CN103360840A - Metal protective paint and application thereof, and hot-dip metal material - Google Patents
Metal protective paint and application thereof, and hot-dip metal material Download PDFInfo
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- CN103360840A CN103360840A CN2012100919407A CN201210091940A CN103360840A CN 103360840 A CN103360840 A CN 103360840A CN 2012100919407 A CN2012100919407 A CN 2012100919407A CN 201210091940 A CN201210091940 A CN 201210091940A CN 103360840 A CN103360840 A CN 103360840A
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- water
- soluble
- forming resin
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Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 111
- 239000002184 metal Substances 0.000 title claims abstract description 111
- 239000007769 metal material Substances 0.000 title claims abstract description 10
- 239000002519 antifouling agent Substances 0.000 title abstract 5
- 239000011248 coating agent Substances 0.000 claims abstract description 97
- 238000000576 coating method Methods 0.000 claims abstract description 97
- 239000011347 resin Substances 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 19
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 19
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2R,3R,4S,5R,6S)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2S,3R,4S,5R,6R)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2R,3R,4S,5R,6R)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 18
- 229920000591 gum Polymers 0.000 claims description 18
- 229920000609 methyl cellulose Polymers 0.000 claims description 18
- 239000001923 methylcellulose Substances 0.000 claims description 18
- HNJBEVLQSNELDL-UHFFFAOYSA-N 2-Pyrrolidone Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- -1 Natvosol Polymers 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 5
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 5
- XAPRFLSJBSXESP-UHFFFAOYSA-N Oxycinchophen Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=C(O)C=1C1=CC=CC=C1 XAPRFLSJBSXESP-UHFFFAOYSA-N 0.000 claims description 5
- 210000001138 Tears Anatomy 0.000 claims description 5
- 238000005269 aluminizing Methods 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 5
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 5
- 229940071676 hydroxypropylcellulose Drugs 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-phenylpropan-1-ol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002118 epoxides Chemical class 0.000 claims description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-ethylpyrrolidin-2-one Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 3
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-methylthiourea Chemical group CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000001681 protective Effects 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 7
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- 239000000758 substrate Substances 0.000 abstract 2
- 229910000831 Steel Inorganic materials 0.000 description 22
- 239000010959 steel Substances 0.000 description 22
- 238000005039 chemical industry Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 11
- 229910018137 Al-Zn Inorganic materials 0.000 description 10
- 229910018573 Al—Zn Inorganic materials 0.000 description 10
- 238000007639 printing Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 235000019353 potassium silicate Nutrition 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920000126 Latex Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000007601 warm air drying Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 244000174681 Michelia champaca Species 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N Potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 229920002803 Thermoplastic polyurethane Polymers 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-Aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N Fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229940099259 Vaseline Drugs 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000994 depressed Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive Effects 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004544 spot-on Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Abstract
The invention provides a metal protective paint which is prepared by uniformly mixing a raw material mixture, wherein the raw material mixture contains water-soluble silicate, silicon oxide filler, accelerator, water-soluble film-forming resin, (CH3CH2O)3Si(CH2)2Si(OCH2CH3)3 and water; and the accelerator is composed of at least two of first accelerator, second accelerator and third accelerator. The invention also discloses application of the metal protective paint in preparation of metal materials. The invention also provides a hot-dip metal material which comprises a hot-dip metal substrate and a coating attached to the hot-dip metal substrate, wherein the coating is the cured product of the metal protective paint. The protective film formed by the metal protective paint provided by the invention has very excellent corrosion resistance, water resistance, heat resistance and fingerprint resistance.
Description
Technical field
The present invention relates to the metal protection field, particularly, relate to a kind of metal protection coating, the purposes of this metal protection coating and a kind of hot-dip metal plated material.
Background technology
Hot-dip metal plated material comprises hot-dip galvanized metal material and hot-dip aluminizing zinc metallic substance, in order to prevent corrosion, and all can be at the surface of hot-dip metal plated material coating layer of metal protective coating to form protective film.Thereby the performance of metal protection coating is very important for the rust protection of hot-dip metal plated material.
For example, CN101608306A discloses a kind of passivating solution, also belongs to a kind of metal protection coating, it is characterized in that, this passivating solution is the aqueous solution that contains water-soluble molybdenum compound, boric acid, water soluble organic substance and silicon sol, and wherein, described water soluble organic substance is the mixture of pure and mild organic carboxyl acid.
But the solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing that experiment showed, the protective film that this metal protection coating forms are still relatively poor.
Summary of the invention
The objective of the invention is to overcome the relatively poor defective of solidity to corrosion, water tolerance, thermotolerance and anti-finger printing of the protective film that existing metal protection coating forms, provide a kind of and can form the preferably metal protection coating of protective film of solidity to corrosion, water tolerance, thermotolerance and anti-finger printing.
To achieve these goals, the invention provides a kind of metal protection coating, this metal protection coating obtains after being mixed by a kind of raw mix, and described raw mix contains water-soluble silicate, cilicon oxide filler, promotor, water-soluble film-forming resin, (CH
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3And water; Described promotor is at least two kinds in the first promotor, the second promotor and the 3rd promotor; Described the first promotor is at least a in pyrrolidone, N-Methyl pyrrolidone and the N-ethyl pyrrolidone; Described the second promotor is thiocarbamide and/or urea; Described the 3rd promotor is at least a in methylcellulose gum, ethyl cellulose, Natvosol, hydroxypropylcellulose, Vltra tears and the Xylo-Mucine.
The present invention also provides the purposes of above-mentioned metal protection coating in the preparation metallic substance.
The present invention also provides a kind of hot-dip metal plated material, this hot-dip metal plated material comprises hot-dip metal plated base material and the coating that is attached on this hot-dip metal plated base material, described hot-dip metal plated base material is pot galvanize metal base and/or hot-dip aluminizing zinc metal base, it is characterized in that described coating is the cured product of aforesaid metal protection coating.
By technique scheme, solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing of the protective film that metal protection coating provided by the invention forms are all very good.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
According to metal protection coating provided by the invention, wherein, this metal protection coating obtains after being mixed by a kind of raw mix, and described raw mix contains water-soluble silicate, cilicon oxide filler, promotor, water-soluble film-forming resin, (CH
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3And water; Described promotor is at least two kinds in the first promotor, the second promotor and the 3rd promotor; Described the first promotor is at least a in pyrrolidone, N-Methyl pyrrolidone and the N-ethyl pyrrolidone; Described the second promotor is thiocarbamide and/or urea; Described the 3rd promotor is at least a in methylcellulose gum, ethyl cellulose, Natvosol, hydroxypropylcellulose, Vltra tears and the Xylo-Mucine.
Wherein, (CH
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3Be called two (1,2-triethoxy is silica-based) ethane, can be used as silane coupling agent, the commercially available various (CH that can be used as silane coupling agent
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3Commodity may be used to the present invention.
Wherein, this metal protection coating is to obtain after described raw mix mixes, and is the liquid of comparatively stable and homogeneous.Under the preferable case, each component in the described raw mix mixed before use at this metal protection coating in 1-180 days.Wherein, the order by merging of each composition is not had special requirement, can directly each component in the described raw mix be carried out simultaneously, in batches or substep mix, as long as can obtain uniform stable phase, preferably make mixing more even by stirring.
According to metal protection coating provided by the invention, wherein, with respect to the described water-soluble silicate of 1 weight part, (CH
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3Consumption can be the 0.5-4.5 weight part, be preferably the 1.4-1.8 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the content of described promotor can be the 0.2-1.8 weight part, is preferably the 0.5-0.7 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of described cilicon oxide filler can be the 0.25-2.2 weight part, is preferably the 0.6-0.85 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, in solid, the consumption of described water-soluble film-forming resin can be the 0.8-6.8 weight part, is preferably the 2.1-2.7 weight part.Herein solid be used for to calculate or the solid implication of expression solid content identical, be remaining composition after the water-soluble film-forming resin desolventizing.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of water is the 10-100 weight part, is preferably the 25-40 weight part.Need to prove that the consumption of said water refers to the amount of the water that adds in addition among the present invention, do not comprise in above-mentioned other component of adding with solution or emulsion mode with the amount of water.
According to metal protection coating provided by the invention, wherein, in order further to improve the performance of described metal protection coating, under the preferable case, described the first promotor is pyrrolidone.
According to metal protection coating provided by the invention, wherein, in order further to improve the performance of described metal protection coating, under the preferable case, described the second promotor is urea.
According to metal protection coating provided by the invention, wherein, described the 3rd promotor is at least a in methylcellulose gum, ethyl cellulose, Natvosol, hydroxypropylcellulose, Vltra tears and the Xylo-Mucine; Wherein, described promotor all can be the commercially available prod of the industrial application of routine, the present invention does not have special requirement, as long as can be for the preparation of water-borne coatings, for example can be in methylcellulose gum, ethyl cellulose, Natvosol, hydroxypropylcellulose, Vltra tears and the Xylo-Mucine of building the makers' various models of additive available from rain field, Feicheng, Shandong chemical industry company limited or Shijiazhuang Clyde at least a; In order further to improve the performance of described metal protection coating, under the preferable case, described the 3rd promotor is methylcellulose gum.Typically, the viscosity of methylcellulose gum (under 20 ℃, in the aqueous solution of 2 % by weight concentration) can be 5-100000mPaS, and methoxy content can be the 26-33 % by weight, but is not limited to this.
Further under the preferable case, described promotor is the mixture of pyrrolidone, urea and methylcellulose gum.Wherein, the weight ratio of pyrrolidone, urea and methylcellulose gum can be 1: (0.1-10): (0.1-10), be preferably 1: (0.5-2): (0.5-2), most preferably be 1: 1: 1.
According to metal protection coating provided by the invention, wherein, described water-soluble silicate can be water glass and/or potassium silicate.
According to metal protection coating provided by the invention, wherein, described cilicon oxide filler does not have special requirement, can be the various fillers take silicon oxide as main body, and for example, described cilicon oxide filler can be nano-silica powder and/or silicon sol; Under the preferable case, described cilicon oxide filler is nano-silica powder, and the particle diameter of described nano-silica powder can be 10-90nm.
According to metal protection coating provided by the invention, wherein, described water-soluble film-forming resin can be for various water miscible and can be used in modification or the unmodified resin of film forming, described resin can use with suitable goods form, water-soluble emulsion for example, at least a in water-soluble solution and the water-soluble solid, the present invention does not have special requirement, as long as the film forming of can be used in, for example, described water-soluble film-forming resin can be the water-soluble polyester film-forming resin (water-soluble film-forming resin that is namely got by polyalcohols monomer and polynary acids monomer polymerization, for example available from Guangzhou Lapo Fine Chemicals Co., Ltd., the vibrin of trade mark CB2200), water-soluble phenylpropyl alcohol film-forming resin (namely by styrene monomer and vinylformic acid (ester) class monomer polymerization and water-soluble film-forming resin, for example available from the super imperial Chemical Industry Science Co., Ltd in Guangzhou, the trade mark is the benzene emulsion of xy-108b), soluble epoxide film-forming resin (the water-soluble film-forming resin that is namely got by the monomer polymerization that contains epoxy group(ing), for example available from Dongguan City Heima Chemical Co., Ltd., the trade mark is the Resins, epoxy of BH620), the aqurous ployurethane film-forming resin (namely by multicomponent isocyanate class monomer and multi-hydroxy compounds monomer polymerization and water-soluble film-forming resin, for example build Hua company available from Jinjiang, Fujian Province, the urethane resin of the trade mark 812), water-soluble silicon the third film-forming resin (namely by silicone based monomer and vinylformic acid (ester) class monomer polymerization and water-soluble film-forming resin, the Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous for example, solid content is 48 % by weight), water-soluble acrylic film-forming resin (the water-soluble film-forming resin that is namely got by vinylformic acid (ester) class monomer polymerization, for example the trade mark available from Guangzhou Ou Peng chemical industry is the acrylic resin of A-3418) and the water-soluble fluorine carbon film-forming resin (water-soluble film-forming resin that is namely got by the fluorinated monomer polymerization, for example available from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I) at least a; Under the preferable case, described water-soluble film-forming resin is at least a in water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin, aqurous ployurethane film-forming resin and the water-soluble polyester film-forming resin.
Except containing mentioned component, metal protection coating of the present invention can also contain other various components that do not affect the metal protection coating property, such as in dyestuff, pigment, dispersion agent and the defoamer one or more.Take the gross weight of this metal protection coating as benchmark, the content of other component is no more than 20 % by weight, preferably is no more than 10 % by weight.Described defoamer can be various defoamer well known in the art, such as in polyethers defoamer, higher alcohols defoamer and the silicon defoamer etc. one or more.More particularly, described defoamer can be for being purchased in the SD-401 of limited liability company of the large Creative Science and Technology Co. Ltd of Dongying dan for example series defoamer one or more.Under the preferable case, take the total amount of described metal protection coating as benchmark, the content of described defoamer is the 0.01-0.05 % by weight.
Metal protection coating of the present invention need not dilution and can directly use.
The present invention also provides the purposes of above-mentioned metal protection coating in the preparation metallic substance.Above-mentioned metal protection coating can be in the mode of this area routine for the preparation of various metallic substance.
According to hot-dip metal plated material provided by the invention, this hot-dip metal plated material comprises pot galvanize metal base and the coating that is attached on this hot-dip metal plated base material, described hot-dip metal plated base material is pot galvanize metal base and/or hot-dip aluminizing zinc metal base, it is characterized in that described coating is the cured product of aforesaid metal protection coating.
Wherein, described pot galvanize metal base can be for containing the metal base of zinc coating, and in the described zinc coating, the content of zinc can be the 92.5-95.5 % by weight.Described zinc coating also can contain other conventional ingredient, such as silicon.
Wherein, described hot-dip aluminizing zinc metallic substance can be for containing the metal base of zinc-aluminium coating, and in the described zinc-aluminium coating, the content of zinc can be the 41.5-43.5 % by weight, and the content of aluminium can be the 51.5-55.0 % by weight.Described zinc-aluminium coating also can contain other conventional ingredient, such as silicon.
According to hot-dip metal plated material provided by the invention, wherein, the thickness of described coating can be the conventional thickness of the erosion shield on the hot-dip metal plated base material, in order to improve the performance of described coating, under the preferable case, the thickness of described coating is the 0.05-2 micron, preferably can be the 0.1-1 micron.
According to hot-dip metal plated material provided by the invention, wherein, the method of adhering to described coating at hot-dip metal plated base material can comprise described metal protection coating is attached on the surface of hot-dip metal plated base material, then dry, dry temperature can be 60-120 ℃, be preferably 90-110 ℃, the time can be 0.5-3 second.The consumption of described metal protection coating can be determined according to the thickness of coating.
Wherein, the method for described drying can be in warm air drying, induction heating and the infrared radiation heating one or more.
Among the present invention, do not do in the situation of opposite explanation, the volume of all liquid and solid all refers to 20 ℃, the volume that 1 standard atmosphere is depressed.
Below will be explained in further detail the present invention by embodiment.
Embodiment 1
Water-soluble silicate (water glass with 1 weight part, moisten rich Industrial Co., Ltd. available from Baoding), (CH of the promotor of 0.6 weight part (pyrrolidone, urea and methylcellulose gum (available from rain field, Feicheng, Shandong chemical industry company limited, the trade mark 55) obtain after mixing by weight 1: 1: 1), 1.6 weight parts
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3(available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-26E), the cilicon oxide filler (nano-silica powder of 0.72 weight part, available from U.S. GE company, RNS-E, mean particle size 20nm), the water-soluble film-forming resin of 2.4 weight parts (in solid) (water-soluble silicon the third film-forming resin (Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous, solid content is 48 % by weight)) and the water of 28 weight parts, under 1500 rev/mins stirring velocity, be mixed to evenly, obtain the metal protection coating of present embodiment.
Comparative Examples 1
Method according to embodiment 1 prepares metal protection coating, and different is to replace (CH with aminopropyl triethoxysilane (available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-1100)
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3
Comparative Examples 2
Method according to embodiment 1 prepares metal protection coating, and different is not add promotor.
Comparative Examples 3
Method according to embodiment 1 prepares metal protection coating, and different is not add water-soluble silicate.
Comparative Examples 4
Method according to embodiment 1 prepares metal protection coating, and different is not add cilicon oxide filler.
Embodiment 2
Water-soluble silicate (potassium silicate with 1 weight part, moisten rich Industrial Co., Ltd. available from Baoding), (CH of the promotor of 0.5 weight part (pyrrolidone, urea and methylcellulose gum (available from rain field, Feicheng, Shandong chemical industry company limited, the trade mark 55) obtain after mixing by weight 1: 1: 1), 1.4 weight parts
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3(available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-26E), the cilicon oxide filler (nano silicon of 0.6 weight part, available from U.S. GE company, RNS-E, mean particle size 20nm), the water of the water-soluble film-forming resin of 2.1 weight parts (take solid) (water-soluble acrylic film-forming resin (available from the trade mark of the Guangzhou Ou Peng chemical industry acrylic resin as A-3418)) and 25 weight parts, under 1500 rev/mins stirring velocity, be mixed to evenly, obtain the metal protection coating of present embodiment.
Embodiment 3
Water-soluble silicate (water glass with 1 weight part, moisten rich Industrial Co., Ltd. available from Baoding), (CH of the promotor of 0.7 weight part (pyrrolidone, urea and methylcellulose gum (available from rain field, Feicheng, Shandong chemical industry company limited, the trade mark 55) obtain after mixing by weight 1: 1: 1), 1.8 weight parts
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3(available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-26E), the cilicon oxide filler of the 0.85 weight part (silicon sol of 30 % by weight, usage quantity is in solid), (the aqurous ployurethane film-forming resin (is built Hua company available from Jinjiang, Fujian Province for the water-soluble film-forming resin of 2.7 weight parts (in solid), and the water of 40 weight parts the urethane resin of the trade mark 812)), under 1500 rev/mins stirring velocity, be mixed to evenly, obtain the metal protection coating of present embodiment.
Embodiment 4
Water-soluble silicate (water glass with 1 weight part, moisten rich Industrial Co., Ltd. available from Baoding), (CH of the promotor of 0.3 weight part (pyrrolidone, urea and methylcellulose gum (available from rain field, Feicheng, Shandong chemical industry company limited, the trade mark 55) obtain after mixing by weight 1: 1: 1), 0.6 weight part
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3(available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-26E), the cilicon oxide filler (nano-silica powder of 2.1 weight parts, available from U.S. GE company, RNS-E, mean particle size 20nm), the water-soluble film-forming resin of 6.5 weight parts (in solid) (water-soluble silicon the third film-forming resin (Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous, solid content is 48 % by weight)) and the water of 90 weight parts, under 1500 rev/mins stirring velocity, be mixed to evenly, obtain the metal protection coating of present embodiment.
Embodiment 5
Water-soluble silicate (water glass with 1 weight part, moisten rich Industrial Co., Ltd. available from Baoding), (CH of the promotor of 1.7 weight parts (pyrrolidone, urea and methylcellulose gum (available from rain field, Feicheng, Shandong chemical industry company limited, the trade mark 55) obtain after mixing by weight 1: 1: 1), 4.5 weight parts
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3(available from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-26E), the cilicon oxide filler (nano-silica powder of 0.3 weight part, available from U.S. GE company, RNS-E, mean particle size 20nm), the water-soluble film-forming resin of 1.0 weight parts (in solid) (water-soluble silicon the third film-forming resin (Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous, solid content is 48 % by weight)) and the water of 15 weight parts, under 1500 rev/mins stirring velocity, be mixed to evenly, obtain the metal protection coating of present embodiment.
Embodiment 6
Method according to embodiment 1 prepares metal protection coating, and different is, use pyrrolidone and urea with the mixed mixture of 1: 1 weight ratio as promotor.
Embodiment 7
Method according to embodiment 1 prepares metal protection coating, and different is, use pyrrolidone and methylcellulose gum (available from rain field, Feicheng, Shandong chemical industry company limited, the trade mark 55) with the mixed mixture of 1: 1 weight ratio as promotor.
Embodiment 8
Method according to embodiment 1 prepares metal protection coating, and different is, use urea and methylcellulose gum (available from rain field, Feicheng, Shandong chemical industry company limited, the trade mark 55) with the mixed mixture of 1: 1 weight ratio as promotor.
Embodiment 9
Method according to embodiment 1 prepares metal protection coating, and different is to use water-soluble phenylpropyl alcohol film-forming resin (available from the super imperial Chemical Industry Science Co., Ltd in Guangzhou, the trade mark is the benzene emulsion of xy-108b) as water-soluble film-forming resin.
Embodiment 10
Method according to embodiment 1 prepares metal protection coating, and different is to use soluble epoxide film-forming resin (available from Dongguan City Heima Chemical Co., Ltd., the trade mark is the aqueous epoxy resin emulsion of BH620) as water-soluble film-forming resin.
Embodiment 11
Method according to embodiment 1 prepares metal protection coating, and different is to use water-soluble polyester film-forming resin (available from chemical industry company limited of the poly-section of Yancheng, Jiangsu Province, the trade mark is the waterborne polyester of PE-10030-P) as water-soluble film-forming resin.
Preparation Example 1
Get the metal protection coating that embodiment 1-11 and Comparative Examples 1-4 obtain and be coated on respectively steel plate galvanized (available from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX54D, contain zinc 95 % by weight in the zinc coating) the surface, 90-110 ℃ of lower warm air drying 2 seconds, the steel plate galvanized 1-15 after obtaining processing.Wherein, coating amount is so that the thickness of the coating on the steel plate galvanized 1-15 is 0.8 micron.The thickness of coating is the numerical value of measuring with XRF (fluorescence spectrophotometer) survey meter.
Preparation Example 2
Get the metal protection coating that embodiment 1-11 and Comparative Examples 1-4 obtain and be coated on respectively Al-Zn coated steel (available from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX51D+AZ, contain zinc 42.5 % by weight in the aluminum-zinc alloy layer, contain aluminium 52.3 % by weight) the surface, 90-110 ℃ of lower warm air drying 2 seconds, the Al-Zn coated steel 1-15 after obtaining processing.Wherein, coating amount is so that the thickness of the coating on the Al-Zn coated steel 1-15 is 0.8 micron.The thickness of coating is the numerical value of measuring with XRF (fluorescence spectrophotometer) survey meter.
Test implementation example 1
By the requirement of regulation among the GB/T 10,125 1997, carry out neutral salt spray test, measure the corrosion resistance nature of steel plate galvanized 1-15 and Al-Zn coated steel 1-15.It is qualified to be considered as by " salt-fog test 96h, corrosion area＜20% ".
As follows, measure the water resistance of steel plate galvanized 1-15 and Al-Zn coated steel 1-15.
Surface at steel plate galvanized 1-15 and the Al-Zn coated steel 1-15 of horizontal positioned, drip about 2 milliliters boiling water, after seasoning in 24 hours, adhere to the 3M adhesive tape place of will dripping, to the counting of the spot under being stained with on the adhesive tape, according to the counting of sticking lower spot on every square centimeter of adhesive tape, judge the quality of rete water tolerance, spot under sticking is more, and water tolerance is poorer.
As follows, measure the thermotolerance of steel plate galvanized 1-15 and Al-Zn coated steel 1-15.
Steel plate galvanized 1-15 and Al-Zn coated steel 1-15 are placed in the hotblast stove, 300 ℃ of lower bakings 20 minutes, then take out and observe the coatingsurface morphology change, and adopt Δ L (brightness variable), Δ a (red green variable), the Δ b (champac variable) of color difference meter test baking front and back specimen surface to be worth, and calculate Δ E (aberration)=(Δ L
2+ Δ a
2+ Δ b
2)
1/2The less coating of Δ E namely has better thermotolerance.
As follows, measure the anti-finger printing of steel plate galvanized 1-15 and Al-Zn coated steel 1-15.
Adopt Δ L (brightness variable), Δ a (red green variable), Δ b (champac variable) value of color difference meter test steel plate galvanized 1-15 and 0.5 g/m of Vaseline front and back of Al-Zn coated steel 1-15 coating, and calculate Δ E (aberration)=(Δ L
2+ Δ a
2+ Δ b
2)
1/2, the less coating of Δ E namely has better anti-finger printing energy.
Aforesaid test result is as shown in table 1.
Table 1
According to the data of table 1 as seen, solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing of the protective film that forms of metal protection coating provided by the invention are all very good.And according to the data of table 1 as seen, with respect to the described water-soluble silicate of 1 weight part, the content of described promotor is the 0.5-0.7 weight part, (CH preferably
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3Consumption be the 1.4-1.8 weight part, the consumption of described cilicon oxide filler is the 0.6-0.85 weight part, in solid, the consumption of described water-soluble film-forming resin is the 2.1-2.7 weight part, the consumption of water is in the situation of 25-40 weight part, can further improve solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing of the protective film of described metal protection coating formation.And, according to the data of table 1 as seen, in the situation of the mixture that preferred described promotor is pyrrolidone, urea and methylcellulose gum, can further improve solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing of the protective film of described metal protection coating formation.
More than describe preferred implementation of the present invention in detail; but the present invention is not limited to the detail in the above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove in addition, each concrete technical characterictic described in above-mentioned embodiment in reconcilable situation, can make up by any suitable mode, for fear of unnecessary repetition, the present invention is to the no longer separately explanation of various possible array modes.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. metal protection coating, this metal protection coating obtains after being mixed by a kind of raw mix, and described raw mix contains water-soluble silicate, cilicon oxide filler, promotor, water-soluble film-forming resin, (CH
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3And water; Described promotor is at least two kinds in the first promotor, the second promotor and the 3rd promotor; Described the first promotor is at least a in pyrrolidone, N-Methyl pyrrolidone and the N-ethyl pyrrolidone; Described the second promotor is thiocarbamide and/or urea; Described the 3rd promotor is at least a in methylcellulose gum, ethyl cellulose, Natvosol, hydroxypropylcellulose, Vltra tears and the Xylo-Mucine.
2. metal protection coating according to claim 1, wherein, with respect to the described water-soluble silicate of 1 weight part, (CH
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3Consumption be the 0.5-4.5 weight part, the consumption of described cilicon oxide filler is the 0.25-2.2 weight part, and the content of described promotor is the 0.2-1.8 weight part, in solid, the consumption of described water-soluble film-forming resin is the 0.8-6.8 weight part, and the consumption of water is the 10-100 weight part.
3. metal protection coating according to claim 2, wherein, with respect to the described water-soluble silicate of 1 weight part, the content of described promotor is the 0.5-0.7 weight part, (CH
3CH
2O)
3Si (CH
2)
2Si (OCH
2CH
3)
3Consumption be the 1.4-1.8 weight part, the consumption of described cilicon oxide filler is the 0.6-0.85 weight part, in solid, the consumption of described water-soluble film-forming resin is the 2.1-2.7 weight part, the consumption of water is the 25-40 weight part.
4. the described metal protection coating of any one according to claim 1-3, wherein, described promotor is the mixture of pyrrolidone, urea and methylcellulose gum.
5. the described metal protection coating of any one according to claim 1-3, wherein, described cilicon oxide filler is nano-silica powder and/or silicon sol.
6. the described metal protection coating of any one according to claim 1-3, wherein, described water-soluble film-forming resin is at least a in water-soluble polyester film-forming resin, water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, aqurous ployurethane film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin and the water-soluble fluorine carbon film-forming resin.
7. the described metal protection coating of any one according to claim 1-3, wherein, described raw mix also contains one or more in dispersion agent, defoamer and the stablizer.
Among the claim 1-7 the described metal protection coating of any one in the purposes of preparation in the metallic substance.
9. hot-dip metal plated material, this hot-dip metal plated material comprises hot-dip metal plated base material and the coating that is attached on this hot-dip metal plated base material, described hot-dip metal plated base material is pot galvanize metal base and/or hot-dip aluminizing zinc metal base, it is characterized in that described coating is the cured product of the described metal protection coating of any one among the claim 1-7.
10. hot-dip metal plated material according to claim 9, wherein, the thickness of described coating is the 0.1-1 micron.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256922A (en) * | 2019-06-27 | 2019-09-20 | 安徽鼎旺环保材料科技有限公司 | Latex sealer and preparation method thereof |
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|---|---|---|---|---|
| CN1242805A (en) * | 1997-01-09 | 2000-01-26 | 辛辛那提大学 | Method of preventing corrosion of metals using silanes |
| CN1730570A (en) * | 2005-08-02 | 2006-02-08 | 陈国军 | High temperature energy-saving corrosion-resisting paint , preparation and usage |
| CN1936101A (en) * | 2006-09-09 | 2007-03-28 | 重庆工学院 | Method for silane reinforcing magnesium alloy cathode electrophoretic corrosion-proof layer |
| CN101760736A (en) * | 2008-12-26 | 2010-06-30 | 汉高（中国）投资有限公司 | Galvanized steel sheet surface treating agent, galvanized steel sheet and preparation methods thereof |
-
2012
- 2012-03-31 CN CN201210091940.7A patent/CN103360840B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242805A (en) * | 1997-01-09 | 2000-01-26 | 辛辛那提大学 | Method of preventing corrosion of metals using silanes |
| CN1730570A (en) * | 2005-08-02 | 2006-02-08 | 陈国军 | High temperature energy-saving corrosion-resisting paint , preparation and usage |
| CN1936101A (en) * | 2006-09-09 | 2007-03-28 | 重庆工学院 | Method for silane reinforcing magnesium alloy cathode electrophoretic corrosion-proof layer |
| CN101760736A (en) * | 2008-12-26 | 2010-06-30 | 汉高（中国）投资有限公司 | Galvanized steel sheet surface treating agent, galvanized steel sheet and preparation methods thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110256922A (en) * | 2019-06-27 | 2019-09-20 | 安徽鼎旺环保材料科技有限公司 | Latex sealer and preparation method thereof |
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