CN100528990C - Manufacturing method of epoxy modification acrylate latex automatic deposit paint - Google Patents
Manufacturing method of epoxy modification acrylate latex automatic deposit paint Download PDFInfo
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- CN100528990C CN100528990C CNB2007100273460A CN200710027346A CN100528990C CN 100528990 C CN100528990 C CN 100528990C CN B2007100273460 A CNB2007100273460 A CN B2007100273460A CN 200710027346 A CN200710027346 A CN 200710027346A CN 100528990 C CN100528990 C CN 100528990C
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Abstract
This invention relates to preparation method of a epoxy modified acrylic latex automotive sediment dope. It adopts ethoxyline resin to modify acrylate, take acrylics monomer as solvent to dissolve ethoxyline resin, emulsify it to gain micro milk particle, then adopt hud emulsion polymerization craft to gain latices. It takes glycollic acid , iodic acid, citric acid as accelerating component of self- sediment painting. Add this self- sediment dope into obtained copolymer emulsion, not at all use organic solvent, avoid harm to environment.
Description
Technical field
The present invention relates to the making method of the making method of auto deposition coating, particularly a kind of epoxy modification acrylate latex automatic deposit paint.
Background technology
Auto deposition coating is called again from the swimming lacquer, and auto deposition coating is the aqueous solution normally, and the form of latex or dispersion makes coating cover the full immersed type aqueous coating of steel surface automatically by chemical reaction.Advanced both at home and abroad at present auto deposition coating is the auto deposition coating that adopts ACRYLIC EMULSION or adopt Resins, epoxy to make as basic material, the ACRYLIC EMULSION auto deposition coating has good weathering resistance, water tolerance and chemical resistance, but its shortcoming is the ACRYLIC EMULSION auto deposition coating and easily produces the hot sticky cold crisp phenomenon, anti-after tackiness, thermotolerance are not good, and the outdoor weatherability of Resins, epoxy is relatively poor.
Summary of the invention
The objective of the invention is at above-mentioned shortcoming, develop a kind of preparation method of epoxy modification acrylate latex automatic deposit paint, adopt Resins, epoxy to acrylate modified, making solvent with acrylic ester monomer dissolves Resins, epoxy, pre-emulsification is the micro emulsion particle, adopt core-shell emulsion polymerization technology to make good, the stable hybridisation emulsion of film forming properties again, make and a kind ofly have that intensity height, adhesivity are good, the characteristic of good corrosion resistance, can adapt to the epoxy modification acrylate latex automatic deposit paint of metal base.
Another object of the present invention is with oxyacetic acid, and acid iodide, citric acid are the promotion component of auto-deposition application.In making copolymer latices, add dispersible pigment color paste, oxyacetic acid, acid iodide, the auto deposition coating of citric acid and deionized water preparation, its paint film have good surface appearance, good solvent resistance, salt spray resistance, impact resistance and good metal attachment fastness.
The object of the present invention is achieved like this:
1, the composition of raw materials of epoxy modification acrylate latex
Below by the epoxy modification acrylate latex total weight percent:
(1), wherein one or both of 10%～50% Resins, epoxy Epon 828 or epoxy resin E-44;
(2), wherein one or more of 50%～80% methyl acrylate (MA), ethyl propenoate (EA), butyl acrylate (BA), cyclohexyl acrylate, methyl methacrylate (MMA), vinylbenzene (ST), vinyl cyanide (AN) or methacrylonitrile;
(3), 1%～10% hydrophilic monomer, as wherein one or more of vinylformic acid (AA), methacrylic acid (MAA) or methylene-succinic acid (ITA);
(4), 0.5%～5% polymerizable self-emulsifying functional monomer, as wherein one or both of sodium vinyl sulfonate (SVS), allyloxy hydroxide sodium dimercaptosulphanatein (COPS-1) or hydroxyethyl methacrylate propanesulfonic acid sodium (HPMAS);
(5), 0.5%～5% emulsifying agent: wherein one or more of sodium lauryl sulphate (K12), Sodium dodecylbenzene sulfonate (SDS), disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate (DB-45), polyoxyethylene nonylphenol ether (NP-9), ethoxylated alkylphenol ammonium sulfate, polyoxyethylene octylphenol ether;
(6) 0.1～1% initiator: wherein one or both of ammonium persulphate (APS) or Potassium Persulphate (KPS);
Below by weight:
(1), the epoxy modification acrylate latex of 100 weight parts;
(2), the dispersible pigment color paste of 1～10 weight part: wherein one or more of carbon black color slurry, phthalocyanine blue mill base, diarylide yellow mill base or lemon mill base;
(3), auto-deposition promoter component: the acid iodide of the oxyacetic acid of 2～15 weight parts, 5～15 weight parts, the citric acid and the appropriate amount of deionized water of 0.5～3 weight part are made into.
2, the synthesis technique step of epoxy modification acrylate latex automatic deposit paint is as follows:
(1), pre-emulsion preparation:
Above-mentioned quantitative Resins, epoxy, acrylic ester monomer, hydrophilic monomer, partial emulsifier and part deionized water are put into stainless steel cauldron, at room temperature stir 0.3h～0.7h, rotating speed 400～800rpm produces pre-emulsion.
(2), seed emulsion hud polymerization:
In another stainless steel cauldron, put into proper amount of deionized water, remaining emulsifying agent and polymerizable self-emulsifying function monomer stirring and dissolving, being warmed up to 65 ℃～85 ℃ adding part initiators and part propylene acid esters monomer examines, question response blueing light, the while adds the pre-emulsion and the remaining initiator of above-mentioned preparation slowly in 2h～4h.
(3), slaking: after above-mentioned technology is finished, be warmed up to 75 ℃～95 ℃ slaking 0.3h～0.7h, lower the temperature then, check, discharging.
(4) join lacquer: take by weighing the above-mentioned homemade epoxy modification acrylate latex of 100 weight parts, add the dispersible pigment color paste of 1～10 weight part, the oxyacetic acid of 2～15 weight parts, the acid iodide of 5～15 weight parts, the citric acid and the appropriate amount of deionized water of 0.5～3 weight part simultaneously, stir and make epoxy modification acrylate latex automatic deposit paint.
With the latex particle size 80～250nm of the inventive method preparation, solid content is about 40～45%.
The present invention combines acrylate and Resins, epoxy, gives full play to their characteristics, and fully not with an organic solvent, avoids environment is worked the mischief.Adopt synthetic latex of the present invention to be coated on metallic substrate surface on the basis of automatic depositing operation and to form corrosion resistant films using, have that intensity height, adhesivity are good, the characteristic of good corrosion resistance,, solvent resistance, salt spray resistance, impact resistance and good metal attachment fastness, be widely used in the application of automobile frame, hardware and metal base.
Specific embodiments
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1: the composition of raw materials of epoxy modification acrylate latex automatic deposit paint and synthesis technique (black):
1, preparation pre-emulsion
Take by weighing 30 kilograms Resins, epoxy Epon 828, take by weighing 3 kilograms methacrylic acid (MAA), take by weighing 35 kilograms butyl acrylate (BA), take by weighing 40 kilograms methyl methacrylate (MMA), take by weighing 10 kilograms vinylbenzene (ST), take by weighing 60 kilograms of deionized waters, take by weighing 1.2 kilograms of sodium lauryl sulphate (K12), take by weighing 0.6 kilogram of polyoxyethylene nonylphenol ether (NP-9), put into stainless steel cauldron and stir 0.3h～0.7h under room temperature, rotating speed 400～800rpm forms pre-emulsion.
2, seed emulsion hud polymerization
In another stainless steel cauldron, with 40 kilograms of deionized waters, 0.2 kilogram of sodium lauryl sulphate (K12), 1 kilogram of allyloxy hydroxide sodium dimercaptosulphanatein (COPS-1) stirring and dissolving, be warmed up to 75 ℃ and add 0.1 kilogram of Sodium Persulfate and 5 kg water solution, when temperature is warming up to 78 ℃, adding 5 kilograms of vinylbenzene (ST), 3 kilograms of butyl acrylates (BA), 1 kilogram of methacrylic acid (MAA) examines, question response blueing light adds the pre-emulsion of above-mentioned preparation, 0.3 kilogram of Sodium Persulfate and 40 kg water solution slowly in 3h.
3, slaking: after above-mentioned technology is finished, be warmed up to 88 ℃ of slaking 0.5h, lower the temperature then, check, make epoxy modification acrylate latex.
4, join lacquer: take by weighing the above-mentioned homemade epoxy modification acrylate latex of double centner, add 7.4 kilograms carbon black color slurry, 8 kilograms oxyacetic acid, 6 kilograms acid iodide, 1 kilogram citric acid and 300 kilograms deionized water simultaneously, stir and make epoxy modification acrylate latex automatic deposit paint.
Embodiment 2: the composition of raw materials of epoxy modification acrylate latex automatic deposit paint and synthesis technique (yellow):
1, preparation pre-emulsion
Take by weighing 25 kilograms epoxy resin E-44, take by weighing 2 kilograms methacrylic acid (MAA), take by weighing 37 kilograms butyl acrylate (BA), take by weighing 36 kilograms of methyl methacrylates (MMA), take by weighing 10 kilograms vinylbenzene (ST), take by weighing 2 kilograms vinyl cyanide (AN), take by weighing 60 kilograms of deionized waters, take by weighing 1.5 kilograms of Sodium dodecylbenzene sulfonatees (SDS), take by weighing 0.8 kilogram of polyoxyethylene nonylphenol ether (NP-9), put into stainless steel cauldron and stir 0.3h～0.7h under room temperature, rotating speed 400～800rpm forms pre-emulsion.
2, seed emulsion hud polymerization
In another stainless steel cauldron, with 40 kilograms of deionized waters, 0.2 kilogram of Sodium dodecylbenzene sulfonate (SDS), 1 kg ethylene base sodium sulfonate (SVS) stirring and dissolving, be warmed up to 75 ℃ of solution that add 0.2 kilogram of ammonium persulphate (APS) and 5 kg water, when temperature is warming up to 78 ℃, adding 5 kilograms of vinylbenzene (ST), 3 kilograms of butyl acrylates (BA), 1 kilogram of methacrylic acid (MAA) examines, question response blueing light adds pre-emulsion, 0.4 kilogram of ammonium persulphate (APS) and the 40 kg water solution of above-mentioned preparation slowly in 3h.
3, slaking: after above-mentioned technology is finished, be warmed up to 88 ℃ of slaking 0.5h, lower the temperature then, check, make epoxy modification acrylate latex.
4, join lacquer: take by weighing the above-mentioned homemade epoxy modification acrylate latex of double centner, add 8 kilograms diarylide yellow mill base, 10 kilograms oxyacetic acid, 8 kilograms acid iodide, 1 kilogram citric acid and 300 kilograms deionized water simultaneously, stir and make epoxy modification acrylate latex automatic deposit paint.
Claims (1)
1, the making method of epoxy modification acrylate latex automatic deposit paint is characterized in that realizing by following technology:
The composition of raw materials of A, epoxy modification acrylate latex
Below by the epoxy modification acrylate latex total weight percent:
(1), wherein one or both of 10%～50% Resins, epoxy Epon 828 or epoxy resin E-44;
(2), wherein one or more of 50%～80% methyl acrylate, ethyl propenoate, butyl acrylate, cyclohexyl acrylate, methyl methacrylate, vinylbenzene, vinyl cyanide or methacrylonitrile;
(3), 1%～10% hydrophilic monomer, as wherein one or more of vinylformic acid, methacrylic acid or methylene-succinic acid;
(4), 0.5%～5% polymerizable self-emulsifying functional monomer, as wherein one or both of sodium vinyl sulfonate, allyloxy hydroxide sodium dimercaptosulphanatein or hydroxyethyl methacrylate propanesulfonic acid sodium;
(5), 0.5%～5% emulsifying agent: wherein one or more of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, polyoxyethylene nonylphenol ether, ethoxylated alkylphenol ammonium sulfate, polyoxyethylene octylphenol ether;
(6) 0.1～1% initiator: wherein one or both of ammonium persulphate or Potassium Persulphate;
Below by weight:
(1), the epoxy modification acrylate latex of 100 weight parts;
(2), the dispersible pigment color paste of 1～10 weight part: wherein one or more of carbon black color slurry, phthalocyanine blue mill base, diarylide yellow mill base or lemon mill base;
(3), auto-deposition promoter component: the acid iodide of the oxyacetic acid of 2～15 weight parts, 5～15 weight parts, the citric acid and the appropriate amount of deionized water of 0.5～3 weight part are made into;
The synthesis technique step of B, epoxy modification acrylate latex automatic deposit paint is as follows:
(1), pre-emulsion preparation:
Above-mentioned quantitative Resins, epoxy, acrylic ester monomer, hydrophilic monomer, partial emulsifier and part deionized water are put into stainless steel cauldron, at room temperature stir 0.3h～0.7h, rotating speed 400～800rpm produces pre-emulsion,
(2), seed emulsion hud polymerization:
In another stainless steel cauldron, put into proper amount of deionized water, remaining emulsifying agent and polymerizable self-emulsifying function monomer stirring and dissolving, being warmed up to 65 ℃～85 ℃ adding part initiators and part propylene acid esters monomer examines, question response blueing light, the while adds the pre-emulsion and the remaining initiator of above-mentioned preparation slowly in 2h～4h;
(3), slaking: after above-mentioned technology is finished, be warmed up to 75 ℃～95 ℃ slaking 0.3h～0.7h, lower the temperature then, check, discharging;
(4) join lacquer: take by weighing the above-mentioned homemade epoxy modification acrylate latex of 100 weight parts, add the dispersible pigment color paste of 1～10 weight part, the oxyacetic acid of 2～15 weight parts, the acid iodide of 5～15 weight parts, the citric acid and the appropriate amount of deionized water of 0.5～3 weight part simultaneously, stir and make epoxy modification acrylate latex automatic deposit paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100273460A CN100528990C (en) | 2007-03-30 | 2007-03-30 | Manufacturing method of epoxy modification acrylate latex automatic deposit paint |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100273460A CN100528990C (en) | 2007-03-30 | 2007-03-30 | Manufacturing method of epoxy modification acrylate latex automatic deposit paint |
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| CN101045844A CN101045844A (en) | 2007-10-03 |
| CN100528990C true CN100528990C (en) | 2009-08-19 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974194B (en) * | 2010-09-29 | 2012-05-16 | 江苏科技大学 | Epoxy modified styrene-acrylate emulsion and preparation method thereof |
| CN103282451B (en) * | 2010-12-20 | 2017-02-22 | 汉高股份有限及两合公司 | Glossy improved appearance auto-eposition coating, and methods of applying same |
| US9228109B2 (en) | 2010-12-20 | 2016-01-05 | Henkel Ag & Co. Kgaa | Glossy improved appearance auto-deposition coating, and methods of applying same |
| CN102603998B (en) * | 2012-02-23 | 2014-08-20 | 青岛德鑫汽车涂料有限公司 | Preparation method of high solid content epoxy modified acrylic resin emulsion |
| CN102993355A (en) * | 2012-12-19 | 2013-03-27 | 青岛海尔软件有限公司 | Preparation method of acrylate microemulsion with high solid content |
| CN102977287A (en) * | 2012-12-24 | 2013-03-20 | 青岛海尔软件有限公司 | Epoxy-acrylate composite emulsion and method for preparing same |
| CN102964536B (en) * | 2012-12-24 | 2015-05-20 | 青岛佰众化工技术有限公司 | Epoxy acrylate composite emulsion and preparation method thereof |
| CN106220792A (en) * | 2016-07-29 | 2016-12-14 | 常熟林润氟硅材料有限公司 | A kind of preparation method of epoxy resin modified aqueous acrylic emulsion |
| CN108570132B (en) * | 2017-03-10 | 2021-04-06 | 北京金汇利应用化工制品有限公司 | Hybrid emulsion of epoxy ester resin aqueous dispersion and acrylic resin |
| CN107446456B (en) * | 2017-08-03 | 2019-04-16 | 杭州五源科技实业有限公司 | Auto-deposition coating problems agent and its preparation method and application before steel coating |
| CN111518450A (en) * | 2020-06-11 | 2020-08-11 | 金陵科技学院 | Preparation method of graphene oxide/acrylate-epoxy resin composite anticorrosive paint |
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