CN106634516A - Highly anti-corrosion water-based electroplating sealing agent and preparation method thereof - Google Patents
Highly anti-corrosion water-based electroplating sealing agent and preparation method thereof Download PDFInfo
- Publication number
- CN106634516A CN106634516A CN201611226949.9A CN201611226949A CN106634516A CN 106634516 A CN106634516 A CN 106634516A CN 201611226949 A CN201611226949 A CN 201611226949A CN 106634516 A CN106634516 A CN 106634516A
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- Prior art keywords
- aqueous
- parts
- plate close
- agent
- corrosion
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 50
- 238000005260 corrosion Methods 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000009713 electroplating Methods 0.000 title abstract description 6
- 238000007789 sealing Methods 0.000 title abstract 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 14
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000013530 defoamer Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- -1 sodium sulfonates Chemical class 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- GLBHAWAMATUOBB-UHFFFAOYSA-N 6,6-dimethylheptane-1,1-diamine Chemical compound CC(C)(C)CCCCC(N)N GLBHAWAMATUOBB-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- QDPMLKBAQOZXEF-UHFFFAOYSA-N ethanesulfonic acid;sodium Chemical compound [Na].CCS(O)(=O)=O QDPMLKBAQOZXEF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 claims 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 19
- 238000000576 coating method Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 238000007747 plating Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 2
- 229920000570 polyether Polymers 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 229910010272 inorganic material Inorganic materials 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000011651 chromium Substances 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of fine polymers and particularly relates to a highly anti-corrosion water-based electroplating sealing agent and a preparation method thereof. The electroplating sealing agent is a water-based emulsion prepared by taking a carbon dioxide copolymer polyhydric alcohol as a basic raw material and through organic-inorganic compound modification. According to the invention, the carbon dioxide copolymer polyhydric alcohol is applied to the electroplating sealing agent for the first time; through the good oxygen isolation property of the carbon dioxide copolymer polyhydric alcohol, the corrosion resistance of the plating is remarkably improved; and through organic-inorganic compounding, a sealing agent with high hardness and high corrosion resistance is obtained. Meanwhile, by adopting the carbon dioxide copolymer polyhydric alcohol, the defects that the hardness of a water-based coating prepared from polyether polyol is low and the water-based coating prepared from polyether polyol is easily dehydrated and then falls off are overcome, and an electroplating sealing agent integrating hardness and toughness is formed.
Description
Technical field
The present invention relates to fine polymer technical field, and in particular to it is a kind of with high anti-corrosion aqueous plate close agent and
Its preparation method.
Background technology
Metal material can produce in use, at different conditions corrosion, and after metal erosion it can be significantly reduced
Plasticity and toughness, substantially reduce the service life of metal.To improve its corrosion resistance, usually to ferrous metal plating zinc on surface simultaneously
Process is passivated, to improve its decay resistance, while products appearance can also be improved, there is provided certain dicoration.Tradition
Zinc and kirsite passivation technology typically adopt chromating, its is with low cost, and using simple, corrosion resistance is good, in aviation, electricity
Son and other industrial circles are used widely.Chromium mainly exists with sexavalence and trivalent form in chromate passivation film, trivalent chromium
Used as the skeleton of passivating film, Cr VI can again be passivated to the exposed section coating of passivating film, and further suppression is played to corrosion
Make and use.But Cr VI has certain carcinogenicity, a large amount of health for using serious environment pollution and affecting the mankind, European Union is
RoHS instructions are formally implemented on July 1st, 2006, to limit chromic use.Trivalent chromium has in many aspects very
Similar to chromic characteristic, while trivalent chromium has the advantages that toxicity is relatively low.
Chromium coating inevitably results from some holes and crackle in electroplating process, because trivalent chromium passivation film does not possess
Self-healing ability, reduces in hole and cracks corrosion resistance, many at present to be plated using sealer in order to strengthen chromium coating anti-corrosion property
Micropore and crack in one layer of macromolecule resin blocking of layer surface application and closing coating, to the erosion for completely cutting off foreign substance.
19) etc. (research of Passivation Technology with Trivalent Chromium for Zinc Coating, corrosion and protection, 2007,28 (1), 13-16, exist Ren Yanping
Acrylic resin is added in passivating solution, the crackle for finding trivalent chromium passivation film surface is completely covered by acrylic resin, film layer is caused
Density is improved.Using trivalent chromium plus acrylic resin passivation can postpone the time that white rust occurs in zinc coat, with the same terms but
Not plus the film layer of acrylic resin is compared, corrosion resistance is significantly improved.Acrylic resin resistance to water is poor, draws on the contrary after long-term water logging
Play corrosion.It is aqueous that Chinese patent CN102719121A describes a kind of low-temperature setting of hybrid inorganic-organic silane material preparation
Anticorrosive metal paint.But existing some researchs point out that alone waterborne organic silicon resin makees sealer, and its salt spray resistance is simultaneously
It is undesirable.Chinese patent CN103923560B uses organic-silicon-modified polyethylene glycol type aqueous polyurethane, prepares water-soluble envelope
Close agent, salt spray resistance has and significantly lifted.But because polyethylene glycol is water-soluble polymer, product is easily inhaled in use
Tide, produces corrosion, while layer of polyurethane hardness itself is relatively low, long-term wearability is poor.
The content of the invention
First purpose of the present invention is to provide a kind of with high anti-corrosion aqueous plate close for the deficiencies in the prior art
Agent.
It is a further object to provide a kind of preparation method with high anti-corrosion aqueous plate close agent.
In order to realize object above, the present invention provides technical scheme below：
A kind of aqueous plate close agent anti-corrosion with height, including the component of following weight portion：
It is a kind of with high anti-corrosion aqueous plate close agent as preferred, including the component of following weight portion：
As preferred, the carbon dioxide-base copolymer polyols be with carbon dioxide as initiation material, initiator,
Under catalyst action with epoxypropane copolymerization into glycol, its hydroxy functionality be 2, molecular weight is 2000-4000.
It is further preferred that the molecular weight of the carbon dioxide copolymer polyalcohol is 3000-4000.
Used as preferred, the aliphatic diisocyanate is IPDI, the isocyanic acid of hexa-methylene two
Any one or a few mixture in ester, hydrogenated diphenyl methane diisocyanate.
Used as preferred, the hydrophilic chain extender is ethylenediamine base ethyl sulfonic acid sodium, BDO -2-2 sodium sulfonates, dihydroxy
Any one or a few mixture in methylbutanoic acid, dihydromethyl propionic acid.
Used as preferred, the catalyst is any one in stannous octoate, stannous iso caprylate, dibutyl tin laurate
Plant or several mixtures.
Used as preferred, the nertralizer is the one kind or several in triethylamine tripropyl amine (TPA), tri-n-butylamine, NaOH, ammoniacal liquor
The mixture planted.
Used as preferred, the chain extender is in ethylenediamine, trimethylhexane diamine, TEPA, diethylenetriamine
Any one or a few mixture.
Used as preferred, the aqueous levelling agent is water-soluble for the silok-8255 aqueous levelling agents that mass percent is 5%
Liquid.
Used as preferred, the aqueous defoamer is silcolapse C546 waterborne organic silicons that mass percent is 5%
The defoamer aqueous solution.
A kind of preparation method of aqueous plate close agent, comprises the following steps：
Take 60 parts of carbon dioxide-base copolymer polyols, aliphatic diisocyanate 20-60 parts, hydrophilic chain extender 3-6 parts,
Catalyst 0.05-0.5 parts, are warming up to 80-95 DEG C, react 3-5h, cool to 35 DEG C or so, add nertralizer neutralization until pH value
7 are reached, adds KH-560 0.5-2 parts, stirring reaction 1-2h the emulsification of 150-200 parts deionized water to be added, after adding 0.5-2 parts
Chain extender chain extension, is subsequently adding the own ester of the positive silicic acid of 3-5 parts, adds ammoniacal liquor to adjust pH value to 8-10, stirs 1-2h, adds 1-5 parts
Aqueous levelling agent, the aqueous defoamer of 1-5 parts obtains described aqueous plate close agent.
Used as preferred, the nertralizer is any one in triethylamine tripropyl amine (TPA), tri-n-butylamine, NaOH, ammoniacal liquor
Or several mixtures.
Compared with prior art, the device have the advantages that being：
The present invention provides a kind of with high anti-corrosion aqueous plate close agent and preparation method thereof, described plate close agent
It is the raw material based on carbon dioxide-base copolymer polyols, the water-based emulsion of the preparation that is modified by Organic-inorganic composite.This
It is bright first carbon dioxide copolymer polyalcohol to be used for into plate close agent, using the excellent oxygen barrier of carbon dioxide copolymer polyalcohol
Property, increase substantially the corrosion resistance of coating；By Organic-inorganic composite, the sealer of high rigidity, high-wearing feature is obtained.Simultaneously
Using carbon dioxide copolymer polyols preparation, the aqueous coating hardness for overcoming PPG to prepare is low, PEPA system
Standby aqueous coating easily hydrolyzes the shortcoming for coming off, and forms the plate close agent of hardness and toughness combination.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, but do not constitute to the present invention it is any
Limit.
In example 1 below -5, the standard of the detection method of products obtained therefrom is as follows:Electrodeposited coating adhesive force presses GB/T9286-
1998 tests；Salt spray resistance experiment is tested by GB/T10125-2012；Water-fast experiment is tested by the method 1 in GB/T1733-93.
Embodiment 1.
Take 60 parts of carbon dioxide-base copolymer polyols, 25 parts of IPDI, hydrophilic chain extender dihydroxy first
4.7 parts of base propionic acid, 0.1 part of stannous octoate is warming up to 80 DEG C, reacts 3h, cools to 35 DEG C or so, adds triethylamine to be neutralized to pH
Value 7 or so, adds 1 part of KH-560, stirring reaction 1-2h to add 200 parts of deionized water emulsifications, add chain extension after 1 part of ethylenediamine
Agent chain extension, is subsequently adding 3 parts of own esters of positive silicic acid, adds ammoniacal liquor to adjust pH value to 8-10, stirs 2h, adds 5 parts of quality percentage
Than for the 5% silok-8255 aqueous levelling agent aqueous solution, 5 parts of aqueous defoamer, obtaining described aqueous plate close agent.
It is 0 grade that experiment test obtains the sealer with electrodeposited coating adhesive force, salt spray resistance experiment 144h, water-fast experiment 168h,
Heat-proof water tests 5h.
Embodiment 2.
Take 60 parts of carbon dioxide-base copolymer polyols, 20 parts of diisocyanate, hydrophilic chain extender dihydromethyl propionic acid 3
Part, 0.2 part of catalyst is warming up to 80 DEG C, reacts 5h, cools to 35 DEG C or so, adds nertralizer to be neutralized to pH value 7 or so, plus
Enter 0.5 part of KH-560, stirring reaction 1h adds 150 parts of deionized water emulsifications, adds 0.5 part of diethylenetriamine rear chain extender to expand
Chain, is subsequently adding 3 parts of own esters of positive silicic acid, adds ammoniacal liquor to adjust pH value to 10, stirs 1h, adds 1 part of aqueous levelling agent, 1 part
Aqueous defoamer, obtain described aqueous plate close agent.
It is 0 grade that experiment test obtains the sealer with electrodeposited coating adhesive force, salt spray resistance experiment 168h, water-fast experiment 240h,
Heat-proof water tests 8h.
Embodiment 3.
Take 60 parts of carbon dioxide-base copolymer polyols, 60 parts of hydrogenated diphenyl methane diisocyanate, hydrophilic chain extender
6 parts of dimethylolpropionic acid, 0.5 part of stannous octoate is warming up to 80 DEG C, reacts 3h, cools to 35 DEG C or so, adds triethylamine neutralization
To pH value 7 or so, 2 parts of KH-560, stirring reaction 2h is added to add 200 parts of deionized water emulsifications, add 2 parts of rear chain extenders to expand
Chain, is subsequently adding 5 parts of own esters of positive silicic acid, adds ammoniacal liquor to adjust pH value to 10, stirs 2h, and the mass percent for adding 5 parts is 5%
The silok-8255 aqueous levelling agent aqueous solution, 5 parts of aqueous defoamer obtains described aqueous plate close agent.
It is 0 grade that experiment test obtains the sealer with electrodeposited coating adhesive force, and salt spray resistance experiment 96h, water-fast experiment 168h are resistance to
Hydrothermal experiment 5h.
Embodiment 4.
Take 60 parts of carbon dioxide-base copolymer polyols, 20 parts of IPDI, the isocyanic acid of hexa-methylene two
5 parts of ester, 4.7 parts of hydrophilic chain extender dihydromethyl propionic acid, 0.2 part of stannous octoate is warming up to 90 DEG C, reacts 4h, cools to 35 DEG C
Left and right, adds ammoniacal liquor to be neutralized to pH value 7 or so, adds 1 part of KH-560, stirring reaction 2h to add 180 parts of deionized water emulsifications,
1.5 parts of rear chain extender chain extensions are added, 4 parts of own esters of positive silicic acid are subsequently adding, adds ammoniacal liquor to adjust pH value to 8, stir 2h, add 5
The mass percent of part is the 5% silok-8255 aqueous levelling agent aqueous solution, and 5 parts of aqueous defoamer obtains described water
Property plate close agent.
It is 0 grade that experiment test obtains the sealer with electrodeposited coating adhesive force, salt spray resistance experiment 144h, water-fast experiment 196h,
Heat-proof water tests 6h.
Embodiment 5.
Take 60 parts of carbon dioxide-base copolymer polyols, 25 parts of IPDI, hydrophilic chain extender dihydroxy first
4.7 parts of base propionic acid, 0.1 part of stannous octoate is warming up to 90 DEG C, reacts 4h, cools to 35 DEG C or so, adds triethylamine to be neutralized to pH
Value 7 or so, adds 1.5 parts of KH-560, stirring reaction 1-2h to add 150 parts of deionized water emulsifications, add 1 part of rear chain extender to expand
Chain, is subsequently adding 3.5 parts of own esters of positive silicic acid, adds ammoniacal liquor to adjust pH value to 8, stirs 2h, and the mass percent for adding 5 parts is
The 5% silok-8255 aqueous levelling agent aqueous solution, 5 parts of aqueous defoamer obtains described aqueous plate close agent.
It is 0 grade that experiment test obtains the sealer with electrodeposited coating adhesive force, salt spray resistance experiment 144h, water-fast experiment 168h,
Heat-proof water tests 5h.
Carbon dioxide copolymer polyalcohol is used for plate close agent by the present invention first, polynary using carbon dioxide copolymer
Excellent barrier of alcohol, increases substantially the corrosion resistance of coating；By Organic-inorganic composite, high rigidity, high-wearing feature are obtained
Sealer.Carbon dioxide copolymer polyols preparation is used simultaneously, and the aqueous coating hardness for overcoming PPG to prepare is low, gathers
Aqueous coating prepared by ester polyol easily hydrolyzes the shortcoming for coming off, and forms the plate close agent of hardness and toughness combination.
The above embodiments are only the preferred embodiments of the present invention, it is impossible to the interest field of the present invention is limited with this, because
This, the equivalent variations made according to scope of the present invention patent still belong to the scope that the present invention is covered.
Claims (10)
1. it is a kind of with high anti-corrosion aqueous plate close agent, it is characterised in that including the component of following weight portion：
2. it is according to claim 1 with high anti-corrosion aqueous plate close agent, it is characterised in that including following weight portion
Component：
3. it is according to claim 1 and 2 with high anti-corrosion aqueous plate close agent, it is characterised in that the titanium dioxide
Carbon-based copolymer polyols are with carbon dioxide as initiation material, with epoxypropane copolymerization under initiator, catalyst action
Into glycol, its hydroxy functionality be 2, molecular weight is 2000-4000.
4. it is according to claim 1 and 2 with high anti-corrosion aqueous plate close agent, it is characterised in that the aliphatic
Diisocyanate is in IPDI, hexamethylene diisocyanate, hydrogenated diphenyl methane diisocyanate
Any one or a few mixture.
5. it is according to claim 1 and 2 with high anti-corrosion aqueous plate close agent, it is characterised in that the hydrophilic expansion
Chain agent is any in ethylenediamine base ethyl sulfonic acid sodium, 1,4- butanediol -2-2 sodium sulfonates, dimethylolpropionic acid, dihydromethyl propionic acid
One or more mixtures.
6. it is according to claim 1 and 2 with high anti-corrosion aqueous plate close agent, it is characterised in that the catalyst
For any one or a few mixture in stannous octoate, stannous iso caprylate, dibutyl tin laurate.
7. it is according to claim 1 and 2 with high anti-corrosion aqueous plate close agent, it is characterised in that the chain extender
For any one or a few mixture in ethylenediamine, trimethylhexane diamine, TEPA, diethylenetriamine.
8. it is according to claim 1 and 2 with high anti-corrosion aqueous plate close agent, it is characterised in that the aqueous flow
Flat agent is the silok-8255 aqueous levelling agent aqueous solution that mass percent is 5%, and the aqueous defoamer is mass percent
For the 5% silcolapse C546 waterborne organic silicon defoamer aqueous solution.
9. a kind of preparation method of aqueous plate close agent, it is characterised in that comprise the following steps：
Take 60 parts of carbon dioxide copolymer polyalcohol, aliphatic diisocyanate 20-60 parts, hydrophilic chain extender 3-6 parts, catalyst
0.05-0.5 parts, are warming up to 80-95 DEG C, react 3-5h, cool to 35 DEG C or so, add in nertralizer and reach 7 up to pH value,
KH-560 0.5-2 parts, stirring reaction 1-2h is added to add the emulsification of 150-200 parts deionized water, add 0.5-2 part rear chain extenders
Chain extension, is subsequently adding the own ester of the positive silicic acid of 3-5 parts, adds ammoniacal liquor to adjust pH value to 8-10, stirs 1-2h, adds the aqueous of 1-5 parts
Levelling agent, the aqueous defoamer of 1-5 parts obtains described aqueous plate close agent.
10. the preparation method of aqueous plate close agent according to claim 9, it is characterised in that the nertralizer is three
Any one or a few mixture in ethamine tripropyl amine (TPA), tri-n-butylamine, NaOH, ammoniacal liquor.
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Cited By (1)
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| CN113402689A (en) * | 2021-06-23 | 2021-09-17 | 科文特亚环保电镀技术（江苏）有限公司 | Sealing agent for corrosion-resistant electroplated nickel layer |
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| CN103923560A (en) * | 2014-04-30 | 2014-07-16 | 武汉迪赛新材料有限公司 | Waterborne electro-plating sealant and preparation method thereof |
| CN104059498A (en) * | 2013-05-03 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Waterborne plating layer sealing agent and preparation method and use thereof, and hot-dip plated metal material |
| WO2016166165A1 (en) * | 2015-04-13 | 2016-10-20 | Repsol, S.A. | New formulations for polyurethane applications |
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| CN104059498A (en) * | 2013-05-03 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Waterborne plating layer sealing agent and preparation method and use thereof, and hot-dip plated metal material |
| CN103923560A (en) * | 2014-04-30 | 2014-07-16 | 武汉迪赛新材料有限公司 | Waterborne electro-plating sealant and preparation method thereof |
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