CN100365086C - Aqueous nano zinc-riched epoxy silicane paint - Google Patents
Aqueous nano zinc-riched epoxy silicane paint Download PDFInfo
- Publication number
- CN100365086C CN100365086C CNB2006100542852A CN200610054285A CN100365086C CN 100365086 C CN100365086 C CN 100365086C CN B2006100542852 A CNB2006100542852 A CN B2006100542852A CN 200610054285 A CN200610054285 A CN 200610054285A CN 100365086 C CN100365086 C CN 100365086C
- Authority
- CN
- China
- Prior art keywords
- paint
- silane
- silicane
- epoxy
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
The present invention relates to water-based zinc-rich epoxy silane nanometer paint which is provided with two components. The recipe of the present invention is characterized in that the weight of the total components is 100%, and an A component (by the weight ratio) comprises 65% to 80% of nanometer zinc powder with 800 to 1000 meshes, 8% to 25% of self-emulsion type epoxy resin, 0.1% to 5% of ethanol, 0.5% to 5% of deionized pure water, 0.1% to 1% of thickening agents and 0.1% to 3% of anti-settling agents; a B component comprises 1.5% to 5% of silicane combination (bis-silyl aminosilane and propionic acid vinyl ester silicane) and 3% to 8% of curing agents; the combination proportioning ratio of two kinds of silane is from 0.15 to 0.30.
Description
Technical field
This patent is being the non-solvent water-repellent preservation priming paint that is mainly used in the metallic surface (or being called end property coating) of main raw material from newborn type Resins, epoxy and silane and nano zinc powder.
Background technology
Traditional coating mostly is solvent-borne type greatly, and the content height of volatile organic compounds (VOC) causes environmental pollution.Water-borne coatings since VOC content seldom, construction process does not have fire hazard, is environmental friendliness coating, obtains global greatly developing, and has now surpassed 50% of total consumption.
In waterborne metal anti-corrosive paint (priming paint) field that this patent relates to, there are three big R﹠D directions to be worth paying close attention to: 1. traditional aqueous inorganic zinc-enriched coating, the history in more than 50 year of its development experience, its ground and marine atmosphere, hot environment that surface corrosion is not removed fully all shows excellent performance.When the place of coating local failure is subjected to water or ionogen erosion, zinc-rich coating and metal body constitute corrosion cell, suppress the corrosion on metal body (negative electrode) surface to sacrifice zinc powder (anode) on one's own initiative, thereby play electro-chemical protection effect the metal body; But there is gap aspect the excellent characteristic of modern organic coatings such as film-forming properties, molecule interpenetrating(polymer)networks connectivity.2. aqueous epoxide resin paint, it is the hot topic of current research and development, the prescription kind is also more, and Resins, epoxy itself has good physical chemistry film forming properties, and the selection of other compositions of the key of research and development in prescription promotes effect to Resins, epoxy in conjunction with the physical chemistry over-all properties that produces; Current performance preferably the anticorrosion epoxypaint of water-based metal mainly in the electrophoretic paint field.3. Waterborne Silicon-Contained Polymer Coatings, with siloxane bond (is that the polysiloxane (silicone resin) that skeleton is formed belongs to macromolecular compound partly organic, half inorganic structure Si-O-Si-), they have organic and inorganic characteristic concurrently, the chemical physical stability of inorganic nature can be that other macromolecular materials are not available, is the paint field of current tool development prospect.The nineteen fifty-nine U.S. " DOW CORNING " company has begun to apply for since the poly-silicon coating patent that various countries drop into a large amount of research and development ability exploitation silane coatings in this field, the organosilane monomer of research and development and polymkeric substance diversity, and various coating are very impressive; Have remarkable thermotolerance, erosion resistance and can be widely used in fields such as aviation, ships, machinery, building, weaving, leather.But water-fast vapour permeability is relatively poor, and the water solvent ratio is excessive, and surface drying is slow, the cementability relative mistake.
Rose in 1992 by U.S. Department of Defense's Air Research Laboratory and subsidize the silane process of surface treatment research of carrying out metal in material system of U.S. University of Cincinnati energetically, more strong, the research tendency in this school of inventor's long-term follow is so that avoiding detours aspect the silane additives of coating.It can be relevant representative by disclosed CN 1360644A of 2002.7.24 day in Chinese patents; " aqueous mixture with vinyl silanes and bis-silyl aminosilane is handled the protectiveness of metallic surface " proposed; this patent proposed multiple combination silane component and deal (account for mixture total concn about 6%) thereof; it is the place that this patent will be used for reference; other compositions are about 94%---water, optional solvents, optional PH conditioning agent, the ratio of water and solvent can be water entirely or is solvent entirely from 0~~95%.The inventor herein carries out verification experimental verification with this prescription; when " water " composition 50%; natural room temperature can be not dry with interior moisture in 20 60 seconds above times of degree---is not inconsistent with the effect of this patent statement; there was not drying in 60 minutes yet; retaining of moisture content can be accelerated corrosion of metal rather than protection anti-corrosion of metal; this patent makes this professional those of ordinary skill can not implement or realize after having seen this technical scheme, does not meet publicity, the practical principle of patent application and mandate.This patent claims the preservative effect of zinc-plating material is better than non-zinc-plating material, can infer not contain zinc in the solution or content is few.In addition, this patent is if its solvent composition of rapid drying will be higher than 50% at least, and this is the superseded coating class of non-environmental protection---and can not be called " water-based ", should be " solvent-borne type ".
Its patent at U. S. application has tens, is relevant representative with disclosed No. 2005179011 patent Superprimer of 2005.8.18 day, and main points are at What is claimed is:
1.A hydrophilic composition capable of coating a substrate and curing to provide a hydrophobicfilm inhibiting corrosion,the composition comprising:a bis-silane comprising between about 5percent to about 40 percent of the composition;a water soluble or dispersible polymer;a watersoluble solvent;and nanoparticles having a mean particle size of ranging between about 0.01nanometers to about 500 nanometers.
5.The composition of claim 1,wherein:the bis-silane comprises between about 10 percent toabout 25 percent of the composition;the nanoparticles comprise between about 5 percent to about25 percent of the composition;the water soluble or dispersible polymer comprises between about10 percent to about 30 percent of the composition;and the water soluble solvent comprisesbetween about 10 to about 87 percent of the composition.
8.The composition of claim 1,wherein the water soluble or dispersible polymer and thenanoparticles comprise more than 50 percent of the composition
9.The composition of claim 1,wherein the water soluble or dispersible polymer includes an epoxyresin.
In " super priming paint " prescription: two silane account for 5~~40%, nano powder 5~~25%, polymkeric substance 10~~30%, water solvent 10~~87%.CN 1360644A and No. 2005179011 patents with enumerate a large amount of silane compositions and mutually combination determine too wide right face---compare the example that its concrete enforcement can be verified, substantially exceeded the supported degree of embodiment, have one to be false or one of not creative or three property in the hundreds of prescription, this patent will be false or part is false.
Rust-preventing characteristic and Corrosion Protection excellence through the metallic surface that silane treatment is crossed, the statement that these are a large amount of in numerous data.Since the later stage nineties in last century, certain research was done to the Corrosion Protection that silane is used for ferrous metal and non-ferrous metal surface by domestic University Of Chongqing, Tongji University, Zhejiang University, East China University of Science, the Chinese Academy of Sciences and some enterprises.
With three big advantages: waterborne zinc-rich coating, aqueous epoxide resin paint, the Waterborne Silicon-Contained Polymer Coatings complementary simultaneously limitation separately that combines is current forward position research direction, also is the direction and the purpose of this patent research.
Consult the relevant data of water-borne coatings, think that " water-borne coatings " book of " organosilicon macromolecule and the application thereof " book of 2004.6 months first versions of Chemical Industry Press and 2006.2 months first versions can summarize the substance in current domestic and international water-borne coatings and silane field.2006.4.1 day retrieval Chinese patent database is with title: coating or lacquer AND summary: epoxy and silane and zinc, retrieval obtains two parts of patent: CN91103183.9, CN01140874X; With: summary: epoxy and silane and zinc, retrieval obtains seven parts of patents.Wherein: CN01140874.X and this patent are more approaching, and its content Description is as follows: on December 7th, 2005 was announced, patent No. CN01140874.X title: water two-component protective paint composition; Form, fill a prescription:
A) first kind of component: (i) 3-aminopropyltriethoxywerene werene; (ii) formic acid, its consumption is enough to reach pH value 7-9; (iii) a kind of compound is selected from 3-glyceryl oxygen propyl trimethoxy silicane and 3-glyceryl oxygen propyl-triethoxysilicane, and the amido hydrogen equivalent in several-aminoalkyl group trialkoxysilanes that its consumption makes is 4--6 with the ratio of the epoxide equivalent of described compound; (iv) one or more pigment, wherein at least 50 weight % have electroconductibility; B) second kind of component: (v) finely disintegrated zinc, zinc is 1 with the gross weight ratio of pigment: 1-4: 1; Solid binder is 1 with the ratio of zinc and total pigment weight: 20-1: 60.
Mainly form by following steps:
(i) water is mixed with at least a aminosilane, form first kind of mixture; (ii) be up under 40 ℃ the temperature, add at least a strong acid in first kind of mixture, usage quantity is enough to reach pH value 7-9, forms second kind of mixture; (111) with one or more colo(u)rant dispersion in second kind of solution, wherein said pigment at least 25 weight % have electroconductibility, form the third mixture; (iv) be up under 40 ℃ the temperature, add at least a epoxy silane in the third mixture, the amido hydrogen equivalent in the aminosilane and the epoxy equivalent (weight) of epoxy silane be than being 3-7, thereby obtain first kind of component.
2006.4.1 day retrieval United States Patent (USP) database, patent retrieval from calendar year 2001 with: ACLM/ZINC ANDACLM/EPOXY AND ACLM/SILANE retrieval obtains 107 parts of patents; 2006.4.28 day obtain 85 parts of patents with: ACLM/EPO$AND ACLM/VINYL$AND ACLM/BIS$AND ACLM/ (ZINE OR ZN) retrieval, add AND ACLM/ (COATING OR PAINT) just only retrieval obtain 27 parts of patents.Think dependency after all reading all not as good as No. 2005179011 above-mentioned patents, therefore be the no longer statement of saving space.
From above retrieval situation, with three big advantages: waterborne zinc-rich coating, aqueous epoxide resin paint, the Waterborne Silicon-Contained Polymer Coatings complementary simultaneously circumscribed achievement in research quantity and seldom but begun to take shape and all concentrate control in world-class large-size chemical industrial separately that combines, domestic enterprise and research and development institution also do not have the place.The main points of coating research are in the raw material of recipe ingredient, the selection of ratio, difficulty will digest a large amount of domestic and international forward position data, will screen from a large amount of raw materials and ratio, make up, verify repeatedly its performance, perhaps a little difference of component, ratio just determines the quality of coating.
Summary of the invention
The aqueous nano zinc-riched epoxy silicane paint prescription is achieved in that
Weight with whole components is 100%, below is the weight ratio of each component:
The A component: 800~~1000 order nano zinc powders 65%~80%,
From newborn type Resins, epoxy 8%~25%,
Ethanol 0.1%~5%, deionization pure water 0.5%~5%,
Viscosifying agent 0.1%~1%, the heavy agent 0.1%~3% of anti-branch;
B component: bis-silyl aminosilane, vinyl silanes combination: 1.5%~5%, the combination matching rate of these two kinds of silane between 0.15~0.30, solidifying agent 3%~8%.
B component 1: bis-silyl aminosilane, vinyl silanes combination, be selected from: vinyl acetoxysilane and two-(trimethoxy-silylpropyl) amine 1.5%~5%, the combination matching rate of these two kinds of silane between 0.15~0.30, solidifying agent 3%~8%.
B component 2: bis-silyl aminosilane, vinyl silanes combination, can be selected from: vinyltriacetoxy silane and two-(triethoxysilylpropyltetrasulfide) amine 1.5%~5%, the combination matching rate of these two kinds of silane between 0.15~0.30, solidifying agent 3%~8%;
Perhaps: vinyltriacetoxy silane and two-(trimethoxy-silylpropyl) amine 1.5%~5%, the combination matching rate of these two kinds of silane between 0.15~0.30, solidifying agent 3%~8%;
Perhaps: vinyltriethoxysilane and two-(trimethoxy-silylpropyl) amine 1.5%~5%, the combination matching rate of these two kinds of silane between 0.15~0.30, solidifying agent 3%~8%;
Perhaps: vinyltriethoxysilane and two-(triethoxysilylpropyltetrasulfide) amine 1.5%~5%, the combination matching rate of these two kinds of silane between 0.15~0.30, solidifying agent 3%~8%;
Perhaps: vinyltrimethoxy silane and two-(trimethoxy-silylpropyl) amine 1.5%~5%, the combination matching rate of these two kinds of silane between 0.15~0.30, solidifying agent 3%~8%;
Perhaps: vinyltrimethoxy silane and two-(triethoxysilylpropyltetrasulfide) amine 1.5%~5%, the combination matching rate of these two kinds of silane between 0.15~0.30, solidifying agent 3%~8%.
Aqueous nano zinc-riched epoxy silicane paint be on the basis of reference CN 1360644A patent to inventor herein's patent formerly: application number: 200610054213.8, further development and innovation, the silane combination of wherein having digested and assimilated CN 1360644A patent: [bis-silyl aminosilane, vinyl silanes]---be that this patent B component 2 has carried out innovation again with other composition and formula rate and obtains good effect.
Aqueous nano zinc-riched epoxy silicane paint primer film surface drying 5 minutes, after 20 minutes paint film can be anti-the nickel coin scraping, with the cementability of metal be 5B, for non-zinc-plating material excellent performance is arranged; Overcome a large amount of waters of CN 1360644A patent or used solvent---the shortcoming of the slow and non-environmental protection of surface drying.
Aqueous nano zinc-riched epoxy silicane paint is patent formerly: application number: 200610054213.8, component and ratio further optimize and expansion, make the right formula range of original single silane combination that bigger selectivity and adaptability to different initial conditions be arranged, thus to the different metal base material further select pointedly prescription with improve antiseptic property, cost can reduce pointedly.
Embodiment
Prepare the A component: after various material requesteds in this component are chosen by weight percent recited above, earlier in stirrer, stirring together 10~20 minutes from newborn type Resins, epoxy, ethanol, deionization pure water, again zinc powder is put into lentamente in the liquid that is stirred, needed to stir 20 minutes.Add viscosifying agent then, prevent dividing heavy agent stirring airtight after 10~20 minutes.
Preparation B component: silane is made up stirring in stirrer 20 minutes with modification fat amine curing agent.
Preparation A, B component: after the A for preparing, B component mixed and stir 30 minutes, pH value was controlled in 6~8, makes.
The contrast protection against corrosion detects: epoxy zinc-rich paint, a kind of of aqueous nano zinc-riched epoxy silicane paint are brushed respectively on the steel plate sample of equal amts, treat that the detected result after its curing is as shown in the table:
Test item | Neutral salt spray test (NSS), film thickness measurement, sticking power (cross-hatching) |
The sample title: | Epoxy zinc-rich paint steel plate sample, aqueous nano zinc-riched epoxy silicane paint steel plate sample |
Detect foundation: evaluating basis: | GB/T1771-1991、GB/T9286-1998、GB/T4956-1985 ASTMD1654-1992、GB/T9286-1998 |
Sample was through 480 hours neutral salt spray test detected results
The sample title | Thickness average value (μ m) | The monolateral corrosion width of drawn area (mm) | The corrosion grading |
Epoxy zinc-rich paint steel plate sample | (71.0 paint film thickness is 3.88 times of water base silane primer) | 1.0 | 7 |
Aqueous nano zinc-riched epoxy silicane paint steel plate sample | 18.3 | (0.2 being better than 5 times of epoxy zinc-rich paint) | 9 (being better than 2 grades of epoxy zinc-rich paint) |
Sticking power (cross-hatching) detected result
The sample title | Sticking power (cross-hatching) grade |
Epoxy zinc-rich paint steel plate sample | 2 |
Aqueous nano zinc-riched epoxy silicane paint steel plate sample | 1 (being better than 1 grade of epoxy zinc-rich paint) |
By detected result as can be known, as anti-corrosion primer, aqueous nano zinc-riched epoxy silicane paint is higher than 1 grade of epoxy zinc-rich paint commonly used to the tack of metallic matrix, and erosion-resisting ability is better than 5 times of epoxy zinc-rich paint.Anti-scratch characteristic, quick-drying behind the aqueous nano zinc-riched epoxy silicane paint film surface drying and be lower than the VOC value that environmental protection standard limits, be epoxy zinc-rich paint and existing other heavy anti-corrosion primer paint film incomparable.
But every liter of this water-based paint is 5 times of every liter of coated area of epoxy zinc rich primer with 25 square metres of 0.35 millimeter thickness overcoatings, every square metre few 0.2 yuan of price.Have excellent non-corrosibility and to each metalloid and paint cementability, but attenuate zinc-rich paint layer thickness.
This environment-friendly water-based nano zinc-riched epoxy silicane paint rete protection against corrosion phase reaches 6-8, but and overcoating.Purposes: can be used for the sea transport freight container, bridge, steelframe, pipeline, railing and all kinds of hardware.
The basic parameter of aqueous nano zinc-riched epoxy silicane paint
Packing | 2 components | ||||
Color | Grey is unglazed | ||||
Flash-point | N/A (water-based) | ||||
Density | 1.67g/cm 2 | ||||
Viscosity | 60-170 Centistokes,(10-15sec,#4 Zahn Cup) | ||||
Solids content | ~84% | ||||
Theoretical consumption | Can be coated with 25 square metres/every liter, thick 35 μ m calculate with rete | ||||
Time of drying (25 ℃) | Surface drying: 3~5 minutes, can anti-nickel coin scraping after 20 minutes | ||||
Completely solidified: 6-8 hour | |||||
Thermostability | >150℃ | ||||
Supporting paint class | Resins, epoxy, chlorinated rubber, Polyurethane, ethene and solubility finish paint etc. | ||||
VOC | Organic volatile 96 grams/every liter | ||||
Surface preparation | The processing of sandblasting, cleaning is also dry, surperficial oil stains-less | ||||
Coating process | Airless spraying, aerial spraying, roller coating is brushed | ||||
Construct duration of service | Packing is opened the operational time of back: more than 8 hours | ||||
The priming paint shelf life | 12 months | ||||
Build | 20-50μm | ||||
Surface drying time (in minute) | Temperature | 5℃ | 20℃ | 50℃ | 80℃ |
Shortest time | N/A | 3min | 2min | 1min | |
Maximum duration | N/A | 7min | 5min | 3min |
Claims (3)
1. an aqueous nano zinc-riched epoxy silicane paint has two kinds of components, and its prescription feature is:
Weight with whole components is 100%, below is the weight ratio of each component:
The A component: 800~~1000 order nano zinc powders 65%~80%,
From newborn type Resins, epoxy 8%~25%,
Ethanol 0.1%~5%, deionization pure water 0.5%~5%,
Viscosifying agent 0.1%~1%, the heavy agent 0.1%~3% of anti-branch;
B component: bis-silyl aminosilane, vinyl silanes combination: 1.5%~5%,
The combination matching rate of these two kinds of silane between 0.15~0.30,
Solidifying agent 3%~8%.
2. a kind of aqueous nano zinc-riched epoxy silicane paint according to claim 1, its prescription feature is:
In the B component: bis-silyl aminosilane, vinyl silanes combination are selected from:
Vinyl acetoxysilane and two-(trimethoxy-silylpropyl) amine.
3. a kind of aqueous nano zinc-riched epoxy silicane paint according to claim 1, its prescription feature is:
In the B component: bis-silyl aminosilane, vinyl silanes combination are selected from:
Vinyltriacetoxy silane and two-(triethoxysilylpropyltetrasulfide) amine;
Perhaps: vinyltriacetoxy silane and two-(trimethoxy-silylpropyl) amine;
Perhaps: vinyltriethoxysilane and two-(trimethoxy-silylpropyl) amine;
Perhaps: vinyltriethoxysilane and two-(triethoxysilylpropyltetrasulfide) amine;
Perhaps: vinyltrimethoxy silane and two-(trimethoxy-silylpropyl) amine;
Perhaps: vinyltrimethoxy silane and two-(triethoxysilylpropyltetrasulfide) amine.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2006100542852A CN100365086C (en) | 2006-05-12 | 2006-05-12 | Aqueous nano zinc-riched epoxy silicane paint |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2006100542852A CN100365086C (en) | 2006-05-12 | 2006-05-12 | Aqueous nano zinc-riched epoxy silicane paint |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1844279A CN1844279A (en) | 2006-10-11 |
CN100365086C true CN100365086C (en) | 2008-01-30 |
Family
ID=37063248
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2006100542852A Expired - Fee Related CN100365086C (en) | 2006-05-12 | 2006-05-12 | Aqueous nano zinc-riched epoxy silicane paint |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN100365086C (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100551982C (en) * | 2006-12-14 | 2009-10-21 | 自贡市斯纳防锈蚀技术有限公司 | Douple-component water-thinned epoxy zinc-rich silane metal paint |
CN101104771B (en) * | 2007-08-20 | 2010-06-23 | 维新环保涂料(深圳)有限公司 | Water-based epoxy zinc-rich primer |
CN102304704A (en) * | 2011-09-09 | 2012-01-04 | 重庆大学 | Aqueous silane treatment agent for improving metal surface protection performance |
CN108893034B (en) * | 2018-08-20 | 2021-06-15 | 常州市天安特种涂料有限公司 | Anti-corrosion bactericidal coating for ship drinking water tank and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1346861A (en) * | 2000-09-25 | 2002-05-01 | 西格玛涂层公司 | Water two-component protective paint composition |
CN1360644A (en) * | 1999-07-19 | 2002-07-24 | 辛辛那提大学 | Protective treatment of metal surfaces with aqueous mixture of vinyl silane and bis-silyl aminosilane |
-
2006
- 2006-05-12 CN CNB2006100542852A patent/CN100365086C/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1360644A (en) * | 1999-07-19 | 2002-07-24 | 辛辛那提大学 | Protective treatment of metal surfaces with aqueous mixture of vinyl silane and bis-silyl aminosilane |
CN1346861A (en) * | 2000-09-25 | 2002-05-01 | 西格玛涂层公司 | Water two-component protective paint composition |
Also Published As
Publication number | Publication date |
---|---|
CN1844279A (en) | 2006-10-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105838195B (en) | A kind of water corrosion-resistant epoxy paint and preparation method thereof containing graphene oxide | |
JP5543581B2 (en) | Water-based coating composition and coating film forming method | |
CN106047075A (en) | Preparation method of water-based priming paint, intermediate paint, finishing paint and varnish applied to 25 type passenger car | |
CN102174291A (en) | Organosilicon-modified alkyd resin paint composite and preparation method thereof | |
CN106590335A (en) | One-coat high gloss aqueous air dry coating composition and preparation method thereof | |
CN100365086C (en) | Aqueous nano zinc-riched epoxy silicane paint | |
CN103834264A (en) | Aluminum oxide-containing polyaniline zinc powder flake epoxy heavy anti-corrosion coating and preparation method thereof | |
CN109517516A (en) | A kind of cerium bentonite modified watersoluble polyurethane paint and preparation method thereof | |
CN112552796A (en) | Metal flake type bi-component heavy-duty anticorrosive paint and preparation method thereof | |
CN104059412A (en) | Sealing agent and preparation method and use thereof, and hot-dip plated metal material | |
CN104974625B (en) | A kind of water-soluble anti-rust insulated paint and preparation method thereof | |
AU2017301461B2 (en) | Water based sealer with superior durability | |
CN106833200B (en) | Impact-resistant high-weather-resistance water-based industrial coating and preparation method thereof | |
CN104059478B (en) | Anticorrosive coating and its production and use and hot-dip metal plated material | |
CN104059473B (en) | A kind of coating composition and its production and use and hot-dip metal plated material | |
CN101225280A (en) | Dual-component silicane polymeric metal heavy-duty aqueous industrial coating | |
KR101746954B1 (en) | Cr-free modified epoxy wash primer high adhesion anti-corrosive coating composition and a method of manufacturing the same | |
CN106085123A (en) | A kind of aqueous epoxy resin emulsion, the water-thinned epoxy zinc-rich coating and preparation method thereof of railway bearing | |
CN104059489B (en) | A kind of metal surface chemical pretreatment solution and its production and use and hot-dip metal plated material | |
CN104059492B (en) | A kind of anticorrosion passivating solution and its production and use and a kind of hot-dip metal plated material | |
CN104059507A (en) | Surface treatment agent and preparation method and use thereof, and hot-dip plated metal material | |
CN104059486A (en) | Environment-friendly surface treatment agent and preparation method and use thereof, and hot-dip plated metal material | |
CN107083132A (en) | A kind of outdoor steel construction one pack system acrylic coating and preparation method thereof | |
CN103788737B (en) | A kind of metal protection coating and its production and use and hot-dip metal plated material | |
CN104059411B (en) | The method preparing Protective reagent and the Protective reagent prepared by the method and uses thereof and hot-dip metal plated material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080130 Termination date: 20100512 |