CN1307268C - Ultraviolet light curing cathodic electrophoretic coating and preparation thereof - Google Patents
Ultraviolet light curing cathodic electrophoretic coating and preparation thereof Download PDFInfo
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- CN1307268C CN1307268C CNB2004100543894A CN200410054389A CN1307268C CN 1307268 C CN1307268 C CN 1307268C CN B2004100543894 A CNB2004100543894 A CN B2004100543894A CN 200410054389 A CN200410054389 A CN 200410054389A CN 1307268 C CN1307268 C CN 1307268C
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Abstract
The present invention relates to an ultraviolet light curing cathodic electrophoretic coating and a preparation method thereof. The ultraviolet light curing cathodic electrophoretic coating is composed of 100 portions of modified acrylic resin with ethenyl capable of ultraviolet light curing and amino of negative electrode electro-depositing performance, and 0.1 to 10 portions of one type, or multiple types of initiators capable of absorbing the radiation of ultraviolet light within the range from 200 to 400 nm. The surface of a coating film is level and smooth and has excellent adhesiveness to base material, and what is more important, the ultraviolet light curing of the coating film can be realized at the normal temperature; thus, the present invention can be applied to the base material of plastics of thermal sensitivity, etc.
Description
Technical field
The present invention relates to a kind of coating, especially, relate to a kind of ultraviolet light polymerization cathode electrophoresis dope and preparation method thereof.
Background technology
Cathode electrophoresis dope is since the development seventies in 20th century and obtaining industrial applications, with its superior corrosion resistance, high throwing power, high coulomb efficiency, do not dissolve advantages such as coated article, tank liquor are stable, level of automation height, obtain widespread use in industries such as automotive industry, household electrical appliance, instrument, military project, building materials, progressively replace anode electrophoresis dope, and become one of most important application mode in the world today.
Present cathode electrophoresis dope adopts the thermofixation mode crosslinked, and not only the storing temperature height is generally 170～180 ℃, and storing time is long, generally greater than 20 minutes.Even the low temperature thermofixation cathode electrophoresis dope that latest developments are got up, its solidification value also is higher than 120 ℃, this has just limited its application in the thermo-sensitivity plastic basis material greatly, and most electrophoretic paint is in curing process, can discharge small organic molecule, contaminate environment can discharge small molecules as present widely used blocked isocyanate curing agent in solidification process.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of by the acrylic resin modified ultraviolet light polymerization cathode electrophoresis dope of making.
This goal of the invention is achieved through the following technical solutions: a kind of ultraviolet light polymerization cathode electrophoresis dope is characterized in that it mainly is made up of 100 parts of acrylic resin modified, 0.1～10 part of photoinitiators and 200～2000 parts of deionized waters; Wherein, described acrylic resin modified be to comprise the vinyl of uV curable simultaneously and have the single acrylic copolymeric resin of the amido of galvanic deposit.
The present invention also aims to provide a kind of preparation method of above-mentioned ultraviolet light polymerization cathode electrophoresis dope.
This goal of the invention is achieved through the following technical solutions: the preparation method of the described ultraviolet light polymerization cathode electrophoresis dope of a kind of claim 1, it is characterized in that, and may further comprise the steps:
(1) preparation acrylic resin: 5～26wt% contains the acrylic ester monomer of tertiary amine groups, acrylic ester monomer, other acrylic ester monomer of 45～70wt% and the copolyreaction under the initiator effect of 0～30wt% vinyl monomer of 15～30wt% hydroxyl made.
(2) preparation is acrylic resin modified: acrylic resin and contain the isocyanic ester of vinyl or product prepared in reaction under catalyst action that the acrylate monomer of polyisocyanates and hydroxyl reacts, in the acrylic resin in hydroxyl and the isocyanic ester mol ratio of isocyanato be 1: 0.3～1.0.
(3) preparation ultraviolet light polymerization cathode electrophoresis dope: in acrylic resin modified, add photosensitizers,, and, be mixed with electrophoretic paint through high-speed stirring with the deionized water dilution with the acid neutralization.
The present invention has following technique effect: room temperature fast-curing, energy-conservation, environmental friendliness both can be used for the conventional metals base material, can be used for the plastic basis material of thermo-sensitivity again.
Embodiment
The acrylic resin molecular weight is 2000～30000, has tertiary amine groups and hydroxyl on the side chain.It is formed by the copolymerization under the initiator effect of following several monomers, described monomer comprises that (a) contains (methyl) acrylic ester monomer of tertiary amine groups, its content is 5～26wt%, (b) (methyl) acrylic ester monomer of hydroxyl, its content is 15～30wt%, and (c) other acrylic ester monomer, its content are 45～70wt%, (d) vinyl monomer, its content are 0～30wt%.
The described unsaturated monomer (a) that contains tertiary amine groups, comprise (methyl) vinylformic acid dimethylamine ethyl ester, (methyl) vinylformic acid diethylamine ethyl ester, (methyl) vinylformic acid dimethylamine n-propyl, (methyl) vinylformic acid diethylamine n-propyl, (methyl) vinylformic acid diethylamine methyl esters, N dimethylamine ethyl acrylamide, N dimethylamine ethyl-methyl acrylamide, N dimethylamine base ethyl acrylamide, N dimethylamine ethyl-methyl acrylamide etc., and other contains the vinyl substituted heterocycle of tertiary amine groups, as vinyl pyridine, N-vinyl imidazole, N-vinyl pyrrolidone etc.
The unsaturated comonomer of above-mentioned hydroxyl (b) comprises (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid-3-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxy butyl ester, (methyl) vinylformic acid-2-hydroxypropyl acrylate.
Above-mentioned other acrylic ester monomer (c) comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid n-pentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) ethyl acrylate etc.
Above-mentioned vinyl monomer (d) comprises vinyl cyanide, vinylbenzene, vinyl acetate etc.
Monomer (a) contains tertiary amine groups, and it gives resin cationic electrodeposition characteristic, and the content in comonomer is 5～26wt%.When content is too low, acrylic resin modified can not in water, the dispersion well, can not form uniform electrodeposition coating; When content is too much, can produce undesired deposition.
(methyl) acrylic ester monomer (b) of hydroxyl and other monomer copolymerizable, can improve the dispersiveness of resin in water on the one hand, improve the sticking power of itself and substrate, on the other hand can with the isocyanate reaction that contains vinyl, make the vinyl of introducing uV curable in the resin.Its content is 15～30wt%, but content is when too much, easily make electrophoresis film in water-content increase.
Monomer (c) give film snappiness and smoothness, and its consumption can be adjusted in very wide scope as required.
Monomer (d) can improve water tolerance, the chemical proofing of filming, reduce cost.Its consumption is too much, and the fragility of filming is increased.
Can select suitable solvent, adopt solution polymerization process to prepare acrylic resin.Solvent can adopt aromatic hydrocarbon solvents such as toluene, dimethylbenzene, ketones solvents such as methyl ethyl ketone.Initiator amount is 0.5～5wt% of comonomer, can adopt azo or peroxide initiator, perhaps mixed initiator.The number-average molecular weight of the acrylic resin of copolymerization gained is between 2000～30000.
The acrylic resin that makes is under catalyst actions such as zinc octoate, ferric acetyl acetonade, dibutyl tin laurate, organo-bismuth, hydroxyl in the acrylic resin obtains acrylic resin modified with the isocyanato reaction that contains in the isocyanic ester of vinyl, make in the resin vinyl of introducing uV curable, wherein in the acrylic resin in hydroxyl and the isocyanic ester mol ratio of isocyanato be 1: 0.3～1.0.Consumption as if the isocyanic ester that contains vinyl is very few, then is unfavorable for the ultraviolet light polymerization that electrophoresis is filmed; Consumption is too much, then influences the sticking power of coating to base material.
Above-mentioned isocyanic ester can be the monoisocyanates that contains vinyl, as a pseudoallyl-α, α-Er Jiajibianji isocyanic ester (TMI), methacrylic acid-2-isocyanato ethyl ester (MOI), it also can be the polyisocyanates that contains the different isocyanato of active degree, as tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), 2,6-two isocyanato methyl caproates (LDI), 2,2,4-trimethylammonium hexamethylene diisocyanate (TMDI), Methylcyclohexyl diisocyanate (HTDI), the unsaturated monomer such as the 2-hydroxyethyl methacrylate of dimer acid diisocyanate (DDI) etc. and hydroxyl, the product of reaction such as methacrylic acid-3-hydroxypropyl acrylate.
The ultraviolet light polymerization cathode electrophoresis dope also contains photoinitiator.The photoinitiator that is fit to comprises benzophenone and derivative, phenylbenzyl ketone and derivative thereof, methyl phenyl ketone and derivative thereof, st-yrax ethers and derivative thereof etc.They both can use separately, also can mix use, and its consumption is 0.5～10% of a resin quality.
Acrylic resin modified with acid neutralization preparation.The used acid that neutralizes comprises organic acid and mineral acid, organic acid such as formic acid, acetate, lactic acid, propionic acid, butyric acid, methanesulfonic, ethane sulfonic acid, propane sulfonic acid, hydroxyethanesulfonic acid, hydroxypropanesulfonic acid etc., mineral acid example hydrochloric acid, sulfuric acid, phosphoric acid etc.The consumption of acid changes with the content of tertiary amine groups in the resin, but resin is evenly dispersed in the water, and the degree of neutralization of tertiary amine groups is generally between 0.5～1.0.
As required, in the ultraviolet light polymerization cathode electrophoresis dope, add dyestuff or pigment and other additive such as tensio-active agent, antioxidant etc.Preferred dyestuff such as mordanting dye.Pigment comprises pigment dyestuff and mineral dye, pigment dyestuff such as azo-type, phthalein cyanogen type, metal complex salt etc.; Metallic compounds such as mineral dye such as titanium oxide, ferric oxide, barium sulfate.Carbon black also can be used as pigment, and its consumption should be less than the 20wt% of resin.
The acid neutral is acrylic resin modified, and to be diluted to solids constituent content with deionized water be 5～30wt%, and regulating the pH value is 5～7, and high-speed stirring forms stable water dispersion.In the electrophoresis groove liquid temperature is that 18～30 ℃, voltage are to carry out electrophoretic deposition under the condition of 10～250V, obtains filming of even compact.After the small amount of moisture during flash distillation is removed and filmed, the crosslinked ultraviolet light polymerization ability cathode electrophoresis that obtains of ultraviolet light polymerization is filmed at normal temperatures.
The invention will be further described below in conjunction with embodiment, but the present invention is not limited thereto.
Embodiment 1
One, the preparation of acrylic resin
The Diisopropyl azodicarboxylate that accounts for monomer mass 3% is dissolved in the monomer, wherein methyl methacrylate, vinylbenzene, butyl methacrylate and 2-hydroxyethyl methacrylate consumption are respectively 79,21,22 and 44.4g, and the consumption of methacrylic diethylammonium salt ethyl ester is 16.8g.Slowly splash in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed at 75 ℃ of following monomers, solvent is a butanone, and its consumption is 1.5 times of monomer mass, reacts 4 hours, and monomer conversion is reached more than 98%.
Two, acrylic resin modified preparation
In the synthetic acrylic resin, add catalyzer 0.5wt% dibutyl tin laurate, slowly drip pseudoallyl-α between 42.4 g, α-Er Jiajibianji isocyanic ester down at 60 ℃, reacted 3 hours, add an amount of dehydrated alcohol, remove unreacted isocyanic ester, vacuum extracts solvent.
Three, the preparation of ultraviolet light polymerization cathod coating
The adding mass ratio is 1: 1 2-hydroxy-2-methyl Propiophenone and a 1-methylcyclohexane benzophenone photoinitiator in acrylic resin modified, its consumption is the 1.5wt% of resin, is 6.0 with lactic acid neutralization to the pH value, and to be diluted to solid content with deionized water be 15%, is mixed with the ultraviolet light polymerization cathode electrophoresis dope through high speed dispersion.
Four, ultraviolet light polymerization cathode electrophoresis dope Performance Detection
With the preparation the ultraviolet light polymerization cathode electrophoresis dope as electrophoresis groove liquid, under 25 ℃ of temperature, voltage 20V, electrophoretic painting is carried out on the stainless steel plate surface.Stainless steel plate after the application was 60 ℃ of following flash distillations 10 minutes, and curing cross-linked is 55 seconds under room temperature, 1kW high pressure Hg lamp irradiation.Recording coating thickness is 25 μ m, appearance of film light, fine and smooth smooth, and pencil hardness＞6H, the two-way wiping examination of acetone is filmed and is not seen the loss of gloss phenomenon 150 times, shows that curing of coating is abundant.
Embodiment 2
One, the preparation of acrylic resin
The dilauroyl peroxide that accounts for monomer mass 3.5% is dissolved in the monomer, wherein methyl methacrylate, vinyl acetate, butyl methacrylate and 2-hydroxyethyl methacrylate consumption are respectively 82,18,20 and 42.8g, and the consumption of dimethylaminoethyl methacrylate is 15.7g.Slowly splash in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed at 80 ℃ of following monomers, reaction medium is a toluene, and its consumption is 1.5 times of monomer mass, reacts 8 hours, and monomer conversion is reached more than 98%.
Two, acrylic resin modified preparation
The molecule mol ratio be 1: 1 isophorone diisocyanate and 2-hydroxyethyl methacrylate under the katalysis of 0.5wt% dibutyl tin laurate, 30 ℃ of reactions 6 hours down generate the isocyanic ester of band vinyl.The isocyanic ester of 42.4g synthetic band vinyl is added drop-wise in the synthetic acrylic resin, and under the effect of 0.6wt% octoate catalyst zinc, 60 ℃ were reacted 4 hours, added an amount of dehydrated alcohol, removed unreacted isocyanic ester, and vacuum extracts solvent.
Three, the preparation of ultraviolet light polymerization cathode electrophoresis dope
The adding mass ratio is 1: 1.5 2-methyl isophthalic acid-[4-methylthio phenyl]-2-morpholino acetone-1 and a 1-methylcyclohexane benzophenone photoinitiator in acrylic resin modified, its consumption is the 1.0wt% of resin, through the propionic acid pH value that neutralizes is 6.0, and to be diluted to solid content with deionized water be 15%, is mixed with the ultraviolet light polymerization cathode electrophoresis dope through high speed dispersion.
Four, ultraviolet light polymerization cathode electrophoresis dope Performance Detection
With the preparation the ultraviolet light polymerization cathode electrophoresis dope as electrophoresis groove liquid, under 25 ℃ of temperature, voltage 30V, the ABS plate that surperficial conductive processing is crossed carries out electrophoretic painting.60 ℃ of flash distillation 10min of model after the application, curing cross-linked is 60 seconds under room temperature, 1kW high pressure Hg lamp irradiation.Recording coat-thickness is 25 μ m, paint film appearance light, fine and smooth smooth, and pencil hardness 6H, the two-way wiping examination of acetone coating is not seen the loss of gloss phenomenon 150 times, shows that film curing is abundant.
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (10)
1, a kind of ultraviolet light polymerization cathode electrophoresis dope is characterized in that, it is mainly acrylic resin modified by 100 mass parts, 0.1～10 mass parts photoinitiator and 200～2000 mass parts deionized waters are formed; Wherein, described acrylic resin modified be to comprise the vinyl of uV curable simultaneously and have the single acrylic copolymeric resin of the amido of galvanic deposit.
2. ultraviolet light polymerization cathode electrophoresis dope according to claim 1, it is characterized in that, described acrylic resin modified acrylic resin by hydroxy functional groups reacts under catalyst action with the isocyanic ester that contains vinyl and forms, and the mol ratio of isocyanato is 1: 0.3～1.0 in described acrylic resin modified middle hydroxyl and the isocyanic ester.
3. ultraviolet light polymerization cathode electrophoresis dope according to claim 1 is characterized in that, described photoinitiator is made up of one or more of benzophenone and derivative, phenylbenzyl ketone and derivative thereof and benzoin ether and derivative thereof.
4. ultraviolet light polymerization cathode electrophoresis dope according to claim 2, it is characterized in that, described acrylic resin by 5～26wt% contain the acrylate monomer of tertiary amine groups, acrylate monomer, other acrylate monomer of 45～70wt% and the copolymerization under the initiator effect of 0～30wt% vinyl monomer of 15～30wt% hydroxyl forms.
5. ultraviolet light polymerization cathode electrophoresis dope according to claim 2 is characterized in that, described catalyzer is zinc octoate, ferric acetyl acetonade, dibutyl tin laurate or organic bismuth catalyst.
6, ultraviolet light polymerization cathode electrophoresis dope according to claim 2 is characterized in that, the product of the acrylate monomer reaction that the described isocyanic ester that contains vinyl is monoisocyanates or polyisocyanates and hydroxyl.
7. ultraviolet light polymerization cathode electrophoresis dope according to claim 4 is characterized in that, described initiator is azo initiator or peroxide initiator.
8. the preparation method of the described ultraviolet light polymerization cathode electrophoresis dope of claim 1 is characterized in that, may further comprise the steps:
(1) preparation acrylic resin: 5～26wt% contains the acrylate monomer of tertiary amine groups, acrylate monomer, other acrylate monomer of 45～70wt% and the copolyreaction under the initiator effect of 0～30wt% vinyl monomer of 15～30wt% hydroxyl made;
(2) preparation is acrylic resin modified: acrylic resin and contain the isocyanic ester of vinyl or product prepared in reaction under catalyst action that the acrylate monomer of polyisocyanates and hydroxyl reacts, in the acrylic resin in hydroxyl and the isocyanic ester mol ratio of isocyanato be 1: 0.3～1.0;
(3) preparation ultraviolet light polymerization cathode electrophoresis dope: in acrylic resin modified, add photosensitizers,, and, be mixed with electrophoretic paint through high-speed stirring with the deionized water dilution with the acid neutralization.
9. preparation method according to claim 8 is characterized in that, described initiator is azo or peroxide initiator; Described catalyzer is zinc octoate, ferric acetyl acetonade, dibutyl tin laurate or organic bismuth catalyst.
10. preparation method according to claim 8 is characterized in that, described acid is organic acid or mineral acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100543894A CN1307268C (en) | 2004-09-06 | 2004-09-06 | Ultraviolet light curing cathodic electrophoretic coating and preparation thereof |
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| CNB2004100543894A CN1307268C (en) | 2004-09-06 | 2004-09-06 | Ultraviolet light curing cathodic electrophoretic coating and preparation thereof |
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| CN1307268C true CN1307268C (en) | 2007-03-28 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104151890B (en) * | 2014-07-30 | 2016-08-31 | 中国海洋石油总公司 | A kind of ultraviolet light curing cathodic electrophoretic coating composition |
| CN104987761B (en) * | 2015-07-29 | 2017-06-16 | 湖南省霖辉高新材料科技有限公司 | A kind of UV cathode electrodip paintings and its coating process |
| CN107746444B (en) * | 2017-10-10 | 2021-02-12 | 华南理工大学 | Ultraviolet-cured acrylate electrophoretic coating containing long alkyl side chain and preparation method and application thereof |
| CN109957299B (en) * | 2019-04-16 | 2021-06-04 | 江南大学 | Photo-curing water-based acrylic acid cathode electrophoretic coating |
| CN115521697B (en) * | 2022-10-12 | 2023-10-03 | 韶关市科德新材料有限公司 | Organic-inorganic hybrid UV thermal dual-curing epoxy cathode electrophoretic coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196380A (en) * | 1997-04-15 | 1998-10-21 | 马友存 | Solid regenerative gas desulfurizing agent and preparation and regeneration technology thereof |
| CN1263921A (en) * | 1999-02-18 | 2000-08-23 | 株式会社清水 | Ultraviolet curing coating composite for cation electro-deposition |
| CN1094495C (en) * | 1999-08-16 | 2002-11-20 | 北京石油化工学院 | New-type ultra violet photocureable resin and its preparation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196380A (en) * | 1997-04-15 | 1998-10-21 | 马友存 | Solid regenerative gas desulfurizing agent and preparation and regeneration technology thereof |
| CN1263921A (en) * | 1999-02-18 | 2000-08-23 | 株式会社清水 | Ultraviolet curing coating composite for cation electro-deposition |
| CN1094495C (en) * | 1999-08-16 | 2002-11-20 | 北京石油化工学院 | New-type ultra violet photocureable resin and its preparation |
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