CN104448172A - Photosensitive waterborne acrylic acid-polyurethane dispersion and coating thereof - Google Patents
Photosensitive waterborne acrylic acid-polyurethane dispersion and coating thereof Download PDFInfo
- Publication number
- CN104448172A CN104448172A CN201410790707.7A CN201410790707A CN104448172A CN 104448172 A CN104448172 A CN 104448172A CN 201410790707 A CN201410790707 A CN 201410790707A CN 104448172 A CN104448172 A CN 104448172A
- Authority
- CN
- China
- Prior art keywords
- acrylic acid
- photosensitivity
- water soluble
- polyurethane dispersions
- resin
- 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
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a photosensitive waterborne acrylic acid-polyurethane dispersion. The preparation method comprises the following steps: firstly, carrying out free radical polymerization on an acrylic monomer and a hydroxyl acrylate monomer, so as to prepare hydroxyl acrylic resin; reacting with an isocyanate monomer by adopting unsaturated polyester polyols, so as to synthesize an isocyanate polyurethane prepolymer; carrying out blocking by using the hydroxyl acrylic resin; and finally neutralizing, and adding water to disperse, so as to prepare the photosensitive waterborne acrylic acid-polyurethane dispersion. According to the resin synthesized by the method, the advantages of acrylic acid and polyurethane resin are combined; the molecular weight of the resin and the photocuring reaction speed are improved; a photocuring coating can be prepared from the resin prepared by the method matched with water-based color paste and an initiator; and the coating disclosed by the invention is applied to the industries of buildings and home decoration.
Description
Technical field
The present invention relates to a kind of water soluble acrylic acid-polyurethane hybrid modification technology, particularly a kind of photosensitivity water soluble acrylic acid-polyurethane dispersions obtained with hybrid modification technology, and coating.
Background technology
Photo-cured coating is a kind of environment-friendly type energy-saving coating developed by Bayer A.G late 1960s.China enters photo-cured coating field from the eighties in 20th century.In recent years along with the enhancing of people's energy-conserving and environment-protective consciousness, photo-cured coating varieties and characteristics constantly strengthens, and Application Areas is constantly expanded, and output increases fast, presents swift and violent growth momentum.Photocuring product has been-the energy-conservation and clean and environment-friendly technology of item at electron trade photocuring technology; its save energy---energy consumption is only 1/5th of thermofixation; and containing solvent, have provide protection to ecotope; to airborne release poison gas and carbonic acid gas, therefore can not be described as " green technology ".Photocuring technology (UV) is the UV-irradiation by certain wavelength, makes liquid epoxy acrylic resin high speed of polymerization form solid-state a kind of light complete processing, and photocuring reaction is light-initiated polymerization, crosslinking reaction in essence.Photo-cured coating is the example the earliest of photocuring technology industrially extensive successful Application, is also the maximum product of current photocuring industrial field volume of production and marketing.
Chinese utility model patent ZL201320312949.6 provides a kind of ultraviolet light polymerization floor, comprise substrate layer, ultraviolet light polymerization laser film, ultraviolet cured primer layer and UV-curable finish coat layer, wherein substrate layer is provided with ultraviolet light polymerization laser film described in one deck, above laser film, scribbles ultraviolet cured primer layer and UV-curable finish coat layer successively.
Chinese utility model patent ZL 201320077080.1 provides a kind of UVS photocuring heat-insulating decorative composite board mounting structure and installs anchoring piece.Anchoring piece comprises mounting seat and insertion portion, and mounting seat and insertion portion are all positioned on connection piece, mounting seat has installation datum hole, and mounting seat and insertion portion are positioned at two ends of connection piece.Also comprise UVS photocuring heat-insulating decorative composite board, the side that insertion portion inserts UVS photocuring heat-insulating decorative composite board is fixed.Metope has the installation adjacent to each other of more than one UVS photocuring heat-insulating decorative composite board form insulation and decoration layer, insertion portion inserts in the steam pressure fortifying fibre cement laminates of next-door neighbour's fluorine carbon photocuring finish coat.The problem that new mounting structure solves anchoring piece damage core, loosens, is shifted in core, improves installation stability, extends the kind of UVS photocuring heat-insulating decorative composite board core, be applicable to various core; Improve workman's installation effectiveness.
Summary of the invention
It is high that one object of the present invention is to provide a kind of percentage of grafting, the photosensitivity water soluble acrylic acid-polyurethane dispersions of excellent performance.
Another object of the present invention is to provide a kind of photosensitivity water soluble acrylic acid-polyurethane dispersions, and this resin is equipped with suitable initiator can under UV-irradiation, fast drying excellent performance.
Another object of the present invention is to provide a kind of UV curable waterborne coatings, is applicable to metal, plastics and glass substrate, and rate of drying is fast, excellent performance.
The present invention's polymerization technique used belongs to the general operation technical ability that those of ordinary skill in the art should possess, also can according to " coating process (third edition) " (coating process editorial committee volume, Chemical Industry Press, 1997) guidance of a book prepares.
A kind of photosensitivity water soluble acrylic acid-polyurethane dispersions resin provided by the invention, its preparation process is as follows:
Step one: by weight, by 60-65 part hydroxyl terminated unsaturated polyester, 20-25 part polyisocynate monomer and 5-10 part hydrophilic monomer and solvent (as: acetone) and catalyzer (as: dibutyl tin laurate) blended, reaction generates the urethane resin of end NCO, and demarcation isocyanate group (NCO) value is 5% is reaction end;
Step 2: under solvent (as: acetone) condition, by acrylic ester monomer by free radical synthesizing propylene acid resin, wherein hydroxy acrylate class monomer accounts for 15-25 weight part;
Step 3: step one and resin synthesized by step 2 are pressed usage ratio 1: 1 mixed grafting, then neutralization also thin up, makes photosensitivity water soluble acrylic acid-polyurethane dispersions.
The preparation method of photosensitivity water soluble acrylic acid-polyurethane dispersions resin provided by the invention, the concrete method of its step one as: vacuumize after hydroxyl terminated unsaturated polyester and hydrophilic monomer bottoming, temperature 105 DEG C-112 DEG C, pressure-0.06Mpa, 1 hour time, add N-Methyl pyrrolidone (NMP) and dissolve hydrophilic monomer, temperature is down to 60 DEG C, start to drip isophorone diisocyanate (IPDI), within 1 hour, drip off; Adding dibutyl tin laurate is catalyzer, and 60 DEG C of insulation 1h, are warmed up to 70 DEG C, are incubated 4 hours, add acetone diluted, be terminal when nco value is 5% according to viscosity situation.
The preparation method of photosensitivity water soluble acrylic acid-polyurethane dispersions resin provided by the invention, the concrete method of its step 2 as: add acetone in reaction vessel, mix, use nitrogen replacement air, acrylic ester monomer (as: but being not limited only to MMA, BA, MAA and HEMA etc.) and Diisopropyl azodicarboxylate are added dropwise to container for 50-100: 1 mixture formed in mass ratio, within 4 hours, dropwise; Keep temperature of reaction 80 DEG C-90 DEG C, 2 hours, then add a small amount of Diisopropyl azodicarboxylate and acetone, and to measure hydroxyl value be 60mgKOH/g-70mgKOH/g, be terminal.
The preparation method of photosensitivity water soluble acrylic acid-polyurethane dispersions resin provided by the invention, hydroxyl terminated unsaturated polyester used such as: model is the unsaturated polyesters such as 191,193,195,118 and 138.These resins are used alone or as a mixture and are applied to the present invention.
The preparation method of photosensitivity water soluble acrylic acid-polyurethane dispersions resin provided by the invention, polyisocynate monomer used as: but be not limited only to tolylene diisocyanate, isoflurane chalcone diisocyanate and '-diphenylmethane diisocyanate etc.These monomers are used alone or as a mixture and are applied to the present invention.
The preparation method of photosensitivity water soluble acrylic acid-polyurethane dispersions resin provided by the invention, hydrophilic monomer used is for containing hydroxyl or carboxyl, there is wetting ability, molecular weight is the organic micromolecule compound of 150-250, as: but be not limited only to dimethylol propionic acid, dimethylolpropionic acid, propylene glycol and ethohexadiol etc.These organic molecules are used alone or as a mixture and are applied to the present invention.
The preparation method of photosensitivity water soluble acrylic acid-polyurethane dispersions resin provided by the invention, acrylic monomer used comprises oh type acrylic monomer, and carboxyl type acrylic monomer.Oh type acrylic ester monomer is as Propylene glycol monoacrylate, hy-droxybutyl and Hydroxyethyl acrylate etc.These monomers are used alone or as a mixture and are applied to the present invention.
The preparation method of photosensitivity water soluble acrylic acid-polyurethane dispersions resin provided by the invention, carboxyl type acrylic monomer used as: but be not limited only to vinylformic acid and methacrylic acid etc.These monomers are used alone or as a mixture and are applied to the present invention.
The preparation method of photosensitivity water soluble acrylic acid-polyurethane dispersions resin provided by the invention, neutralizing agent used as: but be not limited only to triethylamine and N, N-dimethylethanolamine etc.These monomers are used alone or as a mixture and are applied to the present invention.
Photosensitivity water soluble acrylic acid-the polyurethane dispersions of gained of the present invention, the coating be equipped with made by suitable mill base and light trigger can be used for metal rust preventing and glass decoration.
The beneficial effect that technical solution of the present invention realizes:
The preparation method of photosensitivity water soluble acrylic acid-polyurethane dispersions resin provided by the invention, hybrid form improves molecular resin amount, makes it alleviate string stress to a certain extent being light-cured in membrane process.
The preparation method of photosensitivity water soluble acrylic acid-polyurethane dispersions resin provided by the invention, molecular weight and the intensity of urethane resin can be improved, the introducing of esters of acrylic acid group improves the snappiness of acrylic resin, particularly low temperature brittleness, over-all properties is also improved, is improved in the sticking power and hardness of metal and glass substrate.
Embodiment
Below describe technical scheme of the present invention in detail.The embodiment of the present invention is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
If the present invention's reagent used does not clearly indicate, then use technical grade.
Embodiment
Step one: as table 1 is filled a prescription, by unsaturated polyester, dimethylol propionic acid, vacuumizes after ethohexadiol bottoming, temperature 105 DEG C-112 DEG C, pressure-0.06Mpa, time 1h, and add NMP and dissolve small molecule monomer, temperature is down to 60 DEG C, and start to drip IPDI, 1h drips off; Adding dibutyl tin laurate is catalyzer, and 60 DEG C of insulation 1h, are warmed up to 70 DEG C, are incubated four hours, add acetone diluted, be terminal when nco value is 5% according to viscosity situation;
Step 2: as table 2 is filled a prescription, add acetone in reaction vessel to mix, use nitrogen replacement air, the mixture be made up of the Acrylic Acid Monomers such as MMA, BA, MAA and HEMA and Diisopropyl azodicarboxylate is added dropwise to container, and about 4h dropwises, and keeps temperature of reaction 80 DEG C-90 DEG C, 2h, then add a small amount of Diisopropyl azodicarboxylate and acetone, and to measure hydroxyl value be 60mgKOH/g-70mgKOH/g, be terminal;
Step 3: step one and resin synthesized by step 2 are pressed usage ratio 1: 1 mixed grafting, then neutralization also thin up, make photosensitivity water soluble acrylic acid-polyurethane dispersions, take glass as ground, gained paint film property is in table 3.
Table 1
Table 2
Table 3 photosensitivity water soluble acrylic acid-polyurethane dispersions performance
Claims (10)
1. photosensitivity water soluble acrylic acid-polyurethane dispersions resin, is characterized in that preparing as follows:
Step one: by weight, by 45-65 part hydroxyl terminated unsaturated polyester, 20-25 part polyisocynate monomer and 10-25 part hydrophilic monomer and solvent and catalyzer blended, reaction generates the urethane resin of end NCO, and to demarcate nco value be 5% is reaction end;
Step 2: under solvent condition, by acrylic ester monomer by free radical synthesizing propylene acid resin, wherein hydroxy acrylate class monomer accounts for 15-25 weight part;
Step 3: step one and the resin synthesized by step 2 are pressed usage ratio 1: 1 mixed grafting, then neutralization also thin up, makes photosensitivity water soluble acrylic acid-polyurethane dispersions.
2. photosensitivity water soluble acrylic acid-polyurethane dispersions resin according to claim 1, is characterized in that described hydroxyl terminated unsaturated polyester is selected from a kind of several unsaturated polyester that model is 191,193,195,118 and 138.
3. photosensitivity water soluble acrylic acid-polyurethane dispersions resin according to claim 1, is characterized in that described lipid acid is selected from one or more of tolylene diisocyanate, isophorone diisocyanate and '-diphenylmethane diisocyanate.
4. photosensitivity water soluble acrylic acid-polyurethane dispersions resin according to claim 1, is characterized in that described hydrophilic monomer is selected from one or more of dimethylol propionic acid, dimethylolpropionic acid, propylene glycol and ethohexadiol.
5. photosensitivity water soluble acrylic acid-polyurethane dispersions resin according to claim 1, is characterized in that described oh type acrylic ester monomer is selected from one or more of Propylene glycol monoacrylate, hy-droxybutyl and Hydroxyethyl acrylate.
6. photosensitivity water soluble acrylic acid-polyurethane dispersions resin according to claim 1, is characterized in that described neutralizing agent is selected from one or more of triethylamine and N, N-dimethylethanolamine.
7. photosensitivity water soluble acrylic acid-polyurethane dispersions resin according to claim 1, it is characterized in that described step one is: vacuumize after described hydroxyl terminated unsaturated polyester and hydrophilic monomer bottoming, temperature 105 DEG C-112 DEG C, pressure-0.06Mpa, 1 hour time, add NMP and dissolve hydrophilic monomer, temperature is down to 60 DEG C, start to drip IPDI, within 1 hour, drip off; Adding dibutyl tin laurate is catalyzer, and 60 DEG C of insulation 1h, are warmed up to 70 DEG C, are incubated 4 hours, add acetone diluted, be terminal when nco value is 5% according to viscosity situation.
8. photosensitivity water soluble acrylic acid-polyurethane dispersions resin according to claim 1, it is characterized in that described step 2 is: in reaction vessel, add acetone, mix, use nitrogen replacement air, acrylic ester monomer and Diisopropyl azodicarboxylate are added dropwise to container for 50-100: 1 mixture formed in mass ratio, within 4 hours, dropwise; Keep temperature of reaction 80 DEG C-90 DEG C, 2 hours, then add a small amount of Diisopropyl azodicarboxylate and acetone, and to measure hydroxyl value be 60mgKOH/g-70mgKOH/g, be terminal.
9. alkyd acrylate resin according to claim 1, is characterized in that described organic solvent is selected from toluene, dimethylbenzene, ethyl acetate, butylacetate, butanone, pimelinketone, one of Virahol and propylene glycol ethers kind or several.
10. a coating, comprises photosensitivity according to claim 1 water soluble acrylic acid-polyurethane dispersions resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410790707.7A CN104448172A (en) | 2014-12-18 | 2014-12-18 | Photosensitive waterborne acrylic acid-polyurethane dispersion and coating thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410790707.7A CN104448172A (en) | 2014-12-18 | 2014-12-18 | Photosensitive waterborne acrylic acid-polyurethane dispersion and coating thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104448172A true CN104448172A (en) | 2015-03-25 |
Family
ID=52894971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410790707.7A Pending CN104448172A (en) | 2014-12-18 | 2014-12-18 | Photosensitive waterborne acrylic acid-polyurethane dispersion and coating thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104448172A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017161607A1 (en) * | 2016-03-24 | 2017-09-28 | 万华化学集团股份有限公司 | Waterborne radiation curing urethane acrylate composition, preparation method therefor and coating |
| CN107674149A (en) * | 2017-09-23 | 2018-02-09 | 江山海维科技有限公司 | A kind of preparation method of polyfunctionality acrylate containing strontium for photosensitive resin |
| CN109942772A (en) * | 2019-04-04 | 2019-06-28 | 深圳职业技术学院 | A kind of preparation method of the UV-Curing Waterborne Resin of adjustable degree of functionality |
| CN111087549A (en) * | 2019-12-31 | 2020-05-01 | 惠州市安品新材料有限公司 | Waterborne polyurethane resin, coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775106A (en) * | 2010-02-03 | 2010-07-14 | 江苏柏鹤涂料有限公司 | Waterborne acrylic ester-polyurethane resin emulsion and application thereof |
| CN101397363B (en) * | 2008-08-19 | 2012-01-04 | 东莞市佳景印刷材料有限公司 | Water ultraviolet light curing epoxy acrylic ester grafted polyurethane and preparation method thereof |
| CN103059316A (en) * | 2012-12-31 | 2013-04-24 | 中科院广州化学有限公司 | Polyurethane/polyacrylate copolymer modified by organic fluoride and ultraviolet curing coating prepared by polyurethane/polyacrylate copolymer |
-
2014
- 2014-12-18 CN CN201410790707.7A patent/CN104448172A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397363B (en) * | 2008-08-19 | 2012-01-04 | 东莞市佳景印刷材料有限公司 | Water ultraviolet light curing epoxy acrylic ester grafted polyurethane and preparation method thereof |
| CN101775106A (en) * | 2010-02-03 | 2010-07-14 | 江苏柏鹤涂料有限公司 | Waterborne acrylic ester-polyurethane resin emulsion and application thereof |
| CN103059316A (en) * | 2012-12-31 | 2013-04-24 | 中科院广州化学有限公司 | Polyurethane/polyacrylate copolymer modified by organic fluoride and ultraviolet curing coating prepared by polyurethane/polyacrylate copolymer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017161607A1 (en) * | 2016-03-24 | 2017-09-28 | 万华化学集团股份有限公司 | Waterborne radiation curing urethane acrylate composition, preparation method therefor and coating |
| CN107674149A (en) * | 2017-09-23 | 2018-02-09 | 江山海维科技有限公司 | A kind of preparation method of polyfunctionality acrylate containing strontium for photosensitive resin |
| CN109942772A (en) * | 2019-04-04 | 2019-06-28 | 深圳职业技术学院 | A kind of preparation method of the UV-Curing Waterborne Resin of adjustable degree of functionality |
| CN109942772B (en) * | 2019-04-04 | 2021-05-18 | 深圳职业技术学院 | Preparation method of ultraviolet curing water-based resin with adjustable functionality |
| CN111087549A (en) * | 2019-12-31 | 2020-05-01 | 惠州市安品新材料有限公司 | Waterborne polyurethane resin, coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106854432B (en) | A kind of radiation solidified aqueous coating resin and preparation method thereof | |
| EP2809696B1 (en) | Polymer, process and composition | |
| CN103232585B (en) | A kind of preparation method of polyfunctionality polyurethane acrylic ester water UV resin | |
| CN104559741B (en) | UV (ultraviolet) finishing varnish for laser roller coating | |
| CN103130977B (en) | Polyurethane polyol dispersion of a kind of aqueous wood lacquer with double components and preparation method thereof | |
| CN109467647B (en) | High-water-resistance high-alcohol-resistance water-based acrylic modified polyurethane resin and synthesis method thereof | |
| CN104448172A (en) | Photosensitive waterborne acrylic acid-polyurethane dispersion and coating thereof | |
| US20090324843A1 (en) | Process for producing multicoat color and/or effect paint systems | |
| US20190343755A1 (en) | Nail polish composition based on solvent-free aqueous polyurethane dispersions | |
| CN103214653A (en) | Ultraviolet cured waterborne polyurethane surface-coating resin and preparation method and application thereof | |
| CN103589324B (en) | The anti-scratch matte varnish of a kind of UV | |
| CN103333314A (en) | Cation photocuring fluorinated polyurethane resin and preparation method thereof | |
| CN109486384A (en) | A kind of polyurea type Polyaspartic Ester-Based Coatings feedstock composition, from its coating and its preparation method and application | |
| CN114854303A (en) | High-performance water-based bi-component UV dual-curing quick-drying type finishing varnish coating and application thereof | |
| CN103666179A (en) | VOC (volatile organic compound)-free epoxy modified water-borne PU (polyurethane) finish paint and preparation method thereof | |
| CN107151306B (en) | Hydrolysis-resistant polyester resin capable of being cured by UV and preparation method thereof | |
| CN102432795B (en) | Sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion and its preparation method | |
| CN114058208B (en) | UV (ultraviolet) silk-screen printing ink for baking varnish surface and preparation method thereof | |
| CN105153926A (en) | Solvent-free type ultraviolet (UV) photocuring texture paint and preparation and use method thereof | |
| CN109294433B (en) | Low-VOC (volatile organic compound) automobile varnish and preparation method thereof | |
| CN114736580A (en) | Water-based release adhesive and preparation method and application thereof | |
| CN110669427A (en) | Two-component water-based UV coating, preparation method and application thereof, and coating piece | |
| CN103214652B (en) | Ultraviolet cured waterborne polyurethane acrylate vacuum coating base-coating resin | |
| CN105153777A (en) | Solvent-free type ultraviolet (UV) photocuring water drop paint and preparation and use method thereof | |
| CN101787241A (en) | Water-based UV-light curing coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150325 |