CN1309754C - Water photosensitive resin emulsion and preparation thereof - Google Patents
Water photosensitive resin emulsion and preparation thereof Download PDFInfo
- Publication number
- CN1309754C CN1309754C CNB2005100943459A CN200510094345A CN1309754C CN 1309754 C CN1309754 C CN 1309754C CN B2005100943459 A CNB2005100943459 A CN B2005100943459A CN 200510094345 A CN200510094345 A CN 200510094345A CN 1309754 C CN1309754 C CN 1309754C
- Authority
- CN
- China
- Prior art keywords
- photosensitive resin
- vinyl
- acid
- performed polymer
- water
- 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
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to water-based photosensitive resin emulsion and a preparation method thereof, which belongs to the technical field of ultraviolet light curing or polymerization. In the present invention, prepolymers containing epoxy groups and amine compounds are used for preparing prepolymers containing tertiary amine groups through an epoxy aminating ring opening reaction, and then the prepared prepolymers react with isocyanate containing vinyl groups for modification. The vinyl groups capable of generating an ultraviolet light curing reaction are introduced into the prepolymers in a controllable introduced proportion to prepare novel photosensitive resin which is water-soluble. The water-based photosensitive resin emulsion prepared from the photosensitive resin can be used for preparing photosensitive emulsion used for cathode electrophoretic paint, water-based ultraviolet light curing paint and printing plate materials. The water-based photosensitive resin emulsion has the advantages of high stability, rapid light curing at low temperature, environmental protection, etc.
Description
Technical field
A kind of water photosensitive resin emulsion and preparation method thereof the present invention relates to a kind of photosensitive resin emulsion, is applicable to cathode electro-coating and UV-curable waterborne coatings, belongs to ultraviolet light polymerization or polymerization technique field.
Background technology
Cathode electrophoresis dope is since the development seventies in 20th century and obtaining industrial applications, with characteristics such as its superior corrosion resistance, mechanical property, throwing power and automation paint abilities, obtain widespread use in industries such as automotive industry, household electrical appliance, instrument, military project, building materials, oneself progressively becomes one of most important application mode in the world today.
The curing of coating mode of at present nearly all cathode electrophoresis dope all turns to the master with thermosetting, and coating takes place to solidify builds bridge the temperature of reaction generally at 140 ℃-180 ℃, so be difficult to promote the use of electrophoretic painting on many materials that are subjected to temperature limitation.And ultraviolet ray (UV) coating material solidified be to utilize UV-irradiation to make the build bridge curing mode of reaction of coating generation polymerization, in the following short period of time of cryogenic condition, just can finish the solidification process of coating.
During traditional radiation curing is formed, because the unsaturated functionality of oligopolymer is fixed substantially, thus monomer play a part crucial, except the viscosity of regulation system, it can also have influence on cure kinetics, the physical properties of the extent of polymerization and the polymkeric substance that generates etc.But, use monomer can bring adverse influence to final transformation efficiency simultaneously, cause containing in the polymeric coating a large amount of residual monomers.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of performed polymer that contains tertiary amine group is provided, in performed polymer, introduce vinyl, and the ratio of introducing is controlled, makes a kind of novel water photosensitive resin emulsion by modification.
Purpose of the present invention still prepares a kind of water photosensitive resin emulsion that can be used for cathode electro-coating, UV-curable waterborne coatings and printing plate, and it has satisfactory stability, low temperature fast setting, advantages of environment protection.
Realize that the object of the invention technical scheme is the performed polymer that is contained tertiary amine group by component (a), component (b) contains the isocyanic ester of vinyl, the water photosensitive resin emulsion that the resin that component (c) light trigger is formed makes through emulsification.Wherein: component (a) is to introduce the performed polymer of tertiary amine group by the epoxy amine addition reaction, it is mixed with component (b) weighing, be warming up to preset temperature reaction certain hour and obtain photosensitive resin, add light trigger and neutralizing agent and stir, add the water photosensitive resin emulsion of the accomplished the object of the invention of deionized water homogenizing emulsifying then.
Water photosensitive resin emulsion of the present invention, be to contain the performed polymer of epoxide group and amine compound to melt the ring reaction by epoxy amine and make the performed polymer that contains tertiary amine group, again with the isocyanate reaction modification that contains vinyl, in performed polymer, introduce the vinyl that can carry out the ultraviolet light polymerization reaction, the ratio of introducing is controlled, make water photosensitive resin, add the light trigger of this resin quality than 1-4wt%, add neutralizing agent acid and deionized water again, be mixed with the photosensitive resin emulsion that resin solid content is 15-30wt%.
The performed polymer that contains tertiary amine group is to melt the ring reaction by pre-polymerization that contains epoxide group and amine compounds object by epoxy amine to make, the used performed polymer that contains epoxide group is the bisphenol A type epoxy resin of different molecular weight, bisphenol f type epoxy resin, or (methyl) glycidyl acrylate is acrylic resin modified, and its epoxy equivalent (weight) is 200-2000; Used amine compound is one or more in diethylamine, dipropyl amine, dibutylamine, Monoethanolamine MEA BASF, diethanolamine, the Mono Methyl Ethanol Amine.
Photosensitive resin is to be made by performed polymer that contains tertiary amine group and the isocyanate reaction that contains vinyl, and the performed polymer that contains tertiary amine group is 1 with the mol ratio that contains the isocyanic ester of vinyl: 1-1: 6.
The isocyanic ester that contains vinyl comprises the monoisocyanates that contains vinyl: pseudoallyl-α, α-Er Jiajibianji isocyanic ester, methacrylic acid-2-isocyanato ethyl ester; Or contain the polyisocyanates and the α of the different isocyanato of active degree, β-vinyl unsaturated monocarboxylic hydroxy ester reaction gained α, β-semiclosed the isocyanic ester of vinyl unsaturated monocarboxylic hydroxy ester, polyisocyanates and α, the mol ratio of β-vinyl unsaturated monocarboxylic hydroxy ester is 1: 0.8-1: 1.5; Polyisocyanates is tolylene diisocyanate, isophorone diisocyanate, 2,6-two isocyanato methyl caproates, 2,2,4-trimethylammonium hexamethylene diisocyanate, Methylcyclohexyl diisocyanate or dimer acid diisocyanate; α, β-vinyl unsaturated monocarboxylic hydroxy ester are (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate or (methyl) vinylformic acid hydroxy butyl ester.
Used light trigger comprises one or more in benzophenone and derivative, benzophenone and derivative thereof, phenylbenzyl ketone and derivative thereof, methyl phenyl ketone and derivative thereof, Propiophenone and derivative thereof, st-yrax ethers and the derivative thereof.
Used neutralizing agent acid is organic acid or mineral acid, organic acid: formic acid, acetate, lactic acid, propionic acid, butyric acid, methanesulfonic, ethane sulfonic acid, propane sulfonic acid, hydroxyethanesulfonic acid or hydroxypropanesulfonic acid, or mineral acid: hydrochloric acid, sulfuric acid, phosphoric acid.With the neutralizing agent acid for adjusting pH value to 4.0-6.5.
It is that acrylic ester monomer, other acrylic ester monomer of 30-70wt% and the copolymerization of 0-30wt% vinyl monomer by 5-20wt% (methyl) glycidyl acrylate, 10-30wt% hydroxyl forms that preparation contains (methyl) glycidyl acrylate that the performed polymer of tertiary amine group uses acrylic resin modified.
The preparation method of water photosensitive resin emulsion of the present invention may further comprise the steps:
(1) preparation contains the performed polymer of tertiary amine group: melt the ring reaction by performed polymer that contains epoxide group and amine compound by epoxy amine and make, containing the epoxide group in the performed polymer of epoxide group and the mol ratio of amine compound is 2: 1-1: 1, reacted 2-5 hour down at 80-120 ℃, making it to react generation amination degree is the performed polymer that contains tertiary amine group of 50%-100% equivalence ratio;
(2) preparation contains the isocyanic ester of vinyl: the isocyanic ester that contains vinyl comprises the monoisocyanates that contains vinyl, or by the polyisocyanates and the α that contain the different isocyanato of active degree, the isocyanic ester that contains vinyl of β-vinyl unsaturated monocarboxylic hydroxy ester reaction gained, the isocyanato of polyisocyanates and α, the mol ratio of β-vinyl unsaturated monocarboxylic hydroxy ester is 1: 0.8-1: 1.5, under catalyst action, reacted 1-5 hour at 20-60 ℃;
(3) preparation water photosensitive resin: in containing the performed polymer of tertiary amine group, introduce vinyl, contain hydroxyl and the isocyanate reaction that contains vinyl in the performed polymer of tertiary amine group, in performed polymer, introduce the vinyl that can carry out the ultraviolet light polymerization reaction, the performed polymer that contains tertiary amine group is 1 with the mol ratio that contains the isocyanic ester of vinyl: 1-1: 6, under catalyst action, made water photosensitive resin in 2-5 hour 80-120 ℃ of reaction;
(4) preparation water photosensitive resin emulsion: in the prepared water photosensitive resin of step (3), add the light trigger of this resin quality than 1-4wt%, adding neutralizing agent acid and deionized water again, to be mixed with the pH value be 4.0-6.5, and resin solid content is the water photosensitive resin emulsion of 10-50wt%.
Beneficial effect of the present invention: the present invention has overcome the deficiencies in the prior art, a kind of performed polymer that contains tertiary amine group is provided, in performed polymer, introduce vinyl again by modification, and the ratio of introducing vinyl is controlled, make a kind of novel photosensitive resin, the outstanding feature of this photosensitive resin is water miscible, the water photosensitive resin emulsion that is mixed with by this photosensitive resin can be used for cathode electro-coating, UV-curable waterborne coatings and printing plate use photosensitive resin emulsion, and has satisfactory stability, the low temperature fast setting, advantages of environment protection.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not limited thereto.
Embodiment 1
1, contains the preparation of the performed polymer of tertiary amine group
In the reactor that thermometer, agitator and reflux exchanger are housed, add the 36g 1-Methoxy-2-propyl acetate, 36g (0.04mol) bisphenol A type epoxy resin E-20, add 8.5g (0.08mol) diethanolamine, carry out epoxy amine according to a conventional method and melt the ring reaction, be warmed up to 90 ℃, reacted 3-4 hour down at 90-100 ℃, just make amination Resins, epoxy (0.04mol).
2, the isocyanic ester that contains vinyl adopts methacrylic acid-2-isocyanato ethyl ester.
3, the preparation of photosensitive resin
Adding catalyzer 0.5wt% dibutyl tin laurate in synthetic amination Resins, epoxy slowly drips 31g (0.2mol) methacrylic acid-2-isocyanato ethyl esters down at 80 ℃, reacts to be warming up to 110 ℃ of insulations 0.5 hour after 3 hours, makes to react completely.
4, the preparation of water photosensitive resin emulsion
Add 2-hydroxy-2-methyl Propiophenone light trigger in photosensitive resin, its consumption is the 4.0wt% of resin, is 6.0 with the phosphoric acid pH value that neutralizes, and to be diluted to solid content with deionized water be 15%, obtains water photosensitive resin emulsion of the present invention through high speed dispersion.
Embodiment 2
1, contains the preparation of the performed polymer of tertiary amine group
With glycidyl methacrylate, methyl methacrylate, vinylbenzene, butyl methacrylate and 2-hydroxyethyl methacrylate are monomer mixture, consumption is respectively 20g, 15g, 12g, 18g and 10g, the dibenzoyl peroxide that accounts for monomer mixture quality 3wt% is dissolved in the above-mentioned monomer mixture, carry out Raolical polymerizable according to a conventional method, slowly splash at 100 ℃ of following monomers agitator is housed, reflux condensing tube, in the four-hole boiling flask of thermometer and 40g 1-Methoxy-2-propyl acetate, dropwised in 3 hours, insulation reaction 4 hours reaches more than 98% monomer conversion.Cool to 80 ℃ then, add the 15g diethanolamine, carry out epoxide group amination ring-opening reaction according to a conventional method, reacted 3-4 hour down, just make the acrylate prepolymer that contains tertiary amine group at 90-100 ℃.
2, contain the isocyanic ester preparation of vinyl
The molecule mol ratio be 1: 1 tolylene diisocyanate and 2-hydroxyethyl methacrylate under the katalysis of 0.5wt% dibutyl tin laurate, 50 ℃ of reactions 3 hours down generate the semiclosed tolylene diisocyanate of band vinyl.
3, the preparation of photosensitive resin
The semiclosed tolylene diisocyanate of 50g synthetic band vinyl is added drop-wise in the acrylate prepolymer that synthetic contains tertiary amine group, 80 ℃ down reaction be warming up to 110 ℃ of insulations 0.5 hour after 3 hours, make to react completely.
4, the preparation of water photosensitive resin emulsion
The adding mass ratio is 1: 1.5 a 1-methylcyclohexane benzophenone light trigger in acrylic resin modified, its consumption is the 1.0wt% of resin, through the acetate pH value that neutralizes is 6.0, and to be diluted to solid content with deionized water be 30%, obtains water photosensitive resin emulsion of the present invention through high speed dispersion.
Embodiment 3
Replace used 8.5g diethanolamine among the embodiment 1 with the 6.5g Monoethanolamine MEA BASF, all the other steps repeat the step of embodiment 1.
Embodiment 4
Replace used bisphenol A type epoxy resin E-20 among the embodiment 1 with 15g (0.04mol) bisphenol f type epoxy resin F830, all the other steps repeat the step of embodiment 1.
Embodiment 5
Replace used 15g diethanolamine among the embodiment 2 with the 11g Monoethanolamine MEA BASF, all the other steps repeat the step of embodiment 2.
Embodiment 6
Replace used methacrylic acid-2 hydroxyl ethyl ester among the embodiment 2 with vinylformic acid-2-hydroxyl ethyl ester, all the other steps repeat
The step of embodiment 2.
Embodiment 7
Replace used semiclosed tolylene diisocyanate among the embodiment 2 with methacrylic acid-2-isocyanato ethyl ester, all the other steps repeat the step of embodiment 2.
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 (8)
1. water photosensitive resin emulsion, it is characterized in that containing the performed polymer of epoxide group and amine compound melts the ring reaction by epoxy amine and makes the performed polymer that contains tertiary amine group, again with the isocyanate reaction modification that contains vinyl, in performed polymer, introduce the vinyl that can carry out the ultraviolet light polymerization reaction, and the ratio of introducing is controlled, make water photosensitive resin, add the light trigger of this resin quality than 1-4wt%, add neutralizing agent acid and deionized water again, be mixed with the photosensitive resin emulsion that resin solid content is 15-30wt%.
2. water photosensitive resin emulsion according to claim 1, it is characterized in that the described performed polymer that contains tertiary amine group, be to melt the ring reaction by performed polymer that contains epoxide group and amine compound by epoxy amine to make, the used performed polymer that contains epoxide group is the bisphenol A type epoxy resin of different molecular weight, bisphenol f type epoxy resin, or (methyl) glycidyl acrylate is acrylic resin modified; Used amine compound is one or more in diethylamine, dipropyl amine, dibutylamine, Monoethanolamine MEA BASF, diethanolamine, the Mono Methyl Ethanol Amine.
3. water photosensitive resin emulsion according to claim 1, it is characterized in that described photosensitive resin is made by performed polymer that contains tertiary amine group and the isocyanate reaction that contains vinyl, the performed polymer that contains tertiary amine group is 1 with the mol ratio that contains the isocyanic ester of vinyl: 1-1: 6.
4. water photosensitive resin emulsion according to claim 1 is characterized in that the described isocyanic ester that contains vinyl, comprises the monoisocyanates that contains vinyl: pseudoallyl-α, α-Er Jiajibianji isocyanic ester, methacrylic acid-2-isocyanato ethyl ester; Or contain the polyisocyanates and the α of the different isocyanato of active degree, β-vinyl unsaturated monocarboxylic hydroxy ester reaction gained α, β-semiclosed the isocyanic ester of vinyl unsaturated monocarboxylic hydroxy ester, polyisocyanates and α, the mol ratio of β-vinyl unsaturated monocarboxylic hydroxy ester is 1: 0.8-1: 1.5; Polyisocyanates is tolylene diisocyanate, isophorone diisocyanate, 2,6-two isocyanato methyl caproates, 2,2,4-trimethylammonium hexamethylene diisocyanate, Methylcyclohexyl diisocyanate or dimer acid diisocyanate; α, β-vinyl unsaturated monocarboxylic hydroxy ester are (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate or (methyl) vinylformic acid hydroxy butyl ester.
5. water photosensitive resin emulsion according to claim 1 is characterized in that described light trigger comprises one or more in benzophenone and derivative, benzophenone and derivative thereof, phenylbenzyl ketone and derivative thereof, methyl phenyl ketone and derivative thereof, Propiophenone and derivative thereof, st-yrax ethers and the derivative thereof.
6. water photosensitive resin emulsion according to claim 1, it is characterized in that described neutralizing agent acid is organic acid or mineral acid, organic acid: formic acid, acetate, lactic acid, propionic acid, butyric acid, methanesulfonic, ethane sulfonic acid, propane sulfonic acid, hydroxyethanesulfonic acid or hydroxypropanesulfonic acid, or mineral acid: hydrochloric acid, sulfuric acid, phosphoric acid; With the neutralizing agent acid for adjusting pH value to 4.0-6.5.
7. water photosensitive resin emulsion according to claim 2, it is characterized in that preparing used (methyl) glycidyl acrylate of the performed polymer that contains tertiary amine group acrylic resin modified is that acrylic ester monomer, other acrylic ester monomer of 30-70wt% and the copolymerization of 0-30wt% vinyl monomer by 5-20wt% (methyl) glycidyl acrylate, 10-30wt% hydroxyl forms.
8. the preparation method of the described water photosensitive resin emulsion of claim 1 is characterized in that may further comprise the steps:
(1) preparation contains the performed polymer of tertiary amine group: melt the ring reaction by performed polymer that contains epoxide group and amine compound by epoxy amine and make, containing the epoxide group in the performed polymer of epoxide group and the mol ratio of amine compound is 2: 1-1: 1, reacted 2-5 hour down at 80-120 ℃, making it to react generation amination degree is the performed polymer that contains tertiary amine group of 50%-100% equivalence ratio;
(2) preparation contains the isocyanic ester of vinyl: the isocyanic ester that contains vinyl comprises the monoisocyanates that contains vinyl, or by the polyisocyanates and the α that contain the different isocyanato of active degree, the isocyanic ester that contains vinyl of β-vinyl unsaturated monocarboxylic hydroxy ester reaction gained, the isocyanato of polyisocyanates and α, the mol ratio of β-vinyl unsaturated monocarboxylic hydroxy ester is 1: 0.8-1: 1.5, under catalyst action, reacted 1-5 hour at 20-60 ℃;
(3) preparation water photosensitive resin: in containing the performed polymer of tertiary amine group, introduce vinyl, contain hydroxyl and the isocyanate reaction that contains vinyl in the performed polymer of tertiary amine group, in performed polymer, introduce the vinyl that can carry out the ultraviolet light polymerization reaction, the performed polymer that contains tertiary amine group is 1 with the mol ratio that contains the isocyanic ester of vinyl: 1-1: 6, under catalyst action, made water photosensitive resin in 2-5 hour 80-120 ℃ of reaction;
(4) preparation water photosensitive resin emulsion: in the prepared water photosensitive resin of step (3), add the light trigger of this resin quality than 1-4wt%, adding neutralizing agent acid and deionized water again, to be mixed with the pH value be 4.0-6.5, and resin solid content is the water photosensitive resin emulsion of 10-50wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100943459A CN1309754C (en) | 2005-09-10 | 2005-09-10 | Water photosensitive resin emulsion and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100943459A CN1309754C (en) | 2005-09-10 | 2005-09-10 | Water photosensitive resin emulsion and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1746204A CN1746204A (en) | 2006-03-15 |
| CN1309754C true CN1309754C (en) | 2007-04-11 |
Family
ID=36165939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100943459A Expired - Fee Related CN1309754C (en) | 2005-09-10 | 2005-09-10 | Water photosensitive resin emulsion and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1309754C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010248297A (en) * | 2009-04-10 | 2010-11-04 | Taiyo Ink Mfg Ltd | Photocurable resin and photocurable resin composition |
| CN102432795B (en) * | 2011-08-30 | 2013-07-24 | 华南理工大学 | Sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion and its preparation method |
| CN106188496B (en) * | 2016-07-16 | 2018-07-27 | 北京化工大学 | A kind of dimer acid modified epoxy acrylate photopolymerization resin lotion and preparation method thereof |
| US10479862B2 (en) * | 2017-12-07 | 2019-11-19 | Covestro Llc | Amine based polymer polyol stabilizers |
| CN110358068A (en) * | 2018-04-11 | 2019-10-22 | 蓝思科技（长沙）有限公司 | A kind of ultraviolet curing prepolymer, preparation method and UV glass protection ink |
| CN112391095B (en) * | 2020-11-17 | 2022-03-18 | 江南大学 | Photo-curing epoxy acrylate cathode electrophoretic coating and preparation and application thereof |
| CN113603850B (en) * | 2021-08-31 | 2023-04-28 | 武汉中科先进材料科技有限公司 | High-wear-resistance hydrophilic resin, high-wear-resistance solvent-free anti-fog coating, and preparation method and application thereof |
| CN115160511B (en) * | 2022-07-14 | 2024-03-26 | 无锡洪汇新材料科技股份有限公司 | Hydroxyl-containing aqueous resin dispersion and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033389A (en) * | 1987-11-30 | 1989-06-14 | 太阳油墨制造株式会社 | Photosensitive thermosetting resin composition and method for forming solder resist pattern using the same |
| CN1128362A (en) * | 1994-11-15 | 1996-08-07 | 赫司特日本有限公司 | Photosensitive resin composition |
| CN1148187A (en) * | 1996-08-28 | 1997-04-23 | 南亚塑胶工业股份有限公司 | Photosensitive resin compound |
| CN1223727A (en) * | 1996-06-28 | 1999-07-21 | 西巴特殊化学品控股有限公司 | Photopolymerizable thermosetting resin composition |
-
2005
- 2005-09-10 CN CNB2005100943459A patent/CN1309754C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033389A (en) * | 1987-11-30 | 1989-06-14 | 太阳油墨制造株式会社 | Photosensitive thermosetting resin composition and method for forming solder resist pattern using the same |
| CN1128362A (en) * | 1994-11-15 | 1996-08-07 | 赫司特日本有限公司 | Photosensitive resin composition |
| CN1223727A (en) * | 1996-06-28 | 1999-07-21 | 西巴特殊化学品控股有限公司 | Photopolymerizable thermosetting resin composition |
| CN1148187A (en) * | 1996-08-28 | 1997-04-23 | 南亚塑胶工业股份有限公司 | Photosensitive resin compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1746204A (en) | 2006-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1218981C (en) | Acrylic polyurethane copolymer emulsion, its preparation method and use | |
| CN110128773A (en) | A kind of method and products thereof of optical and thermal dual cure 3D printing | |
| CN101037497A (en) | Preparation method of special epoxy resin for aqueous ultraviolet solidifying coating | |
| CN1309754C (en) | Water photosensitive resin emulsion and preparation thereof | |
| CN107189032B (en) | Multifunctional UV (ultraviolet) curing polyurethane vegetable oleate prepolymer and preparation method and application thereof | |
| DE19627469A1 (en) | Epoxy resin crosslinking agent and one-component epoxy resin composition | |
| CN112831247A (en) | High-toughness low-temperature curing powder coating and preparation method and application thereof | |
| JP2007046062A (en) | Polyacrylic hydrazide and crosslinking or curing agent for resin | |
| CN101397364A (en) | Method for preparing air drying epoxy vinyl ester resin | |
| CN102898615A (en) | Method for modification of waterborne polyurethane by using epoxy resin | |
| CN111944409A (en) | Water-based two-component polyurethane coating and preparation method thereof | |
| CN1091457C (en) | Ultraviolet cured paint | |
| CN1432030A (en) | Aqueous coating compsn. | |
| CN1710002A (en) | Water-based polyurethane resin and its electrophoretic paint composition and preparing method | |
| CN102993405A (en) | Epoxy resin modified waterborne polyurethane | |
| CN112794982A (en) | Polyurethane acrylate and preparation method and application thereof | |
| CN116444802B (en) | Lignin-acrylic ester water dispersion and preparation method and application thereof | |
| CN117603180A (en) | Preparation of multi-functionality cyclic carbonate and application of multi-functionality cyclic carbonate in epoxy adhesive | |
| CN114591492B (en) | Water-based epoxy curing agent and preparation method and application thereof | |
| CN115433482A (en) | Preparation method of water-resistant coating of water-based polyurethane | |
| DE4222256A1 (en) | Aqueous coating agent and its use | |
| CN1473863A (en) | Process for preparing water dispersion of crosslinking vinyl resin/polyurethane hybrid resin | |
| CN116135935B (en) | High-storage-stability room-temperature self-curing aqueous polyurethane for concrete protection and preparation method thereof | |
| CN116218310B (en) | Silica sol modified acrylic acid anticorrosive paint and preparation method thereof | |
| CN113174025B (en) | Phosphate functional monomer modified waterborne polyurethane composite emulsion and preparation method thereof |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Wuxi Ed adhesive material Co., Ltd. Assignor: Jiangnan University Contract fulfillment period: 2008.11.14 to 2013.11.13 contract change Contract record no.: 2008320001117 Denomination of invention: Water photosensitive resin emulsion and preparation thereof Granted publication date: 20070411 License type: Exclusive license Record date: 2008.12.8 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.11.14 TO 2013.11.13; CHANGE OF CONTRACT Name of requester: WUXI AIDE ADHESIVE MATERIALS CO., LTD. Effective date: 20081208 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070411 Termination date: 20100910 |