CN1076948A - Water-based anticorrosive paint and preparation method thereof - Google Patents
Water-based anticorrosive paint and preparation method thereof Download PDFInfo
- Publication number
- CN1076948A CN1076948A CN 93106438 CN93106438A CN1076948A CN 1076948 A CN1076948 A CN 1076948A CN 93106438 CN93106438 CN 93106438 CN 93106438 A CN93106438 A CN 93106438A CN 1076948 A CN1076948 A CN 1076948A
- Authority
- CN
- China
- Prior art keywords
- anticorrosive paint
- water
- epoxy
- based anticorrosive
- paint according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
A kind of water-based anticorrosive paint that is particularly suitable for the use of food cans inwall, after it directly utilizes high molecular weight bisphenol A type Resins, epoxy and phosphatase reaction to make epoxy phosphate ester, carry out graft copolymerization and introduce hydroxyl with vinylformic acid and esters monomer thereof, make ammonium salt with the organic tertiary amine neutralization again, mixing mutually with the poly-hydroxy thermosetting phenolic compound that dihydroxyphenyl propane, cresols and phenol and so on polyphenol and formaldehyde are made, is 25%～38% with distilled water diluting to solids content at last again.Use the anti-peracid of paint film, shock resistance, anti-bending, anti-sulphur and the sticking power of this protective system good.
Description
The present invention relates to a kind of water-based anticorrosive paint and synthesis technique thereof that the food cans inwall uses that be particularly suitable for.
The major ingredient of the food cans inner-wall paint that uses is Resins, epoxy and resol at present, all adopts organic solvent.Organic solvent all is dispersed into and has caused suitable serious environmental to pollute in the atmosphere in the drying course.Simultaneously, because the limitation of chemical constitution has poor adhesive force, the anti-shortcomings such as dialling poor performance of dashing.Since the seventies, the food cans inner-wall paint has also been made extensive studies abroad.U.S.PAT.NO.4,722,982 to have studied a kind of be the food cans inner-wall paint of raw material with high molecular expoxy resin with formaldehyde and dihydroxyphenyl propane synthetic resol, but still adopt organic solvent; U.S.PAT.NO.4,296,011 usefulness low-molecular-weight epoxy resin and benzoic acids carry out modification and make epoxy ester, carry out copolymerization with acrylic monomer again, thereby make water-borne coatings, but owing to use low-molecular-weight epoxy resin, and the amount of used acrylic monomer is more, so the preservative property of water-borne coatings are bad; U.S.PAT.NO.4,341,678 utilize low-molecular-weight epoxy resin para-amino benzoic acid class to carry out modification, make cure-crosslinking agent with the polyhydroxy phenol aldehyde cpd again, obtain the food cans inner-wall paint of anti-peracid superior performance, but have the unsettled shortcoming of water-based, and synthesis technique is complicated.EUROPEAN PATENT NO.0292317 utilizes resol, Resins, epoxy and epoxy phosphate ester to make shock resistance, high rot-resistant food cans inner-wall paint for main raw material, but still is organic solvent type.U.S.PATNO.4,302,373 aqueous food can drink jar inner-wall paint mainly adopts Resins, epoxy and acrylic monomer to carry out copolymerization and introduces hydroxyl, neutralizes with tertiary amine then, thereby make the good coating of water-based, but that fatal shortcoming is an antiseptic property is poor.
The purpose of this invention is to provide a kind of protective system that the food cans inwall uses that is particularly suitable for, it not only belongs to stabilized aqueous coating, performances such as the anti-peracid of paint film, anti-sulphur, anti-bending, shock resistance and sticking power all surpass or are suitable with the existing organic solvent type coating that uses, and cost is low, and is pollution-free.
Technical scheme of the present invention is: mainly be made up of high molecular weight bisphenol A type Resins, epoxy and polyhydroxy phenol aldehyde cpd, phosphoric acid, organic tertiary amine, unsaturated vinylformic acid and esters monomer thereof.
The technology of preparation water-based anticorrosive paint of the present invention is: directly high molecular weight bisphenol A type Resins, epoxy after the dissolving, was made epoxy phosphate ester in 2～5 hours with phosphoric acid reaction under 90～140 ℃ in the mixed solvent of a small amount of pimelinketone, propyl carbinol and ethylene glycol monobutyl ether; Epoxy phosphate ester and unsaturated vinylformic acid and esters monomer methyl methacrylate thereof, butyl acrylate and ethylenic unsaturation quasi-styrene carry out graft copolymerization under 80～140 ℃, reaction times is 2～8 hours, the vinylformic acid and the esters monomer thereof that react used account for 1%～30% of epoxy phosphate ester weight, wherein Acrylic Acid Monomer weight is 1%～18% of epoxy phosphate ester, add peroxidation type free base initiator during reaction, initiator amount is 1%～5% of a weight epoxy in batches; Then, it is 7.0～7.5 that the acrylic acid graft copolymer that will go up step gained epoxy phosphate ester with tertiary amine is neutralized to pH value, and adds an amount of distilled water diluting; Stirring under the condition of not stopping, slowly drip the polyhydroxy phenol aldehyde cpd and make linking agent again, its weight is 20%～50% of epoxy phosphate ester acrylic copolymer, and adding water move to solids coatings again is 25%～38%, promptly gets water-based anticorrosive paint of the present invention.
The present invention has following several advantage: mainly adopt water solvent preparation coating, reduced the coating cost, reduced environmental pollution, have considerable economic and social benefit; Owing to adopted an amount of vinylformic acid and ester constituents thereof, and Resins, epoxy carried out phosphoric acid modification, improved paint film adhesion and snappiness; Owing to made water-borne coatings, can so be fit to multiple coating process, especially be fit to spraying coating process in the solids content and the viscosity of regulated in wider range coating; Contain the composition that crosslinking curing more easily takes place for tertiary amine, acrylic resin and polyhydroxy phenol aldehyde cpd etc. in this water-borne coatings,, saved the energy so the coating storing temperature is lower about 20 ℃ than existing solvent based coating; And the anti-peracid of the paint film after the present invention's oven dry, Corrosion Protections such as anti-sulphur are suitable with existing organic solvent type coating.
Further specify the present invention below in conjunction with embodiment.
Earlier high molecular weight bisphenol A type Resins, epoxy is dissolved in the organic solvent, molecular weight of epoxy resin is preferably between 2000～5000.Solvent can adopt the mixed solvent of butanone, pimelinketone, Virahol, propyl carbinol ethylene glycol monobutyl ether and the only butyl ether of a condensed ethandiol, and best mixed solvent is the mixture of pimelinketone propyl carbinol and ethylene glycol monobutyl ether; Then, heated solution carries out phosphorylation, phosphoric acid can be used ortho-phosphoric acid, peroxophosphoric acid and polyphosphoric acid, be preferably between 100～120 ℃ backflow certain hour, general 2～5 hours at 90～140 ℃, be preferably 2～3 hours, phosphoric acid and corresponding epoxide group are fully reacted, and phosphoric acid accounts for 0.05%～5% in the epoxy phosphate fat, and preferably 0.2%～2%.Phosphoric acid reagent superfluous mole number in total amount is inappreciable.Through infrared spectra and gel osmoticing chromatogram analysis, the structure that must attain is correct.
About the graft copolymerization of vinylformic acid and esters monomer and epoxy phosphate fat, need under strict condition, carry out.Graft copolymerization adopts peroxidation type free base initiator, and initiator typically commonly used has: persulphate, t～butyl peroxy benzoyl, methyl-ethyl-ketone peroxide and benzoyl peroxide, and like that.Wherein preferably select benzoyl peroxide for use, because the hydrogen-taking capacity of its radical pair trunk is stronger, the grafted tendency is bigger, the efficient height.The consumption of initiator is no less than 2%, and preferably 3%～5% of weight epoxy.Temperature of reaction remains between 80-140 ℃, can have a temperature range to adjust, but temperature is preferably between 90～110 ℃.When temperature was too low, the polyreaction between vinylformic acid and the esters monomer thereof mainly took place, the product water-based instability that obtains, when temperature was too high, decomposition of initiator speed was too fast, and efficiency of initiation reduces, and has caused final product water-based instability.Vinylformic acid and esters monomer thereof can be unsaturated Acrylic Acid Monomer and the low alkyl acrylics that contains hydroxyl, comprise ethyl propenoate, butyl acrylate, methyl methacrylate, methylpropanoic acid isobutyl, vinylformic acid tertiary butyl ester, vinylformic acid amyl group ester etc. as methacrylic acid, esters monomer, also has the carbon-carbon double bond unsaturated compound, as vinylbenzene, Vinylstyrene, divinyl etc.Vinylformic acid and esters monomer weight thereof account for 1%～30% of epoxy phosphate ester, are preferably 12%～20%, and wherein vinylformic acid weight accounts for 1%～18% of epoxy phosphate ester weight, is preferably 3%～5%.
The acrylic acid graft copolymer of epoxy phosphate ester must be with could stably disperseing in water in the tertiary amine He behind the salify.Can select following several amine: trialkyl or alkyl amine, pyridines, pyroles and their mixture.Trialkyl or alcoxyl base class amine comprise: Trimethylamine 99, N, N～dimethylethanolamine, diethoxymethyl amine, ethyl-methyl thanomin, dimethylethyl amine, dimethyl propyl amine, xylidine, diethylmethyl amine, 1-hydroxyl-2-propyl-dimethyl amine and the mixture between them, preferably adopt N, the consumption of N～dimethylethanolamine tertiary amine is as the criterion so that the pH value of final coating is transferred to 7.0～7.5.
The acrylic copolymer of epoxy phosphate ester can be made cure-crosslinking agent with resol, thereby improves anticorrosive, the shock-resistance of paint film.Resol is synthetic polycondensate under acid or alkaline catalysts by phenols and aldehydes.Because polycondensation is progressively carried out, product quite stable in the middle of it, thereby the product of differential responses degree can be separated, but the structure of resin resultant is very complicated.The mol ratio of formaldehyde and phenol is less than 1, and (PH＜3) can synthesize general thermoplastic phenolic fat under the condition of strong acid, when the mol ratio of cresols and phenol greater than 1, under alkaline condition, can synthesize heat-reactive phenolic resin when (PH＞7～11).The main raw material of producing resol is a phenols as phenol, cresols, xylenol, dihydroxy-benzene, phenol A etc., aldehydes such as formaldehyde, aldehyde, aldehyde etc.Also can use mixed phenol, the mixed phenol of the most handy dihydroxyphenyl propane and phenol or dihydroxyphenyl propane and cresols.The mol ratio of dihydroxyphenyl propane and cresols or phenol is 0.5: 0.5～0.8: 0.2; Preferably select 0.65: 0.35～0.7: 0.3.1 mol phenol mixture and 4.0～6.0 molar formaldehyde reactions, preferably 4.5～5.0 mol formaldehyde.Building-up reactions can be used ammoniacal liquor and alkali as a catalyst such as sodium hydroxide, hydrated barta, but preferably selects sodium hydroxide.Catalyst levels is 0.2%～0.5%, reacts between 70～100 ℃ 2～5 hours, promptly can be made into the poly-hydroxy thermosetting phenolic compound of good water solubility.During preparation coating, the weight ratio of the acrylic copolymer of epoxy phosphate ester and poly-hydroxy thermosetting phenolic compound is 0.5: 0.5～0.8: 0.2, is preferably 0.65: 0.35～0.7: 0.3.
Acrylic acid graft copolymer N with epoxy phosphate ester, N～dimethylethanolamine is neutralized to PH=7.0～7.5, behind distilled water diluting, under the condition that stirring does not stop, slowly drip poly-hydroxy thermosetting phenolic compound, adding water move to solids content again is 25%～38%, just can obtain being particularly suitable for the water-based anticorrosive paint that the food cans inwall uses.The weight of organic solvent only accounts for 20%～30% of solvent gross weight in this water-borne coatings.
This coating is suitable for multiple coating process, is coated with and sprays as flow coat, dip-coating, roller coat, electrophoresis, is particularly suitable for spraying.
Example: take by weighing 500 gram EPON1009 Resins, epoxy in wet bulb thermometer is housed, reflux exchanger and machinery stir and block in 1000 milliliters the there-necked flask mixing device, add 200 gram mixed solvents again, mixed solvent is by pimelinketone, butanols and ethylene glycol monobutyl ether 1: 2: 1 by volume are formulated, heating is also stirred, be warming up to about 130 ℃, begin to drip 3 gram phosphoric acid, 0.5 drip off about hour, afterwards, again in 130 times isothermal reactions 2～3 hours, reduce to 80 ℃ then, beginning drips the vinylformic acid of 4 gram benzoyl peroxides and the mix monomer of ester class thereof continuously, wherein vinylformic acid is 10 grams, methyl methacrylate, the gross weight of vinylbenzene and butyl propionate is 61.4 grams, and three's weight ratio is 15: 18: 10, and 1 drips off about little, 80 ℃ of following isothermal reactions, continuous quadratic was added 3 gram initiators every 2 hours.
In the there-necked flask that thermometer, reflux exchanger and electromagnetic mixing apparatus are housed, drop into the mixture of dihydroxyphenyl propane, phenol, mol ratio is 0.65: 0.35, add 37% formaldehyde solution again, its mole number is 4.5 times of preceding mixture, stirring is warming up to the sodium hydrate solid of 40 ℃ of addings 0.2%, continues to be warming up to 85 ℃, and isothermal reaction can make the hot phenolic compound of poly-hydroxy in 3～5 hours.
Acrylic acid graft copolymer N with above gained epoxy phosphate ester, N～dimethylethanolamine is neutralized to PH and approximates 7.5, with distilled water diluting to about 35% solids content, when 60 ℃ of constant temperature, drip the poly-hydroxy thermosetting phenolic compound that has prepared then while stirring, to transfer to solids content be 33% to adding distil water again, promptly gets water-based anticorrosive paint of the present invention.
Table 1 is the paint film property test result of the water-based anticorrosive paint of five kinds of prescriptions when being applied to tin plate food pot.The coating compound method is the same fully.Last hurdle is the performance index of the solvent-borne type food cans inner-wall paint 214 of existing use in the table.
Table 1
Number 12345 214
Be coated with epoxy phosphate ester (gram) 66.7 70 66.7 75 65
Material esters of acrylic acid body (gram) 9.5 10 16.7 10 15
Join polyhydroxy phenol aldehyde cpd 24.8 20 16.3 15 20
Side's (gram)
Lacquer thickness (gram/rice) 8.0 9.2 9.4 7.4 7.4 7.0
The corrosion-resistant rank 1.5 1.5 3 1.5 3 1.5 of film
Property sticking power I I I I I III
Can shock resistance pass through by a small amount of erosion point of a small amount of erosion point by a small amount of erosion point
Anti-Na2S 1% is by by substantially by by substantially by passing through
Claims (21)
1, a kind of water-based anticorrosive paint that is particularly useful for the use of food cans inwall, it is characterized in that: mainly adopting high molecular weight bisphenol A type Resins, epoxy and polyhydroxy phenol aldehyde cpd is raw material, also contains phosphoric acid, organic tertiary amine, unsaturated vinylformic acid and esters monomer thereof.
2, water-based anticorrosive paint according to claim 1 is characterized in that: the molecular weight of Resins, epoxy is preferably between 2000～5000.
3, water-based anticorrosive paint according to claim 1 and 2 is characterized in that: phosphoric acid can be ortho-phosphoric acid, peroxophosphoric acid, polyphosphoric acid, phosphoric acid consumption preferably Resins, epoxy 0.05%～5%.
4, water-based anticorrosive paint according to claim 3 is characterized in that: the polyhydroxy phenol aldehyde cpd is a raw material with polyphenol mixture and formaldehyde, and polyphenol can be dihydroxyphenyl propane, phenol or cresols polyphenol and the mole number ratio of formaldehyde is 4.0～6.0.
5, water-based anticorrosive paint according to claim 4 is characterized in that: unsaturated vinylformic acid and esters monomer thereof comprise acrylic or methacrylic acid, methyl methacrylate, butyl acrylate or ethyl propenoate and ethylenically unsaturated monomers vinylbenzene.
6, water-based anticorrosive paint according to claim 5 is characterized in that: the content of unsaturated vinylformic acid and esters monomer thereof is vinylformic acid 20%～60%, methyl methacrylate 10%～20%, butyl acrylate 5%～10%, vinylbenzene 5%～10%.
7, a kind of method for preparing the described water-based anticorrosive paint of claim 1 is characterized in that:
A, directly use high molecular weight bisphenol A type Resins, epoxy in the mixed solvent of a small amount of pimelinketone, propyl carbinol and ethylene glycol monobutyl ether, to dissolve, made epoxy phosphate ester in 2～5 hours with phosphoric acid reaction under 90～140 ℃, wherein the phosphoric acid consumption accounts for 0.05%～5% of Resins, epoxy;
B, epoxy phosphate ester and unsaturated vinylformic acid and esters monomer methyl methacrylate thereof, butyl acrylate and ethylenic unsaturation quasi-styrene carry out graft copolymerization under 80～140 ℃, vinylformic acid and esters monomer thereof used during reaction account for 1%～30% of epoxy phosphate ester weight, and wherein Acrylic Acid Monomer weight is 1%～18% of epoxy phosphate ester; Add peroxidation type free base initiator during reaction, initiator amount is not less than 2% of weight epoxy in batches;
C, will going up the acrylic acid graft copolymer of the step epoxy phosphate ester that obtains with tertiary amine, to be neutralized to pH value be 7.0～7.5, and add an amount of distilled water diluting;
D, slowly drip the polyhydroxy phenol aldehyde cpd under the condition do not stop and make linking agent stirring, its weight is 20%～50% of epoxy resin acrylic copolymer; Adding water move to solids coatings again is 25%～38%, promptly gets to be particularly suitable for the water-based anticorrosive paint that the food cans inwall uses.
8, the method for preparing water-based anticorrosive paint according to claim 7 is characterized in that: the weight of phosphoric acid accounts for 0.2%～2% of Resins, epoxy in the process of preparation epoxy phosphate ester.
9, according to claim 7 or the 8 described methods that prepare water-based anticorrosive paint, it is characterized in that: in the process of preparation epoxy phosphate ester, temperature of reaction is preferably between 100～120 ℃, is 2～3 hours during reaction.
10, according to claim 7 or 8 described preparation water-based anticorrosive paint methods, it is characterized in that: in carrying out the graft copolymerization process, the gross weight of vinylformic acid and esters monomer thereof is 12～20% of an epoxy phosphate ester, and wherein the weight of Acrylic Acid Monomer is 3～5% of epoxy phosphate ester.
11, the method for preparing water-based anticorrosive paint according to claim 9, it is characterized in that: in carrying out the graft copolymerization process, the gross weight of vinylformic acid and esters monomer thereof is 12～20% of an epoxy phosphate ester, and wherein the weight of Acrylic Acid Monomer is 3～5% of epoxy phosphate ester.
12, the method for preparing water-based anticorrosive paint according to claim 10 is characterized in that: initiator adopts benzoyl peroxide in carrying out the graft copolymerization process, and consumption accounts for 2%～5% of weight epoxy.
13, the method for preparing water-based anticorrosive paint according to claim 11 is characterized in that: initiator adopts benzoyl peroxide in carrying out the graft copolymerization process, and consumption accounts for 2%～5% of weight epoxy.
14, the method for preparing water-based anticorrosive paint according to claim 13 is characterized in that: in carrying out the graft copolymerization process, temperature of reaction is 90～110 ℃.
15, the method for preparing water-based anticorrosive paint according to claim 7, it is characterized in that: under basic catalyst, react by mixed phenol and formaldehyde as the polyhydroxy phenol aldehyde cpd of linking agent and make, temperature of reaction is 70～100 ℃, time is 2～5 hours, and mixed phenol and formaldehyde mole number ratio are 1: 4.0～1: 6.0.
16, the method for preparing water-based anticorrosive paint according to claim 14, it is characterized in that: under basic catalyst, react by mixed phenol and formaldehyde as the polyhydroxy phenol aldehyde cpd of linking agent and make, temperature of reaction is 70～100 ℃, and the time is 2～5 hours; Mixed phenol and formaldehyde mole number ratio are 1: 4.0～1: 6.0.
17, the method for preparing water-based anticorrosive paint according to claim 15 is characterized in that: mixed phenol can be dihydroxyphenyl propane, phenol or dihydroxyphenyl propane and cresols, and both mol ratios are 0.5: 0.5～0.8: 0.2.
18, the method for preparing water-based anticorrosive paint according to claim 16 is characterized in that: mixed phenol can be dihydroxyphenyl propane, phenol or dihydroxyphenyl propane and cresols, and both mol ratios are 0.5: 0.5～0.8: 0.2.
19, the method for preparing water-based anticorrosive paint according to claim 16 is characterized in that: the mole number ratio of mixed phenol and formaldehyde is 1: 4.5～1: 5.0; Temperature of reaction is 80～90 ℃, and the reaction times is 3～4 hours.
20, the method for preparing water-based anticorrosive paint according to claim 17 is characterized in that: the mole number ratio of mixed phenol and formaldehyde is 1: 4.5～1: 5.0; Temperature of reaction is 80～90 ℃, and the reaction times is 3～4 hours.
21, the method for preparing water-based anticorrosive paint according to claim 18 is characterized in that: the mole number ratio of mixed phenol and formaldehyde is 1: 4.5～1: 5.0; Temperature of reaction is 80～90 ℃, and the reaction times is 3～4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93106438 CN1076948A (en) | 1993-06-01 | 1993-06-01 | Water-based anticorrosive paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93106438 CN1076948A (en) | 1993-06-01 | 1993-06-01 | Water-based anticorrosive paint and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1076948A true CN1076948A (en) | 1993-10-06 |
Family
ID=4986237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93106438 Pending CN1076948A (en) | 1993-06-01 | 1993-06-01 | Water-based anticorrosive paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1076948A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136927A (en) * | 1997-09-24 | 2000-10-24 | Ppg Industries Ohio, Inc. | Phosphatized amine chain-extended epoxy polymeric compounds |
| CN100430449C (en) * | 2004-10-13 | 2008-11-05 | 浙江努奥罗散热器有限公司 | Water anti-corrosion paint and its preparing method |
| CN100432613C (en) * | 2004-12-24 | 2008-11-12 | 三星电子株式会社 | Corrosion-resistant agent and heat exchanger with it |
| CN102146248A (en) * | 2011-04-08 | 2011-08-10 | 广州慧谷化学有限公司 | Acid resistance and high temperature resistance antiseptic waterborne coating for inner wall of pop can |
| CN104294283A (en) * | 2014-10-21 | 2015-01-21 | 中国科学院宁波材料技术与工程研究所 | Environment-friendly water-based antirust agent as well as preparation method and application thereof |
| CN105885609A (en) * | 2016-04-23 | 2016-08-24 | 徐挺 | Water-based epoxy coating and method for preparing same |
| CN106566363A (en) * | 2016-10-21 | 2017-04-19 | 广州擎天材料科技有限公司 | Disc-type electrostatic coating process for vehicle transmission shaft aqueous anticorrosion coating material |
| CN107286797A (en) * | 2017-05-11 | 2017-10-24 | 湖北大学 | Self-emulsified aqueous epoxy phosphate anti-corrosion emulsion and preparation method thereof |
| CN108410310A (en) * | 2018-03-27 | 2018-08-17 | 湖南智涂环保科技有限公司 | A kind of coating film forming matter and its preparation method and application |
| CN112979889A (en) * | 2021-03-25 | 2021-06-18 | 西北永新涂料有限公司 | Waterborne acrylic modified epoxy ester resin and preparation method and application thereof |
-
1993
- 1993-06-01 CN CN 93106438 patent/CN1076948A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136927A (en) * | 1997-09-24 | 2000-10-24 | Ppg Industries Ohio, Inc. | Phosphatized amine chain-extended epoxy polymeric compounds |
| CN100430449C (en) * | 2004-10-13 | 2008-11-05 | 浙江努奥罗散热器有限公司 | Water anti-corrosion paint and its preparing method |
| CN100432613C (en) * | 2004-12-24 | 2008-11-12 | 三星电子株式会社 | Corrosion-resistant agent and heat exchanger with it |
| CN102146248A (en) * | 2011-04-08 | 2011-08-10 | 广州慧谷化学有限公司 | Acid resistance and high temperature resistance antiseptic waterborne coating for inner wall of pop can |
| CN102146248B (en) * | 2011-04-08 | 2013-01-30 | 广州慧谷化学有限公司 | Acid resistance and high temperature resistance antiseptic waterborne coating for inner wall of pop can |
| CN104294283A (en) * | 2014-10-21 | 2015-01-21 | 中国科学院宁波材料技术与工程研究所 | Environment-friendly water-based antirust agent as well as preparation method and application thereof |
| CN105885609A (en) * | 2016-04-23 | 2016-08-24 | 徐挺 | Water-based epoxy coating and method for preparing same |
| CN106566363A (en) * | 2016-10-21 | 2017-04-19 | 广州擎天材料科技有限公司 | Disc-type electrostatic coating process for vehicle transmission shaft aqueous anticorrosion coating material |
| CN106566363B (en) * | 2016-10-21 | 2019-06-11 | 广州擎天材料科技有限公司 | A kind of disc type electrostatic spraying technique suitable for water-based anticorrosive paint used for vehicle transmission shaft |
| CN107286797A (en) * | 2017-05-11 | 2017-10-24 | 湖北大学 | Self-emulsified aqueous epoxy phosphate anti-corrosion emulsion and preparation method thereof |
| CN107286797B (en) * | 2017-05-11 | 2019-09-17 | 湖北大学 | Self-emulsified aqueous epoxy phosphate anti-corrosion lotion and preparation method thereof |
| CN108410310A (en) * | 2018-03-27 | 2018-08-17 | 湖南智涂环保科技有限公司 | A kind of coating film forming matter and its preparation method and application |
| CN108410310B (en) * | 2018-03-27 | 2020-02-21 | 湖南智涂环保科技有限公司 | Coating film forming material and preparation method and application thereof |
| CN112979889A (en) * | 2021-03-25 | 2021-06-18 | 西北永新涂料有限公司 | Waterborne acrylic modified epoxy ester resin and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0006334B1 (en) | Process for preparation of self-emulsifiable epoxy ester copolymer mixtures and products obtained thereby | |
| JPS596207A (en) | Bulk polymerization and polymer | |
| EP1047742A1 (en) | Curable coating compositions | |
| CN1076948A (en) | Water-based anticorrosive paint and preparation method thereof | |
| CN1800225A (en) | Latex type hydroxy acryl acid resin possessing core-shell configuration | |
| EP0071429A2 (en) | Process for preparing a water dilutable epoxy coating composition | |
| CN113512159A (en) | Aqueous single-component modified epoxy resin and preparation method and application thereof | |
| CN115368795B (en) | Water-based high-solid amino baking paint and preparation method thereof | |
| CN101962430A (en) | Method for producing ultraviolet curable amino acrylate resin | |
| US6034157A (en) | Process for producing a coating composition | |
| US4661540A (en) | Water reducible coating compositions | |
| AU616886B2 (en) | Hardenable composition on the basis of a michael addition product, process for the manufacture thereof and use thereof | |
| CN105542098A (en) | Modified aldehyde-ketone resin as well as preparation method and application thereof | |
| CN111807961B (en) | High-hydroxyl acrylic emulsion with quick drying and long pot life and synthesis method thereof | |
| US4238573A (en) | Methacrylate coating compositions | |
| CN102060964B (en) | Preparation method and application of amino acrylic resin | |
| US2709690A (en) | Epoxy resins esterified with drying oil fatty acids and phosphoric acid | |
| JPS5937287B2 (en) | Method for producing an aqueous dispersion composition | |
| CN114044883B (en) | Cashew phenol aldehyde amine epoxy resin curing agent containing purine structure and preparation method thereof | |
| CN114230717B (en) | Preparation process of water-based acrylic resin | |
| CA1334462C (en) | Water-dilutable, crosslinkable binder resin | |
| EP0184467A2 (en) | Water reducible coating compositions | |
| US4195004A (en) | Process for preparing water-dispersible resins | |
| CN108641036B (en) | Water-based acrylic resin and preparation method thereof | |
| CN109593157B (en) | Melamine modified waterborne acrylic flame-retardant resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |