense film having excellent corrosion resistance cannot be formed, and the formed film has low mechanical strength. On the other hand, when the amount exceeds 1000 parts by weight, the amount of titanium that does not participate in the bonding increases so much that a uniform and dense film having excellent corrosion resistance cannot be formed, and the mechanical strength of the formed film is lowered.
本発明の表面処理液では、ヘキサフルオロチタン酸を含むことで、このリン酸塩化合物のリン酸基同士を、チタンを介在させた結合(リン酸基−チタン−リン酸基)を形成することができる。この結合形成は、低い焼き付け温度で、皮膜を形成することができる。この皮膜は、チタンを介在させた結合が形成されることによって、耐アルカリ性が高くなり、さらに、機械的強度が高くなる。 In the surface treatment liquid of the present invention, by containing hexafluorotitanic acid, the phosphate groups of this phosphate compound form a bond (phosphate group-titanium-phosphate group) with titanium interposed therebetween. Can do. This bond formation can form a film at a low baking temperature. This film has a high alkali resistance and a high mechanical strength by forming a bond with titanium interposed.
本発明の表面処理液に含有されるキレート剤は、リン酸塩化合物との反応により、網状(ネットワーク)構造をもつ皮膜を形成させることができるものであれば、どのようなキレート剤でも使用することができる。 As the chelating agent contained in the surface treatment liquid of the present invention, any chelating agent can be used as long as it can form a film having a network structure by reaction with a phosphate compound. be able to.
かかるキレート剤としては、たとえばホスホン酸系キレート剤やオキシカルボン酸系キレート剤が挙げられ、本発明においては、特に、ホスホン酸系キレート剤が好ましい。 Examples of such chelating agents include phosphonic acid chelating agents and oxycarboxylic acid chelating agents. In the present invention, phosphonic acid chelating agents are particularly preferred.
ホスホン酸系キレート剤の具体例としては、アミノトリメチレンホスホン酸、１−ヒドロキシアリキリデン−１，１−ジホスホン酸、エチレンジアミンテトラメチレンホスホン酸、ヘキサメチレンジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸またはそれらの塩を挙げることができる。 Specific examples of the phosphonic acid-based chelating agent include aminotrimethylenephosphonic acid, 1-hydroxyalkylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, Mention may be made of their salts.
特に、表面処理液を製造する際の溶解性の観点から、１−ヒドロキシアリキリデン−１，１−ジホスホン酸またはその塩が好ましい。さらに好ましくは、１−ヒドロキシエチリデン−１，１−ジホスホン酸またはその塩である。 In particular, 1-hydroxyalkylidene-1,1-diphosphonic acid or a salt thereof is preferable from the viewpoint of solubility when producing the surface treatment liquid. More preferred is 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof.
上記キレート剤の塩としては、たとえばリチウム、カリウム、ナトリウムなどのアルカリ金属との塩やアンモニウム塩が挙げられる。 Examples of the salt of the chelating agent include salts with alkali metals such as lithium, potassium and sodium, and ammonium salts.
表面処理液中のキレート剤は、前記リン酸塩化合物１００重量部に対して、１０重量部以上１０００重量部以下含有することが好ましい。１０重量部未満では、充分な耐食性を得ることができず、１０００重量部を超えると、形成された皮膜がべたつきを生じることがある。 The chelating agent in the surface treatment liquid is preferably contained in an amount of 10 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the phosphate compound. If it is less than 10 parts by weight, sufficient corrosion resistance cannot be obtained, and if it exceeds 1000 parts by weight, the formed film may be sticky.
本発明の表面処理液は、キレート剤を含むことで、リン酸塩化合物のリン酸基同士の脱水縮合反応に加えて、リン酸塩化合物とキレート剤との反応により、網状(ネットワーク)構造をもつ皮膜が形成される。この皮膜形成は、低い焼き付け温度で、均一で緻密な皮膜を形成することができる。したがって、この表面処理液は、低い焼き付け温度で、優れた耐食性を有する皮膜を亜鉛または亜鉛合金を含む被覆材により被覆処理された締結部品の上に形成することができる。 The surface treatment liquid of the present invention contains a chelating agent, and in addition to the dehydration condensation reaction between the phosphate groups of the phosphate compound, a reaction between the phosphate compound and the chelating agent results in a network (network) structure. A film is formed. This film formation can form a uniform and dense film at a low baking temperature. Therefore, this surface treatment liquid can form a film having excellent corrosion resistance on a fastening part coated with a coating material containing zinc or a zinc alloy at a low baking temperature.
本発明の表面処理液は、前記リン酸塩化合物、ヘキサフルオロチタン酸およびキレート剤の所定量を、水性媒体に溶解させたのち、表面処理液ｐＨが２〜５の範囲となるように調整することによって、製造することができる。 The surface treatment liquid of the present invention is adjusted so that the pH of the surface treatment liquid is in the range of 2 to 5 after dissolving predetermined amounts of the phosphate compound, hexafluorotitanic acid and chelating agent in an aqueous medium. Can be manufactured.
水性媒体としては、水のみであってもよいし、水と水溶性有機溶媒との混合溶媒であってもよいが、水のみであることが好ましい。 The aqueous medium may be water alone or a mixed solvent of water and a water-soluble organic solvent, but is preferably water alone.
また、表面処理液のｐＨを調整するためには、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物やアンモニア水溶液などのアルカリ剤を用いることができる。このうち、塗布して焼き付け中に大半が気散して皮膜に影響を及ぼさないアンモニア水が好ましい。 In order to adjust the pH of the surface treatment solution, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an alkaline agent such as an aqueous ammonia solution can be used. Of these, ammonia water which is mostly diffused during application and baking and does not affect the film is preferred.
表面処理液のｐＨ調整を行わない場合には、ｐＨが低いため、そのまま塗布すると、亜鉛または亜鉛合金を含む被覆層が反応で毀損するか、溶解して消失してしまう。このため耐食性が著しく低下する。 When pH adjustment of the surface treatment liquid is not performed, since the pH is low, if it is applied as it is, the coating layer containing zinc or the zinc alloy is damaged by the reaction or dissolved and disappears. For this reason, corrosion resistance falls remarkably.
表面処理液のｐＨが２より低いと被覆層に対する反応性抑制の効果が小さく、５より大きいと表面処理液の安定性が悪く、密着性が悪くなるので好ましくない。
本発明の表面処理液の、さらに好ましいｐＨの範囲は３〜４である。
If the pH of the surface treatment liquid is lower than 2, the effect of suppressing the reactivity with respect to the coating layer is small, and if it is larger than 5, the stability of the surface treatment liquid is poor and the adhesion is deteriorated.
The more preferable pH range of the surface treatment liquid of the present invention is 3-4.
本発明の表面処理液は、ｐＨ１前後の強酸性からｐＨが上昇するにしたがい、リン酸塩化合物の脱水縮合反応が弱くなる傾向があり、このため脱水縮合反応による被膜形成が不十分となり、結果として被覆材の耐食性が悪くなるという傾向がある。 The surface treatment solution of the present invention tends to weaken the dehydration condensation reaction of the phosphate compound as the pH increases from strong acidity around pH 1, and as a result, film formation by the dehydration condensation reaction becomes insufficient, resulting in As a result, the corrosion resistance of the covering material tends to deteriorate.
これを防ぐために、表面処理液に、さらにマグネシウム化合物を含有させることによって、脱水縮合反応を促進し、ｐＨ３〜４でも安定して密着性の良い皮膜を得ることが出来る。 In order to prevent this, by adding a magnesium compound to the surface treatment liquid, the dehydration condensation reaction is promoted, and a film having good adhesion can be obtained stably even at pH 3-4.
かかるマグネシウム化合物としては、炭酸マグネシウム、水酸化マグネシウムおよび酸化マグネシウムが挙げられ、これらは単独で、または２種以上を併用することができる。 Examples of the magnesium compound include magnesium carbonate, magnesium hydroxide, and magnesium oxide, and these can be used alone or in combination of two or more.
マグネシウム化合物は、前記リン酸塩化合物やヘキサフルオロチタン酸を水性媒体に溶解する際に、加えてもよく、あるいはリン酸塩化合物やヘキサフルオロチタン酸を水性媒体に溶解した後に加えてもよい。 The magnesium compound may be added when the phosphate compound or hexafluorotitanic acid is dissolved in an aqueous medium, or may be added after the phosphate compound or hexafluorotitanic acid is dissolved in an aqueous medium.
このマグネシウム化合物によって、皮膜物性もバラツキが少なく、さらに良好な耐食性を得ることができる。 With this magnesium compound, there is little variation in film physical properties, and better corrosion resistance can be obtained.
マグネシウム化合物は、リン酸塩化合物に対して０．２〜２０重量部となるよう含有させることが好ましい。０．２重量部未満の場合には、アンモニア水溶液でｐＨ３〜４に維持する場合に、皮膜形成に対する改良効果はあまり認められず、２０重量部を超えると安定性が劣る傾向がある。 It is preferable to contain a magnesium compound so that it may become 0.2-20 weight part with respect to a phosphate compound. When the amount is less than 0.2 parts by weight, when the pH is maintained at 3 to 4 with an aqueous ammonia solution, the effect of improving the film formation is not so much observed. When the amount exceeds 20 parts by weight, the stability tends to be inferior.
かくして得られた、本発明の表面処理液は、有害なクロム化合物を含有していないため、従来のクロム化合物の使用による環境汚染などの問題は、発生しない。 Since the surface treatment liquid of the present invention thus obtained does not contain harmful chromium compounds, problems such as environmental pollution due to the use of conventional chromium compounds do not occur.
この表面処理液は、亜鉛または亜鉛合金を含む被覆材で被覆された締結部品の表面に塗布して低温で焼き付けることにより、均一で緻密な膜が形成される。 This surface treatment liquid is applied to the surface of a fastening part coated with a coating material containing zinc or a zinc alloy and baked at a low temperature, whereby a uniform and dense film is formed.
締結部品に表面処理液を塗布するには、この技術分野において常用される方法によって実施することができ、たとえば噴霧、塗布、浸漬などの方法を採用することができる。 The surface treatment liquid can be applied to the fastening part by a method commonly used in this technical field. For example, methods such as spraying, application, and immersion can be adopted.
たとえば、浸漬方法によるときは、亜鉛または亜鉛合金を含む被覆材で被覆された締結部品をこの表面処理液に浸漬し、引き上げて遠心振り切りにより塗布する。これにより、０．２〜５μｍ程度の皮膜を塗布することが可能である。 For example, when the dipping method is used, a fastening part coated with a coating material containing zinc or a zinc alloy is dipped in the surface treatment solution, pulled up, and applied by centrifugal shaking. Thereby, it is possible to apply a film of about 0.2 to 5 μm.
焼き付けは、特に限定されないが、たとえば、熱風式、赤外式、および誘導加熱式などなどの焼き付け方法によって行うことができる。また、焼き付け温度は、５０℃以上２００℃以下で行うことができる。焼き付け温度が５０℃未満では、焼き付けが不十分となり、皮膜形成ができず、２００℃を超えると、皮膜の耐食性の向上が得られず、製造効率が悪くなる。 Although baking is not specifically limited, For example, it can carry out by baking methods, such as a hot air type, an infrared type, and an induction heating type. The baking temperature can be 50 ° C. or higher and 200 ° C. or lower. If the baking temperature is less than 50 ° C., baking will be insufficient and film formation will not be possible, and if it exceeds 200 ° C., the corrosion resistance of the film will not be improved, resulting in poor production efficiency.
このようにして得られた、前記表面処理液で被覆された締結部品の表面に、高耐食や意匠（色彩の付与）などの目的で、さらに上塗り塗料を施すことが可能である。この上塗り塗料は、有機樹脂塗料や無機系塗料などを使用することができる。 A top coating can be further applied to the surface of the fastening part coated with the surface treatment liquid thus obtained for the purpose of high corrosion resistance, design (coloring), and the like. An organic resin paint or an inorganic paint can be used as the top coat.
このような上塗り塗料としては、好ましくは工業用の焼付硬化型有機樹脂塗料を挙げることができ、特に好ましくは、エポキシ系、ポリエステル系、アクリル系または、フッ素系の有機樹脂塗料、またはこれらから選択される２種以上を混合してなる有機樹脂塗料を使用することができる。 As such a top coat, an industrial baking curable organic resin paint is preferable, and an epoxy-based, polyester-based, acrylic-based, or fluorine-based organic resin paint, or selected from these is particularly preferable. An organic resin paint obtained by mixing two or more of them can be used.
有機樹脂塗料をベースとする上塗り塗料の被覆を施す場合、特に無機系の被覆締結部品との密着性が問題となる。たとえば亜鉛めっきされた締結部品の上に直接これら有機樹脂塗料を被覆した場合には、なじみ性、濡れ性が悪く密着性のよい被覆層を形成することが困難である。これに対し、本発明の表面処理液で被覆された締結部品は、上塗り塗料とのなじみ性、濡れ性が良く、結果として密着性が極めて良好であり、耐食性も良好となることがわかった。 When coating with a top coating based on an organic resin coating, adhesion to an inorganic coated fastening component is a problem. For example, when these organic resin paints are directly coated on a galvanized fastening part, it is difficult to form a coating layer with poor conformability and wettability and good adhesion. On the other hand, it was found that the fastening parts coated with the surface treatment liquid of the present invention have good conformability and wettability with the top coating, resulting in extremely good adhesion and good corrosion resistance.
上塗り塗料の塗布法は、好ましくは、本発明の表面処理液で被覆された亜鉛めっき締結部品を上塗り塗料中に浸漬し、引き上げて塗布するかまたは、引上げた後遠心振り切りにより塗布することが可能である。これにより、３〜２０μｍ程度の皮膜を塗布することが可能である。 The method of applying the top coating is preferably such that the galvanized fastening part coated with the surface treatment liquid of the present invention is dipped in the top coating and then pulled up or applied by centrifugation after being pulled up. It is. Thereby, it is possible to apply a film of about 3 to 20 μm.
焼き付けは、特に限定されないが、たとえば、熱風式、赤外式、および誘導加熱式などなどの焼き付け方法によって行うことができる。また、焼き付け温度は、８０℃以上３５０℃以下で行うことができる。 Although baking is not specifically limited, For example, it can carry out by baking methods, such as a hot air type, an infrared type, and an induction heating type. The baking temperature can be 80 ° C. or higher and 350 ° C. or lower.
以下、実施例により本発明を具体的に説明するが、これによって本発明が限定されるものではない。実施例および比較例中、表面処理液の％は、重量％を表し、残部は水である。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by this. In the examples and comparative examples,% of the surface treatment liquid represents weight%, and the balance is water.
実施例１
表面処理液として、第一リン酸アルミニウム（Ａｌ／Ｐ原子比＝０．９／３）８．５％、と、チタンフッ化水素酸４．０％と、チタンフッ化アンモニウム０．８％と、水酸化マグネシウム０．６％と、キレート剤として、１−ヒドロキシエチリデン−１，１−ジホスホン酸７．１％と、水酸化マグネシウム０．６％、残部が水からなる水溶液を調整した。このときのｐＨは１．１であった。さらに、この水溶液にアンモニア水溶液をアンモニア換算で６．８％加えｐＨを３．３に調整することによって、表面処理液を製造した。この表面処理液の安定性を下記に示す方法で評価した。結果を表１に示す。
Example 1
As surface treatment liquid, primary aluminum phosphate (Al / P atomic ratio = 0.9 / 3) 8.5%, titanium hydrofluoric acid 4.0%, titanium ammonium fluoride 0.8%, water An aqueous solution containing magnesium oxide 0.6%, 1-hydroxyethylidene-1,1-diphosphonic acid 7.1%, magnesium hydroxide 0.6% and the balance water was prepared as a chelating agent. The pH at this time was 1.1. Furthermore, an aqueous ammonia solution was added to the aqueous solution in an amount of 6.8% in terms of ammonia to adjust the pH to 3.3, thereby producing a surface treatment liquid. The stability of this surface treatment solution was evaluated by the method shown below. The results are shown in Table 1.
また、締結部品として、電気亜鉛めっき（２級、めっき厚み約５μｍ）を施したねじ（ＰＨ型、径５ｍｍ、長さ２０ｍｍ、脱脂洗浄なし）を用い、次いで、前記で製造した表面処理液に浸漬し、引き上げて遠心振り切りにより表面処理液を塗布した。これを１００℃で焼き付けを行い、被覆量３．５ｇ／ｍ２（付着厚みが約１．５μｍ）の皮膜を形成した。このねじの耐食性の評価（白錆）は下記の方法で行った。結果を表１に示す。 In addition, as a fastening part, a screw (PH type, diameter 5 mm, length 20 mm, no degreasing and washing) subjected to electrogalvanizing (second grade, plating thickness of about 5 μm) was used, and then the surface treatment liquid produced above was used. The surface treatment solution was applied by dipping, pulling up and centrifuging. This was baked at 100 ° C. to form a film having a coating amount of 3.5 g / m 2 (adhesion thickness of about 1.5 μm). Evaluation of corrosion resistance (white rust) of this screw was performed by the following method. The results are shown in Table 1.
（表面処理液の安定性の評価方法）
表面処理液を調整後、差をより明確に把握するため、４０℃で１ヶ月間保持し、沈殿物の状態を目視で確認し評価した。
(Method for evaluating the stability of the surface treatment solution)
After adjusting the surface treatment liquid, in order to grasp the difference more clearly, it was held at 40 ° C. for one month, and the state of the precipitate was visually confirmed and evaluated.
（ねじ部材の耐食性の評価方法）
ねじ部材に表面処理液を塗布し、１００℃で焼き付け後、ＪＩＳ Ｚ−２３７１規格に準拠した塩水噴霧装置を用いて、塩水濃度５％、槽内温度３５℃、噴霧圧力２００ｐｓｉ（１４．１ｋｇ／ｃｍ２）の条件で塩水噴霧環境に曝し、試験９６時間後に表面に白錆の発生したねじの本数を目視にて確認した。
(Method for evaluating the corrosion resistance of screw members)
After applying the surface treatment liquid to the screw member and baking at 100 ° C., using a salt spray device conforming to JIS Z-2371 standard, the salt water concentration is 5%, the temperature in the tank is 35 ° C., the spray pressure is 200 psi (14.1 kg / It was exposed to a salt spray environment under the condition of cm 2 ), and the number of screws having white rust on the surface was visually confirmed after 96 hours of the test.
実施例２〜８
表面処理液の組成を表１に示すとおりとした他は、実施例１と同様に実施することによって、実施例２〜８の表面処理液を製造した。各表面処理液の安定性を実施例１と同じ方法で評価した。結果を表１に示す。また、実施例２〜８の表面処理液を実施例１と同様に亜鉛めっきされたねじに塗布し、その耐食性を実施例１と同様に評価した。
Examples 2-8
The surface treatment liquids of Examples 2 to 8 were produced by carrying out in the same manner as in Example 1 except that the composition of the surface treatment liquid was as shown in Table 1. The stability of each surface treatment solution was evaluated in the same manner as in Example 1. The results are shown in Table 1. In addition, the surface treatment liquids of Examples 2 to 8 were applied to galvanized screws in the same manner as in Example 1, and the corrosion resistance was evaluated in the same manner as in Example 1.
実施例９
実施例１と同様にして亜鉛めっきに皮膜を施したねじの表面に、上塗り塗料として、市販のポリエステル系塗料（大豊塗料株式会社製、商品名マイコート黒色）を用いて、その塗料中に浸漬し引き上げて遠心振り切りにより、この被覆ねじの表面に上塗り塗料による被覆をおこなった。これを１４０℃で焼き付けを行い、被覆量６．５ｇ／ｍ２（付着厚みが約４μｍ）の皮膜を形成した。この上塗り被覆ねじの耐食性の評価（赤錆）を下記の方法で行った。結果を表２に示す。
Example 9
In the same manner as in Example 1, a commercially available polyester paint (made by Taiho Paint Co., Ltd., trade name “My Coat Black”) is used as the top coat on the surface of the screw coated with galvanizing, and immersed in the paint. Then, the surface of the coated screw was covered with a top coating by centrifugally shaking off. This was baked at 140 ° C. to form a film having a coating amount of 6.5 g / m 2 (adhesion thickness of about 4 μm). Evaluation of corrosion resistance (red rust) of this top coat screw was performed by the following method. The results are shown in Table 2.
（被覆ねじの耐食性の評価方法）
赤錆の発生は、亜鉛めっきが犠牲防食により欠落している部分から腐食が発生していることを示しているものと考えられるので、試験５００時間後に赤錆の発生したねじの本数を目視にて確認した。
(Method for evaluating corrosion resistance of coated screws)
The occurrence of red rust is considered to indicate that corrosion has occurred from the part where zinc plating is missing due to sacrificial corrosion protection, so visually confirm the number of screws with red rust after 500 hours of testing. did.
なお、各実施例のねじは、目視による評価では、上塗り被覆層における塗りムラ等の欠陥部分はなく良好であった。 In addition, the screw of each Example was good by visual evaluation without a defective part such as coating unevenness in the top coat layer.
また、各実施例のねじは、粘着テープによる剥離テストにおいて剥離は認められなかった。 In addition, the screws of the respective examples were not peeled off in a peel test using an adhesive tape.
実施例１０〜１６
実施例２〜８と同様にして亜鉛めっきに皮膜を施したねじの表面に、実施例９と同様にして、上塗り塗料による皮膜を形成して、実施例１０〜１６のねじを製造した。この上塗り被覆ねじの耐食性の評価（赤錆）を下記の方法で行った。結果を表２に示す。
Examples 10-16
In the same manner as in Examples 2 to 8, the surface of the screw coated with zinc plating was coated with a top coating film in the same manner as in Example 9 to produce the screws of Examples 10 to 16. Evaluation of corrosion resistance (red rust) of this top coat screw was performed by the following method. The results are shown in Table 2.
比較例１〜４
表面処理液の組成を表１に、ねじ部材への塗布量を表１に、それぞれ示すとおりとした他は、実施例１と同様な方法で比較例１〜４のねじを製造し評価した。結果を表１に示す。
Comparative Examples 1-4
The screws of Comparative Examples 1 to 4 were produced and evaluated in the same manner as in Example 1 except that the composition of the surface treatment liquid was as shown in Table 1 and the amount applied to the screw member was as shown in Table 1. The results are shown in Table 1.
比較例５〜８
比較例１〜４の同様にして亜鉛めっきに皮膜を施したねじの表面に、実施例９と同様にして、上塗り塗料による皮膜を形成して、比較例５〜８のねじを製造し、この上塗り被覆ねじの耐食性の評価（赤錆）を下記の方法で行った。結果を表２に示す。
Comparative Examples 5-8
In the same manner as in Comparative Example 1 to 4, on the surface of the screw coated with galvanizing, a film with a top coat was formed in the same manner as in Example 9 to produce screws of Comparative Examples 5 to 8, Evaluation of corrosion resistance (red rust) of the top coat screw was performed by the following method. The results are shown in Table 2.
表１において、ＰＡは第一リン酸アルミニウム、ＰＭは第一リン酸マグネシウム、ＭＯＨは水酸化マグネシウム、ＭＣＯは炭酸マグネシウムをそれぞれ表す。 In Table 1, PA represents primary aluminum phosphate, PM represents primary magnesium phosphate, MOH represents magnesium hydroxide, and MCO represents magnesium carbonate.
表１の安定性において、◎〜×は以下の結果を示す。
◎：沈殿物なし、○：ごく僅かに沈殿物あり、△：少し沈殿物が認められる、×：全体が白濁またはゲル化
In the stability of Table 1, 〜 to × indicate the following results.
◎: No precipitate, ○: Slightly precipitate, △: Slight precipitate is observed, ×: Whole cloudiness or gelation
表１の耐食性において、◎〜×は以下の結果を示す。
◎：発生数０／５本、○：発生数１／５本、△：発生数２〜３／５本、×：発生数４〜５／５本
In the corrosion resistance of Table 1, ◎ to × indicate the following results.
A: Occurrence number 0/5, O: Occurrence number 1/5, Δ: Occurrence number 2-3 / 5, X: Occurrence number 4-5 / 5
表２の耐食性において、◎〜×は以下の結果を示す。
◎：発生数０／５本、○：発生数１／５本、△：発生数２〜３／５本、×：発生数４〜５／５本
In the corrosion resistance of Table 2, ◎ to × indicate the following results.
A: Occurrence number 0/5, O: Occurrence number 1/5, Δ: Occurrence number 2-3 / 5, X: Occurrence number 4-5 / 5
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011167772A JP5689039B2 (en) | 2011-07-29 | 2011-07-29 | Surface treatment liquid for fastening parts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011167772A JP5689039B2 (en) | 2011-07-29 | 2011-07-29 | Surface treatment liquid for fastening parts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013032554A true JP2013032554A (en) | 2013-02-14 |
| JP5689039B2 JP5689039B2 (en) | 2015-03-25 |
Family
ID=47788640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011167772A Active JP5689039B2 (en) | 2011-07-29 | 2011-07-29 | Surface treatment liquid for fastening parts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5689039B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3663435A1 (en) * | 2018-12-05 | 2020-06-10 | Henkel AG & Co. KGaA | Passivation composition based on mixtures of phosphoric and phosphonic acids |
| CN112135926A (en) * | 2018-05-18 | 2020-12-25 | 汉高股份有限及两合公司 | Trivalent chromium-based passivation composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000328271A (en) * | 1999-05-17 | 2000-11-28 | Yuken Kogyo Kk | Treating solution for rust prevention in metallic material and rust prevention treating method |
| JP2010248600A (en) * | 2009-04-20 | 2010-11-04 | Sumitomo Metal Ind Ltd | Surface treated steel sheet, method for manufacturing surface treated steel sheet, and casing obtained from the steel sheet |
-
2011
- 2011-07-29 JP JP2011167772A patent/JP5689039B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000328271A (en) * | 1999-05-17 | 2000-11-28 | Yuken Kogyo Kk | Treating solution for rust prevention in metallic material and rust prevention treating method |
| JP2010248600A (en) * | 2009-04-20 | 2010-11-04 | Sumitomo Metal Ind Ltd | Surface treated steel sheet, method for manufacturing surface treated steel sheet, and casing obtained from the steel sheet |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112135926A (en) * | 2018-05-18 | 2020-12-25 | 汉高股份有限及两合公司 | Trivalent chromium-based passivation composition |
| EP3663435A1 (en) * | 2018-12-05 | 2020-06-10 | Henkel AG & Co. KGaA | Passivation composition based on mixtures of phosphoric and phosphonic acids |
| WO2020114727A1 (en) * | 2018-12-05 | 2020-06-11 | Henkel Ag & Co. Kgaa | Passivation composition based on mixtures of phosphoric and phosphonic acids |
| CN113166946A (en) * | 2018-12-05 | 2021-07-23 | 汉高股份有限及两合公司 | Passivating composition based on a mixture of phosphoric and phosphonic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5689039B2 (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1404894B1 (en) | Corrosion resistant coatings for aluminum and aluminum alloys | |
| AU2005303936B2 (en) | Method for the coating of metallic surfaces with an aqueous composition comprising silanes silanols siloxanes and polysiloxanes and said composition | |
| JP6026016B2 (en) | Surface treatment composition for galvanized steel sheet, surface treatment method for galvanized steel sheet, and galvanized steel sheet | |
| JP5274560B2 (en) | Chemical treatment solution and treatment method for coating base of steel material | |
| CN103060788B (en) | A kind of fuel tank one-side electroplating zinc chrome-free surface treated steel plate and surface treatment agent | |
| US8728251B2 (en) | Treatment solution for coating metal surface | |
| KR20110028298A (en) | Chemical conversion liquid for metal structure and surface treating method | |
| JP2010090407A (en) | Liquid for treating metal surface, and method for treating metal surface | |
| AU2011322621A1 (en) | Aqueous composition for pretreating a metal surface before applying another coating or for treating said surface | |
| TW201420810A (en) | Aqueous metal surface treatment agent and metal surface treatment method using the same | |
| US9752233B2 (en) | Process and seal coat for improving paint adhesion | |
| FI70599B (en) | SHEET METAL CONSTRUCTION CONVERTIBLE CONTAINERS WITH OVER / ELLER ZINK | |
| HUE025417T2 (en) | Steel sheet including a multilayer coating | |
| CA2612107C (en) | Method for treatment of chemically passivated galvanized surfaces to improve paint adhesion | |
| JP2011068996A (en) | Composition for surface treatment of metallic material, and treatment method | |
| JP4312583B2 (en) | Painted Zn-Al alloy plated steel sheet with excellent corrosion resistance | |
| JP5689039B2 (en) | Surface treatment liquid for fastening parts | |
| WO2014084371A1 (en) | Hot dip galvanized steel sheet | |
| JP5259168B2 (en) | Surface treatment agent and steel plate | |
| JP5697562B2 (en) | Coated fastening parts | |
| CA3107111A1 (en) | Acid zinc sulfate metal pretreatment | |
| WO2009138022A1 (en) | A composition for conversion coating a zinciferous metal substrate, a method for treating a zinciferous metal substrate, a treated zinciferous metal substrate and its use | |
| JP5398310B2 (en) | Painted steel sheet and exterior member | |
| JP6622206B2 (en) | Method for coating metal surface, substrate coated by said method and use thereof | |
| JP2005262526A (en) | Coated aluminium plated steel sheet excellent in corrosion resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140514 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20141110 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20141118 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141224 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150120 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150127 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5689039 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |