CN102070966A - Organic and inorganic mixed fingerprint-resistance coating and preparation method thereof - Google Patents
Organic and inorganic mixed fingerprint-resistance coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an organic and inorganic mixed fingerprint-resistance coating and a preparation method thereof. The coating is prepared from the following chemical components in percentage by weight: 40 to 70 percent of aqueous resin, 3 to 10 percent of modified silica solution, 2 to 15 percent of amino resin, 2 to 10 percent of polyisocyanates, 1 to 5 percent of mineral salt, 1 to 6 percent of aqueous polyethylene wax pulp, 1 to 9 percent of adhesion promoter, 0.1 to 0.5 percent of flatting agent, and 10 to 40 percent of deionized water. And the total weight percentage of the raw materials is 100 percent. The organic and inorganic mixed fingerprint-resistance coating prepared by the method does not contain metal ions which cause pollution to the environment. The coating can be coated on an electrogalvanized steel sheet, hot-dip galvannealed sheet, tin-plated steel sheet or cold-rolled steel sheet, and after being coated, the coating can be baked for only 8 to 15 seconds to be solidified into a transparent coating with high fingerprint resistance, corrosion resistance, high hardness, scraping resistance, conductivity, self-lubricating performance, coating performance and the like.
Description
Technical field
The present invention relates to a kind of protecting metallic surface coating composition, especially a kind of fingerprint-resistant coating based on hybrid and preparation method thereof.
Background technology
In recent years, steel plate galvanized has obtained widespread use in industries such as household electrical appliances, automobile, office appliance and toys, along with improving constantly of people's quality of life, not only requires its product that uses to have aesthetic property, also will possess the feature of environmental protection.Anti-finger print steel plate is a kind of high added value surface treated product, and it is compared with general exposed steel plate galvanized, not only has anti-finger printing, also has erosion resistance, electroconductibility and coating etc. again.Nowadays, grow with each passing day to the demand of anti-finger print steel plate product in market, and this has also just promoted the exploitation to the new Application Areas of anti-fingerprint Processing Technology and fingerprint-resistant coating.The used chemical processing agent of anti-fingerprint processing is the passivator of chromate and the mixture of water-based organic coating in the prior art, owing to wherein contain the very deleterious sexavalent chrome of environment, this makes such coating to environment bigger pollution be arranged in preparation, storage, transportation and use.
At present, the raising that fingerprint-resistant coating is required is embodied in, fingerprint-resistant coating applies the back anti-finger print steel plate and not only has the anti-finger printing and the feature of environmental protection, also will possess multiple performance (high glossiness, erosion resistance, high rigidity, resistance to marring, electroconductibility, self lubricity and coating) in one, the anti-finger print steel plate that can satisfy multiple service requirements just is with a wide range of applications.
In some patents both domestic and external of having announced, the patent of Nihon Parkerizing Co., Ltd. application (publication number: EP1426466A1) disclose a kind of metal conditioner, it is characterized in that compound with the resin of urethane resin, acrylic resin, Resins, epoxy, vibrin and the polyamide resin of cationic or non-ionic type and ad hoc structure and Zr, Ti, V, Mo, W, Mn and Ce cooperates with water and constitutes.This invention does not contain chromium, can give the good solidity to corrosion of metallic substance, alkali resistance and anti-finger printing.(publication number: EP780452A2) application discloses a kind of " water-based paint " to European patent in addition, it directly adopts epoxide modified acrylic resin is membrane-forming agent, but this coating is container to be used, and is to adopt the back coating, for the steel plate galvanized that needs precoated layer to handle and inapplicable.At home, Shanghai Baoshan Iron ﹠ Steel Group Corp. and Shanghai Luo Si chemical building material company limited open in 1996 (publication number: CN1118790) a kind of production method of anti-finger print steel plate, based on aqueous acrylic emulsion, add the aqueous high molecular organic coating that organic silicon solution, film coalescence aid and water are formed.Other have Jiangsu Lanling Macromolecule Materials Co., Ltd application and open (publication number: CN101121860A) a kind of metal conditioner that does not contain chromium of giving superior solidity to corrosion of galvanized sheet and anti-finger printing, it adds the water-borne coatings that silicon sol, water-based tetrafluoroethylene wax slurry, wetting agent, defoamer and film coalescence aid are formed based on aqueous polyurethane.Jiangyin Changfa Fingerprint Resistant Steel Plate Co., Ltd. has applied for (application number: CN200710141563.2) with the fingerprint-resisting water borne coating of zirconium to substitute chromium, open on May 28th, 2008 on August 30th, 2005.Adopting acrylic resin is main membrane-forming agent, adds the metal zirconium ion of 0.5～1.0wt%, and wax becomes to grade.Tongji University on November 6th, 2008 apply for (application number: CN200810202325.2) a kind of environment-friendly type fingerprint-resistant coating patent, and it is open in 2009, this coating mainly is matrix resin with the aqueous epoxy resins, but its composition is A, B two-pack, have complicated operation, can not long-term storage after the allotment etc. problem.Shanghai Baoshan Iron ﹠ Steel Co., Ltd on August 19th, 2009 open (publication number: CN101509131A) a kind of metal conditioner of anti-corrosion anti-finger printing, be a kind of based on organic polymer resin, silicone resin, the aqueous high molecular organic coating of add that water system is cured, nano-oxide, metallic compound, silane mixture and water being formed.Recently, Zhongye Continuous Casting Tech. Engineering Co., Ltd. on December 16th, 2009 open (publication number: CN101602910A) a kind of water base fingerprint-resisting paint that is used for galvanized sheet, it is mainly formed by water-base resin, inorganic salt, silicon sol, auxiliary agent A, auxiliary agent B and water feedstock production, and set time was at 20 seconds～1 minute.Chinese Academy of Sciences Ningbo Material Technology and Engineering Institute application on July 8th, 2010 (application number: CN201010226044.8) a kind of high-hardness fingerprint-resistant coating and preparation method thereof, with the fluorocarbon resin is main film forming substance, add aminoresin, nano particle again, tetrafluoroethylene, polyethylene wax, auxiliary agent and organic solvent combine, but this coating is solvent-borne type, and environment is had certain pollution.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of fingerprint-resistant coating based on hybrid and preparation method thereof.
Technical scheme: the present invention is a kind of fingerprint-resistant coating based on hybrid, its main chemical compositions is that water-base resin, modified silicasol, aminoresin, polyisocyanates, inorganic salt, aqueous polyethylene wax slurry, adhesion promoter, flow agent and deionized water feedstock production form, and the shared weight percent of each raw material is:
Water-base resin 40～70wt%
Modified silicasol 3～10wt%
Aminoresin 2～15wt%
Polyisocyanates 2～10wt%
Inorganic salt 1～5wt%
Aqueous polyethylene wax slurry 1～6wt%
Adhesion promoter 1～9wt%
Flow agent 0.1～0.5wt%
Deionized water 10～40wt%
The shared weight percent of each raw material and be 100%.
Among the present invention, described water-base resin be in water-borne acrylic resin, aqueous epoxy resins or the aqueous polyurethane etc. any.
Among the present invention, the silicon sol of described modified silicasol for crossing through the silane coupling agent surface modification, particle size range is 10～100nm.
Among the present invention, described silane coupling agent be in vinyltriethoxysilane, (methacryloxypropyl) propyl trimethoxy silicane, the γ-glycidoxypropyltrimewasxysilane etc. any.
Among the present invention, described aminoresin is the aminoresin of part methyl-etherified.
Among the present invention, described polyisocyanates is the polyisocyanates emulsion of sealing, and the deblocking temperature is at 90～120 ℃.
Among the present invention, described inorganic salt be in ammonium titanium fluoride, zirconium carbonate ammonium or the ammonium fluozirconate etc. any.
Among the present invention, described adhesion promoter be in titanate coupling agent or the organic phospho acid ester polymer etc. any.
Among the present invention, described flow agent is a kind of organosilyl water-based flow agent that contains.
Wherein, water-base resin is main film forming matter, silicon sol is used to improve the anti-finger printing and the hardness of filming, especially the silicon sol of modification can better be dispersed in the organic resin, do not influence the glossiness of coating, aminoresin and polyisocyanates are solidifying agent, and inorganic salt select the metal zirconium ion to replace heavy metal chromium, mainly are because the oxide film ZrO that the metal zirconium ion forms
2Have solidity to corrosion, play passivation, aqueous polyethylene wax is used to improve self lubricity, scratch resistance and the processing characteristics of filming, and adhesion promoter is used to improve the sticking power of filming.
Among the present invention, the preparation method of the fingerprint-resistant coating of described a kind of hybrid is characterized in that it comprises the steps:
Step 1: with the silicon sol is raw material; According to silicon sol in SiO
2Mass ratio adds silane coupling agent, and (dosage of silane coupling agent is SiO in the silicon sol
2Quality 10%～50%).50～90 ℃ of stirrings of water-bath keep reaction 2～6 hours, promptly get modified silicasol.
Step 2: by the shared weight percent of each raw material, in reactor, drop into water-base resin 40～70wt%, silicon sol 3～10wt%, the inorganic salt 1～5wt%, the aqueous polyethylene wax slurry 1～6wt% that add modification while stirring, add aminoresin 2～15wt%, polyisocyanates 2～10wt% and adhesion promoter 1～9wt% again, in reactor, drop into flow agent 0.1～0.5wt% and remaining deionized water 10～40wt% at last again, continue again to stir 15～45 minutes, promptly obtain the fingerprint-resistant coating of hybrid.
The present invention is the aqueous chromium-free system, does not contain the metal ion of environmental pollution in the component.
The present invention can adopt modes such as dip-coating, spraying, roller coat to be coated on hot-dip galvanizing sheet steel, electrogalvanizing steel plate, the surface of cold-rolled steel plate, and only need apply and be about 0.8～1.2 micron coating in the metallic surface, solidify and get final product after 8～15 seconds, can satisfy the requirement of the required erosion resistance of steel plate galvanized, high glossiness, high rigidity, resistance to marring, electroconductibility, self lubricity and coating after the application, and have anti-finger printing energy and good sticking power, anti-bending and shock resistance.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1:
The concrete proportioning of a kind of fingerprint-resistant coating of preferred hybrid is as follows:
Table 1
In reactor, drop into aqueous epoxy resins 600g, add modified silicasol 80g, zirconium carbonate ammonium 30g, aqueous polyethylene wax slurry 12g while stirring, add aminoresin 71732g, blocked polyisocyanate 48g and adhesion promoter 45g again, in reactor, drop into flow agent 2g and remaining deionized water 260g at last again, continue to stir again 15～45 minutes, and promptly obtained No. 1, the fingerprint-resistant coating of hybrid.
Embodiment 2:
The concrete proportioning of a kind of fingerprint-resistant coating of preferred hybrid is as follows:
Table 2
In reactor, drop into aqueous epoxy resins 750g, add modified silicasol 110g, ammonium titanium fluoride 38g, aqueous polyethylene wax slurry 15g while stirring, add aminoresin 71743g, blocked polyisocyanate 55g and titanate coupling agent 20g again, in reactor, drop into flow agent 2.5g and remaining deionized water 294g at last again, continue to stir again 15～45 minutes, and promptly obtained No. 2, the fingerprint-resistant coating of hybrid.
The fingerprint-resistant coating of the hybrid of preparation gained among embodiment 1 and the embodiment 2 is carried out Performance Detection.
Table 3
Claims (10)
1. fingerprint-resistant coating based on organic inorganic hybridization is characterized in that its chemical composition content:
Water-base resin 40 ~ 70wt%
Modified silicasol 3 ~ 10wt%
Aminoresin 2 ~ 15wt%
Polyisocyanates 2 ~ 10wt%
Inorganic salt 1 ~ 5wt%
Aqueous polyethylene wax slurry 1 ~ 6wt%
Adhesion promoter 1 ~ 9wt%
Flow agent 0.1 ~ 0.5wt%
Deionized water 10 ~ 40wt%.
2. a kind of fingerprint-resistant coating based on organic inorganic hybridization according to claim 1 is characterized in that: described water-base resin be in water-borne acrylic resin, aqueous epoxy resins or the aqueous polyurethane any.
3. the fingerprint-resistant coating based on organic inorganic hybridization according to claim 1 is characterized in that described modified silicasol is prepared from by following method: disperse or the silicon sol of water-dispersion is a raw material with ethanol, according to silicon sol in SiO
2Mass ratio adds silane coupling agent, 50 ~ 90 ℃ of stirrings of water bath heat preservation, and the time kept 2 ~ 6 hours, added deionized water and got modified silicasol, and the particle diameter of modified silicasol is 10 ~ 100nm; Described silane coupling agent is: in vinyltriethoxysilane, (methacryloxypropyl) propyl trimethoxy silicane, the γ-glycidoxypropyltrimewasxysilane any.
4. the fingerprint-resistant coating based on organic inorganic hybridization according to claim 3 is characterized in that: described dosage of silane coupling agent is SiO in the silicon sol
210% ~ 50% of quality.
5. the fingerprint-resistant coating of a kind of organic inorganic hybridization according to claim 1, it is characterized in that: described aminoresin is the aminoresin of part methyl-etherified.
6. a kind of fingerprint-resistant coating based on organic inorganic hybridization according to claim 1 is characterized in that: described polyisocyanates is case type polyisocyanates emulsion, and the deblocking temperature is at 90 ~ 120 ℃.
7. a kind of fingerprint-resistant coating based on organic inorganic hybridization according to claim 1 is characterized in that: described inorganic salt be in ammonium titanium fluoride, zirconium carbonate ammonium or the ammonium fluozirconate any.
8. a kind of fingerprint-resistant coating based on organic inorganic hybridization according to claim 1 is characterized in that: described adhesion promoter be in titanate coupling agent or the organic phospho acid ester polymer any.
9. a kind of fingerprint-resistant coating based on organic inorganic hybridization according to claim 1 is characterized in that: described flow agent is for containing organosilyl flow agent.
10. a kind of fingerprint-resistant coating preparation method according to claim 1 based on organic inorganic hybridization, it is characterized in that it comprises the steps: by the shared weight percent of each raw material, in reactor, drop into water-base resin, add modified silicasol, inorganic salt, aqueous polyethylene wax slurry while stirring, add aminoresin, polyisocyanates and adhesion promoter again, in reactor, drop into flow agent and remaining deionized water at last again, continue again to stir 15 ~ 45 minutes, promptly get the fingerprint-resistant coating of hybrid.
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