JPS63168474A - Coating method to impart corrosion resistance - Google Patents
Coating method to impart corrosion resistanceInfo
- Publication number
- JPS63168474A JPS63168474A JP31581786A JP31581786A JPS63168474A JP S63168474 A JPS63168474 A JP S63168474A JP 31581786 A JP31581786 A JP 31581786A JP 31581786 A JP31581786 A JP 31581786A JP S63168474 A JPS63168474 A JP S63168474A
- Authority
- JP
- Japan
- Prior art keywords
- water
- hexavalent chromium
- soluble
- chromium
- corrosion resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 44
- 238000005260 corrosion Methods 0.000 title abstract description 27
- 230000007797 corrosion Effects 0.000 title abstract description 19
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003973 paint Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims description 7
- 238000010422 painting Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 33
- 238000000034 method Methods 0.000 abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 abstract description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 abstract description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 abstract 2
- 239000011651 chromium Substances 0.000 description 30
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 27
- 229910052804 chromium Inorganic materials 0.000 description 25
- 229910000831 Steel Inorganic materials 0.000 description 19
- 239000010959 steel Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 238000010828 elution Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 9
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/26—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also organic compounds
- C23C22/28—Macromolecular compounds
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、金属、特に、鉄鋼１．メッキ鋼板、アルミニ
ウムもしくは合金等を６価のクロムと水溶性高分子また
は水分散性高分子を含有する水系塗料を用い防食表面処
理する方法に関するものである。アルミニウムもしくは
合金の防食表面処理の応用分野としては、例えば、アル
ミニウム製熱交換器フィン材の親木防食塗装があり、鉄
鋼の防食表面処理の応用分野としては、各種鋼板の耐食
性向上処理がある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is directed to metals, particularly steels. This invention relates to a method for anticorrosive surface treatment of plated steel sheets, aluminum, alloys, etc. using a water-based paint containing hexavalent chromium and a water-soluble or water-dispersible polymer. An example of an application field of anti-corrosion surface treatment of aluminum or alloys is the anti-corrosion coating of parent wood for aluminum heat exchanger fin materials, and an application field of anti-corrosion surface treatment of steel is treatment to improve the corrosion resistance of various steel plates.
上記した防食塗装方法が、工業的に最も広く適用されて
いるのは、アルミニウムと鉄鋼の表面処理であって、ア
ルミニウムについては、熱交換器のフィン材を親水性処
理する際に、その防食性を向上させるために、予めクロ
ム酸クロメート処理等の６価クロム含有処理剤による処
理を施す表面処理として実施されている。かかる防食性
被膜の形成後、水ガラス等の無機系や、ポリアクリル酸
等の有機系の親水性賦与塗料が一般に塗装される。The anticorrosion coating method described above is most widely applied industrially to the surface treatment of aluminum and steel. In order to improve this, surface treatment is carried out by previously applying a treatment using a treatment agent containing hexavalent chromium, such as chromate treatment. After the anticorrosive coating is formed, an inorganic coating such as water glass or an organic hydrophilic coating such as polyacrylic acid is generally applied.
さらに、熱交換器のフィンに無水クロム酸と水溶性高分
子の混合溶液を塗布して、親水性・防食性被膜を形成す
る方法も知られている。Furthermore, a method is also known in which a mixed solution of chromic anhydride and a water-soluble polymer is applied to the fins of a heat exchanger to form a hydrophilic and anticorrosive coating.
一方、鉄鋼への応用では、ポリビニルプチラール、６価
クロム、リン酸を主成分とするいわゆるウォッシュブラ
イマーが、鉄鋼表面の防食塗料として著名である。しか
し、ウォッシュプライマーは、アルコール類を溶剤とす
る塗料であるため、引火等の消防法上の問題があり、水
系の防食塗料の開発が望まれていた。On the other hand, in applications to steel, so-called wash brimer, whose main components are polyvinyl petyral, hexavalent chromium, and phosphoric acid, is well-known as an anticorrosion paint for steel surfaces. However, since wash primer is a paint that uses alcohol as a solvent, there are problems under the Fire Service Act, such as ignition, and there has been a desire to develop a water-based anticorrosive paint.
特公昭５７−４５８３４号公報は、水溶性の重クロム酸
塩またはクロム酸と水溶性樹脂からなる処理液を鋼桟に
塗布後、４０〜８０℃で加熱乾燥する方法を提案してお
り、その特徴とするところは、安定した処理液が得られ
るようにエポキシ樹脂を水溶化する方法にある。Japanese Patent Publication No. 57-45834 proposes a method in which a treatment solution consisting of a water-soluble dichromate or chromic acid and a water-soluble resin is applied to a steel beam and then heated and dried at 40 to 80°C. The unique feature lies in the method of making the epoxy resin water-soluble so that a stable processing solution can be obtained.
特開昭６０−２２８６８２号公報は、Ｃｒｙ、、、水溶
性アクリル樹脂、およびフッ素錯塩よりなる水溶液を亜
鉛系めっきｔ１２１仮のクロメート処理に使用すること
を提案しており、その特徴とするところは、Ｎａ：＋Ａ
ＩＦｂなどのフッ素錯塩およびアクリル樹脂がクロム酸
水溶液に相溶性であれば、これの添加によって耐食性お
よび塗膜密着性の両者が改良されるために、フッ素錯塩
およびアクリル樹脂を添加したところにある。JP-A No. 60-228682 proposes the use of an aqueous solution consisting of Cry, a water-soluble acrylic resin, and a fluorine complex salt for temporary chromate treatment of zinc-based plating T121, and its characteristics are as follows. , Na:+A
If the fluorine complex salt such as IFb and the acrylic resin are compatible with the chromic acid aqueous solution, the fluorine complex salt and the acrylic resin are added because both corrosion resistance and coating adhesion are improved by the addition of the fluorine complex salt and the acrylic resin.
しかし、上記従来の方法によると、過剰の６価クロムが
塗膜中に残存し、アルミニウム製熱交換器への適用の場
合に、熱交換器表面に凝縮した水滴中に溶出し、健康、
環境に悪影響を及ぼすという問題があった。However, according to the above conventional method, excessive hexavalent chromium remains in the coating film, and when applied to an aluminum heat exchanger, it dissolves into water droplets condensed on the heat exchanger surface, causing health problems and
There was a problem that it had a negative impact on the environment.
特公昭５７−４５８３４号公報によると、鋼板に塗布さ
れた処理液が加熱乾燥されているときに樹脂中のヒドロ
キシル基、不飽和二重結合などの酸化が起り、この時Ｃ
ｒ”→Ｃｒ”の反応が起ることが記載されている。しか
し、この公報の方法は、鋼板のペイント塗装前の脱脂工
程でのクロム溶出を防止し、ブライマーの一次防錆力を
保持させるのが目的であって、塗膜中の６価クロムは成
程度減少はするものの、ポリマーとクロムの高分子反応
であるために、一般的には可成りの部分の６価クロムは
未還元のま１残ることは避けられず、本出願の如く、造
膜性のあるポリマー以外に、６価クロムの還元力のある
化合物を積極的に添加して、大部分の６価クロムを還元
不溶化する方法とは本質的に異っている。According to Japanese Patent Publication No. 57-45834, when a treatment liquid applied to a steel plate is heated and dried, oxidation of hydroxyl groups, unsaturated double bonds, etc. in the resin occurs, and at this time C
It is described that the reaction r"→Cr" occurs. However, the method of this publication aims to prevent chromium elution during the degreasing process before painting the steel plate and maintain the primary rust prevention ability of the brimer, and the hexavalent chromium in the paint film is Although it decreases, it is generally inevitable that a considerable portion of hexavalent chromium remains unreduced due to the polymer reaction between the polymer and chromium. This method is essentially different from a method in which a compound capable of reducing hexavalent chromium is actively added to a certain polymer to reduce and insolubilize most of the hexavalent chromium.
本発明者らは、この問題解決について種々検討の結果、
水系の６価クロム含有塗料で、塗布・乾燥後水に浸漬し
ても６価クロムの溶出が殆どない防食塗料を開発した。As a result of various studies to solve this problem, the inventors found that
We have developed a water-based anti-corrosion paint containing hexavalent chromium that hardly elutes hexavalent chromium even when immersed in water after application and drying.
本発明は、６価のクロムと水溶性高分子よりなる造膜成
分を含有する水系塗料を金属表面に塗装する際に、−ｃ
ｏ、ｏｎ基および＞Ｃｌｌ０１１基を１個または２個以
上、ただし、これらの−ｃｕｔｏｏ基および＞Ｃ）１０
８基が１個含有される場合は、−０−基を１個以上、含
有するとともに、沸点が１００℃以上の水溶性有機化合
物を添加した水系塗料を金属表面に塗装した後加熱、乾
燥することを特徴とする防食塗装方法にある。The present invention provides -c
One or more o, on groups and >Cll011 groups, provided that these -cutoo groups and >C1010
If one 8 group is contained, a water-based paint containing one or more -0- groups and a water-soluble organic compound with a boiling point of 100°C or higher is applied to the metal surface, then heated and dried. The anti-corrosion coating method is characterized by the following.
以下、本発明の構成を詳しく説明する。Hereinafter, the configuration of the present invention will be explained in detail.
本発明において、塗膜形成剤として、使用可能な有機高
分子材料は、水溶性もしくは水分散性であること、加熱
乾燥により硬化することなどの条件を満すものであって
、その例としては、本出願人の昭和６１年１２月２７日
付特許出願２件のアクリルアミド系重合体、特公昭５８
−４７２３０号にて公知の（メタ）アクリル酸系重合体
、共重合体等の水溶性高分子などがある。In the present invention, the organic polymer material that can be used as a coating film forming agent is one that satisfies conditions such as being water-soluble or water-dispersible and being hardened by heating and drying. , two patent applications filed by the present applicant on December 27, 1986, for acrylamide-based polymers,
Examples include water-soluble polymers such as (meth)acrylic acid polymers and copolymers known in No. 47230.
また、６価クロムは、無水クロム酸、重クロム酸アンモ
ニウム等の水溶性６価りロム含有無機化合物を配合する
ことにより、処理液中に存在させる。なお、亜鉛めっき
鋼材のクロメート処理において、防錆性を高めるために
６価クロムに加えて、少量の３価クロムをクロメート処
理液に加えることが公知であるが、このように少量の３
価クロムを含有する処理液においても、本発明を実施す
ることができる。Further, hexavalent chromium is made to exist in the treatment liquid by blending a water-soluble hexavalent chromium-containing inorganic compound such as chromic anhydride or ammonium dichromate. In addition, in chromate treatment of galvanized steel, it is known to add a small amount of trivalent chromium to the chromate treatment solution in addition to hexavalent chromium in order to improve rust prevention.
The present invention can also be practiced in a treatment liquid containing valent chromium.
−ＣＩｌｔＯＨ基および＞ＣＨＯＨ基を１個または２個
以上、ただし、これらの−ｃｎｚｏ＋を基および＞Ｃｌ
ｌ０１１基が１個含有される場合は、−〇−基を１個以
上、含有するとともに、沸点が１００℃以上の水溶性有
機化合物としては、例えば、エチレングリコール、ジエ
チレングリコール、トリエチレングリコール、゛エチレ
ングリコールモノメチルエーテル、ジエチレングリコー
ルモノエチルエーテル、プロピレンことができる。-CIltOH group and >CHOH group, one or more, provided that these -cnzo+ groups and >Cl
When one l011 group is contained, water-soluble organic compounds containing one or more -〇- groups and having a boiling point of 100°C or higher include, for example, ethylene glycol, diethylene glycol, triethylene glycol, Can be glycol monomethyl ether, diethylene glycol monoethyl ether, propylene.
上記した水溶性有機化合物を添加した処理液を金属表面
に塗布後、加熱乾規すれば、実施例に示す如く、これら
化合物を添加しない場合に比較して、塗膜中に残存する
６価クロムが塗膜に接する水滴などにより溶出する性質
を格段に抑制し得ることを見出した。加熱乾燥の温度は
塗膜形成成分の樹脂の種類により定まるが、１００〜３
００℃、であることが好ましい。水溶性有機化合物の沸
点が１００℃未満であると、塗膜中における６価クロム
の溶出抑制効果がなくなる。If a treatment solution containing the water-soluble organic compounds mentioned above is applied to a metal surface and then heated to dry, as shown in the example, the amount of hexavalent chromium remaining in the coating film is greater than when these compounds are not added. It has been found that the property of dissolving by water droplets etc. that come into contact with the coating film can be significantly suppressed. The temperature for heating and drying is determined by the type of resin used as the coating film forming component, but is between 100 and 3
The temperature is preferably 00°C. If the boiling point of the water-soluble organic compound is less than 100°C, the effect of suppressing the elution of hexavalent chromium in the coating film is lost.
水溶性有機化合物の添加量は、化合物の種類、６価クロ
ム化合物の濃度等によっても異なるが、一般的に言えば
、０．１〜２０ｇ／ｌ、好ましくは０、５〜Ｌｏｇ／ｊ
’程度で、６価クロムに対してモル比で１／１０〜３、
好ましくは１／３〜１．５程度用いるのが適当である。The amount of water-soluble organic compound added varies depending on the type of compound, the concentration of hexavalent chromium compound, etc., but generally speaking, it is 0.1 to 20 g/l, preferably 0.5 to Log/j.
', the molar ratio to hexavalent chromium is 1/10 to 3,
Preferably, it is appropriate to use about 1/3 to 1.5.
本発明において、−Ｃ１１２０Ｈ蕃、 ＞Ｃ）１０１１
基を有する化合物の添加がクロムの溶出を防止する効果
については、その原因は必ずしも明らかではないが、こ
れらの基を含む上述の化合物が、塗膜中において６価ク
ロムを還元し、６価クロムの溶解度より低い３価クロム
とすると共に、これらの酸化生成物または水溶性高分子
と３価クロムが錯化合物を形成して更に溶出を抑制する
ためと考えられる。In the present invention, -C1120H, >C)1011
The cause of the effect of the addition of compounds having groups on preventing chromium elution is not necessarily clear, but the above-mentioned compounds containing these groups reduce hexavalent chromium in the coating film and reduce hexavalent chromium. It is thought that this is because the solubility of trivalent chromium is lower than that of trivalent chromium, and these oxidation products or water-soluble polymers and trivalent chromium form a complex compound to further suppress elution.
而して、上記化合物は常温では還元性は弱いため、常温
での調合、保存時は可成り安定であり、被塗物試料に塗
布し加熱乾燥に際して６価クロムを完全に還元する効果
を発揮するものと思われる。特に重クロム酸アンモンな
どを用いてｐｌ＋を高く保てば、さらに安定となる。こ
のような作用を実現するためには、水溶性有機化合物は
２個以上の一０１１□０１１または＞Ｃｌｌ０Ｉ＋をも
たなければならず、−Ｃ１１□０１！または＞ＣＨＯＩ
＋が１個の場合は水溶性を増すために一〇−を１個以上
含有しなければならない。Since the above compound has weak reducing properties at room temperature, it is quite stable when prepared and stored at room temperature, and exhibits the effect of completely reducing hexavalent chromium when applied to a sample to be coated and heated and dried. It seems that it will. In particular, if pl+ is kept high using ammonium dichromate or the like, it becomes even more stable. To achieve such an effect, the water-soluble organic compound must have two or more 1011□011 or >Cll0I+, -C11□01! or > CHOI
If there is one +, it must contain one or more 10- to increase water solubility.
以下、実施例により本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
以下の実施例および比較例において試験法は次のとおり
であった。In the following Examples and Comparative Examples, the test methods were as follows.
拭豆法
（１）接触角
試料表面上に静止した直径１〜２龍の小水滴の接触角を
ＦＡＣＥ接触角計ＣＡ−Ｐ型〔協和界面科学■〕を用い
て測定した。Wipe bean method (1) Contact angle The contact angle of a small water droplet of 1 to 2 diameters resting on the sample surface was measured using a FACE contact angle meter CA-P model (Kyowa Interface Science ■).
（２）耐食性
塩水噴霧試験法−ＪＩＳ Ｚ−２３７１−に基づき試
験を行ない、白錆発生面積が５％に達する迄の噴霧テス
ト時間で示した。(2) Corrosion resistance The test was conducted based on the salt spray test method - JIS Z-2371, and the spray test time is shown as the spray test time until the area where white rust occurs reaches 5%.
（３）クロム溶出量
試料７ｄｍを１Ｃ１１角に切断し、３０℃の脱塩水１０
０ｍ１に７日間浸漬後、試料を取出し、洗浄し、洗浄液
と合して５Ｑｍ／まで濃縮し、この液中のＣｒ濃度を原
子吸光法で測定した。(3) Cut a 7 dm sample of the chromium elution amount into 1C11 square pieces, and then
After being immersed in 0ml for 7 days, the sample was taken out, washed, combined with a washing solution and concentrated to 5Qm/, and the Cr concentration in this solution was measured by atomic absorption spectrometry.
比較例１
ポリアクリルアミド１０ｇ／ｌおよび無水クロム酸３ｇ
／ｌを含有する水溶液を０．１ 龍厚のアルミニウム板
（＃ Ａ １１００）に塗布後、１８０℃に３分間加熱
乾燥し、０．１ｇ／ｒｒｒの塗膜を付着させた。Comparative example 1 10 g/l polyacrylamide and 3 g chromic anhydride
After coating an aqueous solution containing 0.1 g/l on an aluminum plate (#A 1100) with a thickness of 0.1 mm, it was heated and dried at 180° C. for 3 minutes to form a coating film of 0.1 g/rr.
この上に３号水ガラス水溶液（４０ｇ／ｉ）を塗布し、
１８０℃で３分間乾燥し０．２μ厚の親木層を付着させ
た。得られた塗装アルミニウム板の耐水接触角は５°以
下、耐食性は２４０時間以上、クロム溶出量は１．１曜
／イであった。On top of this, apply No. 3 water glass aqueous solution (40 g/i),
It was dried at 180° C. for 3 minutes to adhere a 0.2 μ thick parent wood layer. The obtained coated aluminum plate had a water contact angle of 5° or less, a corrosion resistance of 240 hours or more, and a chromium elution amount of 1.1 days/day.
実施例１〜３
下塗り中に、表１に記載した添加剤を添加した以外は比
較例１と同様にして試料を作成し、評価した。耐水接触
角、耐食性は比較例１と同様であったが、クロム溶出量
は表１に示す如く、大１１に低下した。Examples 1 to 3 Samples were prepared and evaluated in the same manner as in Comparative Example 1, except that the additives listed in Table 1 were added during undercoating. Although the water contact angle and corrosion resistance were the same as those of Comparative Example 1, the amount of chromium eluted decreased to 11 as shown in Table 1.
表 １
比較例２
アクリルアミドとジメチルアミノプロピルアクリルアミ
ドの８０７２０共重合体１５ ｇ／ｌ、重クロム酸アン
モニウム２０ ｇ／ｊ！ジルコン弗酸アンモニウム２０
ｇ／ｌの混合水溶液をアルミニウム板に塗布後、１８０
℃に３分間加熱乾燥し、０．３ｇ／Ｍの塗膜を付着させ
た。得られた板の耐水接触角は２５〜３５°、耐食性は
２４０時間以上、クロム溶出量は１．８■／ｄであった
。Table 1 Comparative Example 2 80720 copolymer of acrylamide and dimethylaminopropylacrylamide 15 g/l, ammonium dichromate 20 g/j! Zircon ammonium fluoride 20
After applying a mixed aqueous solution of g/l to an aluminum plate, 180
It was dried by heating at ℃ for 3 minutes, and a coating film of 0.3 g/M was attached. The obtained plate had a water contact angle of 25 to 35°, a corrosion resistance of 240 hours or more, and an amount of chromium leached out of 1.8 μ/d.
実施例４および５
表１に記載した添加剤を添加した以外、比較例２と同様
にして試料を作成して評価した。対水接触角は２０〜３
０°、耐食性は２４０時間以上、クロム溶出量は表１に
示す如くであった。Examples 4 and 5 Samples were prepared and evaluated in the same manner as Comparative Example 2, except that the additives listed in Table 1 were added. Contact angle with water is 20-3
0°, the corrosion resistance was over 240 hours, and the amount of chromium eluted was as shown in Table 1.
本発明による防食塗装法は、アルミニウムおよび鋼材が
湿度の高い大気と接して使用される時の優れた耐食性を
有し、また水との接触による６価クロムの溶出を少なく
する。また、本発明による防食塗装塗膜の上に水ガラス
等の親水性被膜を形成すると、耐食性、親水性に優れ、
かつ６価クロムの溶出が少ない塗膜が得られる。The anticorrosion coating method according to the present invention has excellent corrosion resistance when aluminum and steel materials are used in contact with a humid atmosphere, and also reduces the elution of hexavalent chromium due to contact with water. In addition, when a hydrophilic film such as water glass is formed on the anticorrosive coating film according to the present invention, it has excellent corrosion resistance and hydrophilicity,
Moreover, a coating film with less elution of hexavalent chromium can be obtained.
手続補正書（自発）
昭和６２年３月〈 日
特許庁長官 黒 １）明 雄 殴
１゜事件の表示
昭和６１年特許願第３１５８１７号
２、発明の名称
防食塗装方法
３、補正をする者
事件との関係 特許出願人
名称 日本パー力ライジング株式会社
４、代理人
住所 〒１０５東京都港区虎ノ門−丁目８番ＩＯ号５、
補正の対象
明細書全文
６、補正の内容
明細書全文を別紙のように補正する。Procedural amendment (spontaneous) March 1985 (Japanese Patent Office Commissioner Black 1) Yu Akihito Indication of the 1° case 1985 Patent Application No. 315817 2, Title of invention Anticorrosive coating method 3, Case of the person making the amendment Relationship with Patent applicant name: Nihon Pariki Rising Co., Ltd. 4, agent address: IO-5, Toranomon-8-chome, Minato-ku, Tokyo 105
The entire text of the specification to be amended 6, the contents of the amendment The entire text of the specification shall be amended as shown in the attached sheet.
７、添付書類の目録
全文補正明細書 １通全文補正明細書
１． 発明の名称
防食塗装方法
２、特許請求の範囲
１、 ６価のクロムと水溶性高分子または水分散性高分
子よりなる造膜成分を含有する水系塗料をアルミを除く
金属表面に塗装する防食塗装方法において、
一０１１□ＯＨ基または＞Ｃｌｌ０１１基を１個または
２個以上、ただし、これらの−ＣＨ□ＯＨ基または＞Ｃ
ＨＯＩ＋基が１個含有される場合は、−〇−基を１個以
上、含有するとともに、沸点がｌＯＯ°Ｃ以上の水溶性
有機化合物を添加した水系塗料を前記金属表面に塗装し
た後加熱、乾燥することを特徴とする防食塗装方法。7. List of attached documents, complete statement of amendment 1 copy, complete statement of amendment 1. Title of the invention: Anticorrosion coating method 2, Claim 1: Anticorrosion coating in which a water-based paint containing a film-forming component consisting of hexavalent chromium and a water-soluble or water-dispersible polymer is applied to metal surfaces other than aluminum. In the method, one or more 1011□OH groups or >Cll011 groups, provided that these -CH□OH groups or >C
When one HOI+ group is contained, a water-based paint containing one or more -〇- groups and a water-soluble organic compound with a boiling point of 100°C or higher is applied to the metal surface, and then heated. An anticorrosion coating method characterized by drying.
３、発明の詳細な説明
〔産業上の利用分野〕
本発明は、アルミを除く金属、特に、亜鉛メッキ鋼板を
６価のクロムと水溶性高分子または水分散性高分子を含
有する水系塗料を用い防食表面処理する方法に関するも
のである。この防食表面処理の応用分野としては、各種
鋼板の耐食性向上処理がある。3. Detailed Description of the Invention [Field of Industrial Application] The present invention is directed to coating metals other than aluminum, particularly galvanized steel sheets, with a water-based paint containing hexavalent chromium and a water-soluble or water-dispersible polymer. The present invention relates to a method for anticorrosive surface treatment. Application fields of this anti-corrosion surface treatment include treatment to improve the corrosion resistance of various steel plates.
上記した防食塗装方法が、工業的に最も広（通用されて
いるのは、鋼板の表面処理であって、鋼板への応用では
、ポリビニルブチラール、６価クロム、リン酸を主成分
とするいわゆるウォッシュプライマーが、鉄鋼表面の防
食塗料として著名である。しかし、ウォッシュプライマ
ーは、アルコール類を溶剤とする塗料であるため、引火
等の消防法上の問題があり、水系の防食塗料の開発が望
まれていた。The above anti-corrosion coating method is the most widely used industrially (used for surface treatment of steel plates). Primer is well-known as an anticorrosive paint for steel surfaces.However, since wash primer is a paint that uses alcohol as a solvent, there are problems under the Fire Service Act, such as ignition, so the development of a water-based anticorrosive paint is desired. was.
特公昭５７−４５８３４号公報は、水溶性の重クロム酸
塩またはクロム酸と水溶性樹脂からなる処理液を鋼板に
塗布後、４０〜８０℃で加熱乾燥する方法を提案してお
り、その特徴とするところは、安定した処理液が得られ
るようにエポキシ樹脂を水溶化する方法にある。Japanese Patent Publication No. 57-45834 proposes a method in which a treatment solution consisting of a water-soluble dichromate or chromic acid and a water-soluble resin is applied to a steel plate and then heated and dried at 40 to 80°C. The key point lies in the method of making the epoxy resin water-soluble so that a stable processing solution can be obtained.
特開昭６０−２２８６８２号公報は、Ｃ「０８、水溶性
アクリル樹脂、およびフッ素錯塩よりなる水溶液を亜鉛
系めっき鋼板のクロメート処理に使用することを提案し
ており、その特徴とするところは、Ｎａ５ＡＩ）’６な
どのフッ素錯塩およびアクリル樹脂がクロム酸水溶液に
相溶性であれば、これの添加によって耐食性および塗膜
密着性の両者が改良されるために、フッ素錯塩およびア
クリル樹脂を添加したところにある。JP-A No. 60-228682 proposes the use of an aqueous solution consisting of C"08, a water-soluble acrylic resin, and a fluorine complex salt for chromate treatment of zinc-plated steel sheets, and its features include: If the fluorine complex salt such as Na5AI)'6 and the acrylic resin are compatible with the chromic acid aqueous solution, the addition of the fluorine complex salt and the acrylic resin improves both corrosion resistance and coating adhesion. It is in.
しかし、上記従来の方法によると、過剰の６価クロムが
塗膜中に残存し、健康、環境に悪影響を及ぼすという問
題があった。However, according to the above-mentioned conventional method, there was a problem in that excessive hexavalent chromium remained in the coating film, which adversely affected health and the environment.
特公昭５７−４５８３４号公報によると、鋼板に塗布さ
れた処理液が加熱乾燥されているときに樹脂中のヒドロ
キシル基、不飽和二重結合などの酸化が起り、この時Ｃ
ｒ”→Ｃｒ３＋の反応が起ることが記載されている。し
かし、この公報の方法は、鋼板のペイント塗装前の脱脂
工程でのクロム溶出を防止し、プライマーの一次防錆力
・を保持させるのが目的であって、塗膜中の６価クロム
は成程度減少はするものの、ポリマーとクロムの高分子
反応であるために、−ａ的には可成りの部分の６価クロ
ムは未還元のま＼残ることは避けられず、本出願の如く
、造膜性のあるポリマー以外に、６価クロムの還元力の
ある化合物を積極的に添加して、大部分の６価クロムを
還元不溶化する方法とは本質的に異っている。According to Japanese Patent Publication No. 57-45834, when a treatment liquid applied to a steel plate is heated and dried, oxidation of hydroxyl groups, unsaturated double bonds, etc. in the resin occurs, and at this time C
It is stated that the reaction of ``r'' → Cr3+ occurs. However, the method in this publication prevents chromium elution during the degreasing process before painting the steel plate and maintains the primary rust prevention ability of the primer. The purpose is to reduce the amount of hexavalent chromium in the coating film, but since it is a polymer reaction between the polymer and chromium, a significant portion of hexavalent chromium is unreduced. It is inevitable that some residual hexavalent chromium will remain, so as in this application, in addition to the film-forming polymer, a compound with hexavalent chromium reducing power is actively added to reduce and insolubilize most of the hexavalent chromium. The method is essentially different.
本発明者らは、この問題解決について種々検討の結果、
水系の６価クロム含有塗料で、塗布・乾燥後水に浸漬し
ても６価クロムの溶出が殆どない防食塗料を開発した。As a result of various studies to solve this problem, the inventors found that
We have developed a water-based anti-corrosion paint containing hexavalent chromium that hardly elutes hexavalent chromium even when immersed in water after application and drying.
本発明は、６価のクロムと水溶性高分子よりなる造膜成
分を含有する水系塗料をアルミを除く金属表面に塗装す
る際に、−Ｃ１１，０１１基および＞Ｃｌｌ０１１基を
１個または２個以上、ただし、これらの−ＣＨ，ＯＨ基
および＞ ＣＨＯＨ基が１個含有される場合は、−〇−
基を１個以上、含有するとともに、沸点が１００℃以上
の水溶性有機化合物を添加した水系塗料を前記金属表面
に塗装した後加熱、乾燥することを特徴とする防食塗装
方法にある。In the present invention, when applying a water-based paint containing a film-forming component made of hexavalent chromium and a water-soluble polymer to a metal surface other than aluminum, one or two -C11,011 groups and >Cll011 groups are applied. Above, however, if one of these -CH,OH groups and >CHOH group is contained, -〇-
The present invention provides an anticorrosion coating method, which comprises applying a water-based paint containing one or more groups and adding a water-soluble organic compound having a boiling point of 100° C. or higher to the metal surface, followed by heating and drying.
以下、本発明の構成を詳しく説明する。Hereinafter, the configuration of the present invention will be explained in detail.
本発明において、塗膜形成剤として、使用可能な有機高
分子材料は、水溶性もしくは水分散性であること、加熱
乾燥により硬化することなどの条件を満すものであって
、その例としては、特公昭５８−４７２３０号にて公知
の（メタ）アクリル酸系重合体、共重合体等の水溶性高
分子などがある。In the present invention, the organic polymer material that can be used as a coating film forming agent is one that satisfies conditions such as being water-soluble or water-dispersible and being hardened by heating and drying. , and water-soluble polymers such as (meth)acrylic acid polymers and copolymers known from Japanese Patent Publication No. 58-47230.
また、６価クロムは、無水クロム酸、重クロム酸アンモ
ニウム等の水溶性６価りロム含有無機化合物を配合する
ことにより、処理液中に存在させる。なお、亜鉛めっき
鋼材のクロメート処理において、防錆性を高めるために
６価クロムに加えて、少量の３価クロムをクロメート処
理液に加えることが公知であるが、このように少量の３
価クロムを含有する処理液においても、本発明を実施す
ることができる。Further, hexavalent chromium is made to exist in the treatment liquid by blending a water-soluble hexavalent chromium-containing inorganic compound such as chromic anhydride or ammonium dichromate. In addition, in chromate treatment of galvanized steel, it is known to add a small amount of trivalent chromium to the chromate treatment solution in addition to hexavalent chromium in order to improve rust prevention.
The present invention can also be practiced in a treatment liquid containing valent chromium.
一０１１□０Ｈ基および＞Ｃｌｌ０Ｉ（基を１個または
２個以上、ただし、これらの−Ｃ１ｌ□ＯＨＭおよび＞
ＣＨＯＨ５が１個含有される場合は、−ｏ−４を１個以
上、含有するとともに、沸点が１００℃以上の水溶性を
機化合物としては、例えば、エチレングリコール、ジエ
チレングリコール、トリエチレングリコール、エチレン
グリコールモノメチルエーテル、ジエチレングリコール
モノエチルエーテル、プロピレングリコール、ジプロピ
レングリコール、ブタンジオール、ヘキサンジオール、
グリセリン等を用いることができる。-011□OH group and >Cll0I (one or more groups, provided that these -C1l□OHM and >
When one CHOH5 is contained, examples of water-soluble organic compounds containing one or more -o-4 and a boiling point of 100°C or higher include ethylene glycol, diethylene glycol, triethylene glycol, and ethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, dipropylene glycol, butanediol, hexanediol,
Glycerin or the like can be used.
上記した水溶性有機化合物を添加した処理液をアルミを
除（金属表面に塗布後、加熱乾燥すれば、実施例に示す
如く、これら化合物を添加しない場合に比較して、塗膜
中に残存する６価クロムが塗膜に接する水滴などにより
溶出する性質を格段に抑制し得ることを見出した。加熱
乾燥の温度は塗膜形成成分の樹脂の種類により定まるが
、１００〜３００℃、であることが好ましい。水溶性有
機化合物の沸点が１００℃未満であると、塗膜中におけ
る６価クロムの溶出抑制効果がなくなる。If the above-mentioned water-soluble organic compound-added treatment solution is applied to a metal surface and then heated and dried, aluminum remains in the coating film compared to when these compounds are not added, as shown in the examples. It has been found that the property of hexavalent chromium being eluted by water droplets in contact with the coating film can be significantly suppressed.The heating drying temperature is determined by the type of resin of the coating film forming component, but should be 100 to 300°C. is preferable. If the boiling point of the water-soluble organic compound is less than 100°C, the effect of suppressing the elution of hexavalent chromium in the coating film is lost.
水溶性有機化合物の添加量は、化合物の種類、６価クロ
ム化合物の濃度等によっても異なるが、一般的に言えば
、０６１〜２０ｇ／ｌ、好ましくは０．５〜ＬＯｇ／ｌ
程度で、６価クロムに対してモル比で１／１０〜３、好
ましくは１／３〜１．５程度用いるのが適当である。The amount of water-soluble organic compound added varies depending on the type of compound, the concentration of hexavalent chromium compound, etc., but generally speaking, it is 0.61 to 20 g/l, preferably 0.5 to LOg/l.
It is appropriate to use it in a molar ratio of about 1/10 to 3, preferably about 1/3 to 1.5, relative to hexavalent chromium.
本発明において、 ＣＨｚＯＨ、＞ＣｌｌＯＨ基を有す
る化合物の添加がクロムの溶出を防止する効果について
は、その原因は必ずしも明らかではないが、これらの基
を含む上述の化合物が、塗膜中において６価クロムを還
元し、６価クロムの溶解度より低い３価クロムとすると
共に、これらの酸化生成物または水溶性高分子と３価ク
ロムが錯化合物を形成して更に溶出を抑制するためと考
えられる。In the present invention, the reason why the addition of compounds having CHzOH and >CllOH groups prevents the elution of chromium is not necessarily clear, but the above-mentioned compounds containing these groups have a hexavalent effect in the coating film. This is thought to be because chromium is reduced to trivalent chromium, which has a solubility lower than that of hexavalent chromium, and these oxidation products or water-soluble polymers and trivalent chromium form a complex compound to further suppress elution.
明して、４上記化合物は常温では還元性は弱いため、常
温での調合、保存時は可成り安定であり、被塗物試料に
塗布し加熱乾燥に際して６価クロムを完全に還元する効
果を発揮するものと思われる。特に重クロム酸アンモン
などを用いてｐＨを高く保てば、さらに安定となる。こ
のような作用を実現するためには、水溶性有機化合物は
２個以上の−ｃｕｚｏｕまたは＞ＣＨＯｌｌをもたなけ
ればならず、−ＣＩ！ＯＨまたは＞ ＣＨＯＨが１個の
場合は水溶性を増すために一〇−を１個以上含有しなけ
ればならない。Obviously, the above compound has weak reducing properties at room temperature, so it is quite stable when prepared and stored at room temperature, and it has the effect of completely reducing hexavalent chromium when applied to a sample to be coated and heated and dried. It seems that it will work. In particular, if the pH is kept high using ammonium dichromate or the like, it becomes even more stable. To achieve such an effect, the water-soluble organic compound must have two or more -cuzou or >CHOll, and -CI! When there is one OH or >CHOH, one or more 10- groups must be included to increase water solubility.
以下、実施例により本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
以下の実施例および比較例において試験法は次のとおり
であった。In the following Examples and Comparative Examples, the test methods were as follows.
パ竣抜
（１）耐食イ
塩水噴霧試験法−ＪＩＳ Ｚ−２３７１−に基づき試験
を行ない、白錆発生面積が５％に達する迄の噴霧テスト
時間で示した。Completion (1) Corrosion resistance A test was conducted based on the salt spray test method - JIS Z-2371, and the spray test time is shown as the spray test time until the area where white rust occurs reaches 5%.
（２）クロム溶出量
試料７ｄｒｒｒを１ｃｍ角に切断し、３０℃の脱塩水１
００−に７日間浸漬後、試料を取出し、洗浄し、洗浄液
と合して５０ｍ１まで濃縮し、この液中のＣｒ？！度を
原子吸光法で測定した。(2) Chromium elution amount sample 7drrr was cut into 1cm square pieces, and 1 cm of demineralized water at 30°C was added.
After immersed in 00- for 7 days, the sample was taken out, washed, combined with a washing solution and concentrated to 50ml, and the Cr? ! The concentration was measured by atomic absorption spectrometry.
表 １
■比較例１）
電気亜鉛メッキ鋼板を、リン酸ソーダ及び珪酸ソーダを
主成分とする脱脂剤水溶液にて脱脂、水洗後、水溶性ア
クリル樹脂を固形分換算３０ｇ／ｌ 、Ｃｒ” ３．２
ｇ／（！ 、Ｃｒ” １、Ｏｇ／ｌを含むクロメート
水溶液を塗布後１８０℃で１分間乾燥し、０．２ｇ／ｍ
の塗膜を付着させた。この板の耐食性は１２０時間以上
、クロム溶出量は２．５■／ｍであった。Table 1 ■Comparative Example 1) An electrogalvanized steel sheet was degreased with an aqueous degreasing solution containing sodium phosphate and sodium silicate as main components, and after washing with water, a water-soluble acrylic resin was added at a solid content of 30 g/l, Cr''3. 2
g/(!, Cr” 1. After applying a chromate aqueous solution containing 0g/l, drying at 180°C for 1 minute, 0.2g/m
A coating film was applied. The corrosion resistance of this plate was 120 hours or more, and the amount of chromium eluted was 2.5 μ/m.
◎実施例１〜３）
上記比較例１と同様組成のクロメート水溶液中に表１に
示した添加剤を加え、上記同様に試料を作成した。これ
らの板の耐食性は１２０時間以上と比較例と変らず、ク
ロム溶出量は表１に示す如く、極度に低下した。◎Examples 1 to 3) The additives shown in Table 1 were added to an aqueous chromate solution having the same composition as in Comparative Example 1, and samples were prepared in the same manner as above. The corrosion resistance of these plates was 120 hours or more, which was the same as that of the comparative example, but the amount of chromium eluted was extremely reduced as shown in Table 1.
◎比較例２）
熔融亜鉛メッキ鋼板と、比較例１）と同様に脱脂、水洗
後ポリアクリルアミド１０ｇ／／、重クロム酸アンモニ
ウム３．８ｇ／ｊ’の混合水溶液を塗布し、１８０℃で
３分間乾燥し、０．２ ｇ ／ ｒｄの塗膜を付着させ
た。この板の耐食性は１２０時間以上、クロム溶出量は
１．８■／イであった。◎Comparative Example 2) After degreasing and washing with water in the same manner as in Comparative Example 1), a mixed aqueous solution of 10 g of polyacrylamide and 3.8 g/j' of ammonium dichromate was applied to a hot-dip galvanized steel sheet, and heated at 180°C for 3 minutes. It was dried and a coating of 0.2 g/rd was deposited. The corrosion resistance of this plate was 120 hours or more, and the amount of chromium eluted was 1.8 μ/I.
◎実施例４〜５
上記比較例２と同様組成の塗布液中に表１に示した添加
剤を加え、比較例２と同様に処理して試料を作成した。◎Examples 4 to 5 The additives shown in Table 1 were added to a coating liquid having the same composition as in Comparative Example 2, and the samples were processed in the same manner as in Comparative Example 2.
これらの板の耐食性は比較例２と変らず、クロム溶出量
は表１に示す如く低下した。The corrosion resistance of these plates was the same as that of Comparative Example 2, and the amount of chromium eluted decreased as shown in Table 1.
◎比較例３及び実施例６
使用するポリマーが、メタクリル酸、Ｎ−メ千ロールア
クリルアミド、及びｎ−ブチルアクリレート、メチルメ
タクリレートの４ ： ２ ：１００：１００の共重合
エマルジョンである以外は比較例（１）又は実施例（１
）と同様に処理した。夫々のクロム溶出量は表１に示す
如くであった。◎ Comparative Example 3 and Example 6 Comparative example ( 1) or Example (1)
). The respective amounts of chromium eluted were as shown in Table 1.
Claims (1)
よりなる造膜成分を含有する水系塗料を金属表面に塗装
する防食塗装方法において、−ＣＨ＿２ＯＨ基または＞
ＣＨＯＨ基を１個または２個以上、ただし、これらの−
ＣＨ＿２ＯＨ基または＞ＣＨＯＨ基が１個含有される場
合は、−Ｏ−基を１個以上、含有するとともに、沸点が
１００℃以上の水溶性有機化合物を添加した水系塗料を
金属表面に塗装した後加熱、乾燥することを特徴とする
防食塗装方法。In an anticorrosion coating method in which a water-based paint containing a film-forming component consisting of mono- or hexavalent chromium and a water-soluble polymer or a water-dispersible polymer is applied to a metal surface, -CH_2OH group or >
One or more CHOH groups, provided that these -
If one CH_2OH group or >CHOH group is contained, after painting the metal surface with a water-based paint containing one or more -O- groups and adding a water-soluble organic compound with a boiling point of 100°C or higher. An anticorrosive coating method that involves heating and drying.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31581786A JPS63168474A (en) | 1986-12-29 | 1986-12-29 | Coating method to impart corrosion resistance |
| EP87119190A EP0273408A3 (en) | 1986-12-29 | 1987-12-24 | Process for producing coatings on metal surfaces |
| DE19873744033 DE3744033A1 (en) | 1986-12-29 | 1987-12-24 | METHOD FOR PRODUCING COATINGS ON METAL SURFACES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31581786A JPS63168474A (en) | 1986-12-29 | 1986-12-29 | Coating method to impart corrosion resistance |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4779887A Division JPS63168473A (en) | 1987-03-04 | 1987-03-04 | Method of coating aluminum to impart corrosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63168474A true JPS63168474A (en) | 1988-07-12 |
Family
ID=18069913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31581786A Pending JPS63168474A (en) | 1986-12-29 | 1986-12-29 | Coating method to impart corrosion resistance |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0273408A3 (en) |
| JP (1) | JPS63168474A (en) |
| DE (1) | DE3744033A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001173A (en) * | 1987-05-11 | 1991-03-19 | Morton Coatings, Inc. | Aqueous epoxy resin compositions and metal substrates coated therewith |
| US5082698A (en) * | 1987-05-11 | 1992-01-21 | Morton Coatings, Inc. | Aqueous epoxy resin compositions and metal substrates coated therewith |
| US5252363A (en) * | 1992-06-29 | 1993-10-12 | Morton International, Inc. | Method to produce universally paintable passivated galvanized steel |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5345333A (en) * | 1976-10-06 | 1978-04-24 | Dainippon Ink & Chem Inc | Resin compositions for powder coating |
| JPS56135565A (en) * | 1980-03-27 | 1981-10-23 | Nippon Dakuro Shamrock:Kk | Corrosionproof coat composition |
| JPS58174582A (en) * | 1982-04-05 | 1983-10-13 | Nippon Paint Co Ltd | Weldable painted steel plate |
| JPS6050228A (en) * | 1983-08-29 | 1985-03-19 | Nissan Koki Kk | Turbosupercharging device for internal-combustion engine |
| JPS61211373A (en) * | 1985-03-14 | 1986-09-19 | Toyota Central Res & Dev Lab Inc | Water paint composition and method for forming coating film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3053693A (en) * | 1958-05-29 | 1962-09-11 | Pennsalt Chemicals Corp | Metal coating with hexavalent chromium compound |
| BE670284A (en) * | 1964-09-30 | 1966-01-17 | ||
| US3595704A (en) * | 1967-12-23 | 1971-07-27 | Yawata Iron & Steel Co | Composition for the surface-treating of metals |
| JPS54134043A (en) * | 1978-04-10 | 1979-10-18 | Kawasaki Steel Co | Electromagnetic steel plate having excellent volume ratio* punching property* and weldability for use as laminated ironcore |
-
1986
- 1986-12-29 JP JP31581786A patent/JPS63168474A/en active Pending
-
1987
- 1987-12-24 DE DE19873744033 patent/DE3744033A1/en not_active Withdrawn
- 1987-12-24 EP EP87119190A patent/EP0273408A3/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5345333A (en) * | 1976-10-06 | 1978-04-24 | Dainippon Ink & Chem Inc | Resin compositions for powder coating |
| JPS56135565A (en) * | 1980-03-27 | 1981-10-23 | Nippon Dakuro Shamrock:Kk | Corrosionproof coat composition |
| JPS58174582A (en) * | 1982-04-05 | 1983-10-13 | Nippon Paint Co Ltd | Weldable painted steel plate |
| JPS6050228A (en) * | 1983-08-29 | 1985-03-19 | Nissan Koki Kk | Turbosupercharging device for internal-combustion engine |
| JPS61211373A (en) * | 1985-03-14 | 1986-09-19 | Toyota Central Res & Dev Lab Inc | Water paint composition and method for forming coating film |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0273408A3 (en) | 1989-02-08 |
| EP0273408A2 (en) | 1988-07-06 |
| DE3744033A1 (en) | 1988-07-07 |
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