CN101870756A - Ultraviolet-cured fluorine-containing aqueous urethane acrylate and preparation method thereof - Google Patents
Ultraviolet-cured fluorine-containing aqueous urethane acrylate and preparation method thereof Download PDFInfo
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- CN101870756A CN101870756A CN200910135090A CN200910135090A CN101870756A CN 101870756 A CN101870756 A CN 101870756A CN 200910135090 A CN200910135090 A CN 200910135090A CN 200910135090 A CN200910135090 A CN 200910135090A CN 101870756 A CN101870756 A CN 101870756A
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Abstract
The invention relates to ultraviolet-cured fluorine-containing aqueous urethane acrylate and a preparation method thereof. The invention is characterized by: introducing a fluorine-containing monomer into the system by using the self-emulsion action of an aqueous urethane acrylate macromolecular monomer to prepare fluorine-containing aqueous urethane acrylate composite emulsion; and adding a photoinitiator into the composite emulsion and curing the emulsion in ultraviolet to form a film, namely an aqueous urethane acrylate coating with excellent performance such as water resistance, solvent resistance and weather resistance.
Description
Technical field
The present invention is that the excellent properties with the advantage of ultraviolet light solidfication water polyurethane acrylate and fluorochemical combines, and the photocuring aqueous polyurethane of preparation water tolerance, solvent resistance, weathering resistance, the contour performance of resistance to crocking belongs to chemical technology field.
Background technology
Over nearly 30 years, owing to the restriction of various countries' environmental regulation to volatile organic matter (VOC, Volatile Organic Compound), UV-curing technology has worldwide obtained developing rapidly.UV-curing technology is a kind of new technology of efficient, energy-conservation and environmental protection, after the sixties in 20th century, Germany Bayer company developed first-generation ultraviolet-curing paint, keep development fast always, be widely used in coating, printing ink, tackiness agent, weaving, printed-wiring board (PWB), information technology and biomedical sector at present.
The ultraviolet light polymerization system is divided into two kinds of solvent-borne type and water-baseds usually.Wherein, the aqueous photo-curing system combines the advantage of UV-curing technology and water-borne coatings both techniques, is the new developing direction of UV-curing technology.Its principal feature is: curing speed is fast, and equipment is simple, cost is low, and the energy is saved in ambient cure; Water is cooked thinner environmental protection more; Water is the cheap medium of safety, and is nonflammable, uses safer; Water-based system can more convenient adjusting rheological; Be applicable to that various coating methods (spraying, roller coat, brushing etc.) and equipment are easy to clean; Film and possess high rigidity and high tenacity, excellent property simultaneously.Therefore, the UV-curable waterborne technology obtains wide development.
Aqueous polyurethane acrylate is as aqueous photo-curing architectural study and one of matrix resin that is most widely used, it has excellent hardness, snappiness, cementability and wear resisting property, and these performances can be adjusted in broad range flexibly, and therefore the application at aspects such as coating, printing ink, tamanori and hide finishess enjoys attention.But ultraviolet light solidfication water polyurethane also has many shortcomings that are difficult to overcome, and for example: performances such as the water tolerance of filming, solvent resistance and mechanical property are poorer slightly than conventional solvent type light-cured resin, remains further to be improved.
Fluorochemicals has characteristics such as excellent chemical stability, water and oil repellant, is widely used in fields such as coating, textile auxiliary agent, sizing agent, decorative leather agent.The present invention combines fluorocarbon material and photocuring aqueous polyurethane acrylate; being about to fluorochemicals introduces in the photocuring aqueous polyurethane system; utilize the excellent properties of fluorochemical to improve performances such as the water tolerance of photocuring aqueous polyurethane, anti-solvent, weathering resistance, didirtresistance; obtain high performance ultraviolet-cured fluorine-containing aqueous urethane resin, can be used for fields such as optical fiber coatings, electronic component protective cover, package coating, car paint, building coating.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high performance photo-cured fluorine-containing aqueous polyurethane acrylate.The characteristic of the self-emulsifying of the aqueous polyurethane acrylate of the two keys of present method utilization band is introduced the acrylate containing fluorine monomer in the photocuring aqueous polyurethane system, adds light trigger again, film-forming under UV-irradiation.Present method provides a kind of new thinking and technology for fields such as coating, papermaking, weaving, tackiness agents.
For achieving the above object, the present invention takes following measure, a kind of preparation method of ultraviolet-cured fluorine-containing aqueous urethane acrylate, and its proportioning is:
A fluorine-containing (methyl) acrylic ester monomer 0.5-50wt%
B aqueous polyurethane acrylate macromonomer 10-80wt%
C (methyl) acrylic ester monomer 0-20wt%
D light trigger 0.01-1.5wt%
E water 15-80wt%
Its preparation method is: under the room temperature condition; aqueous polyurethane acrylate macromonomer, water are added mixing in the reaction flask; under nitrogen protection, vigorous stirring 0.5-2 hour, add (methyl) acrylic ester monomer; stirred 0.5-2 hour; add fluorine-containing (methyl) acrylic ester monomer, continued vigorous stirring 0.5-3 hour, add light trigger; stirred 0.5-1 hour, then film-forming under UV-irradiation.
A monomer among the present invention is selected at least a C for use
2-C
18Fluorine-containing (methyl) acrylic ester monomer, be preferably C
5-C
16Fluorine-containing (methyl) acrylic ester monomer.As: vinylformic acid hexafluoro butyl ester, Perfluorocaprylic Acid methacryloxy ethyl ester etc.
C monomer among the present invention is selected at least a methacrylic monomer or acrylic ester monomer for use, preferred methacrylate class monomer.As: methyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester etc.
Light trigger D among the present invention selects at least a oil soluble light trigger or water-soluble light trigger for use, preferably water dissolubility light trigger, as: Irgacure 2959[2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl phenyl ketone].
The monomeric preparation method of B among the present invention: in reaction flask, add solvent, polyisocyanates monomer, polyalcohols monomer, the polyvalent alcohol that contains carboxyl or tertiary amine groups or polynary amine monomer, logical nitrogen 30 minutes is warmed up to 65-90 ℃, reacts 5-8 hour.Cool to 50 ℃, drip (methyl) acrylic acid hydroxy alkyl ester class monomer, reacted 6-10 hour, make the aqueous polyurethane acrylate macromonomer of the two keys of terminal band.
Polyisocyanates monomer among the present invention, can be aliphatic polyisocyante, as: a kind of in isophorone diisocyanate, hexamethylene-diisocyanate, tetramethylene diisocyanate, dimethylene diisocyanate, the methylcyclohexane diisocyanate; Also can be aromatic polyisocyanate, as: a kind of in tolylene diisocyanate, diphenylmethanediisocyanate, phenylene diisocyanate, biphenyl diisocyanate, the naphthalene diisocyanate.
Polyalcohols monomer among the present invention can be a polyether glycol, as: polyoxyethylene glycol, Viscotrol C, polypropylene glycol, polytetrahydrofuran diol, polyoxyethylene-propylene oxide glycol etc.Also can be polyester polyol, as: polyethylene glycol adipate, polypropylene adipate (PPA), poly adipate succinic acid ester, polybutene diacid glycol ester; Or the small molecules polyvalent alcohol, as: ethylene glycol, glycol ether, butyleneglycol etc.Polyvalent alcohol and polyisocyanates are preparation polyurethane macromolecular monomeric main ingredients, and its amount ratio decide by required soft durometer of filming, but all should guarantee-NCO is excessive, with the generation end group are-performed polymer of NCO.
For making the polyurethane macromolecular monomer that certain wetting ability be arranged, also need introduce the polyvalent alcohol or the polyamine compound of hydrophilic radicals such as containing carboxyl or uncle's amino, as: dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, 2,3-dimethylolpropionic acid, methyldiethanolamine, ethyldiethanolamine etc.
(methyl) acrylic acid hydroxy alkyl ester class monomer among the present invention can be hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate etc.
Solvent among the present invention is the solvent that dissolves each other with water, can be N-Methyl pyrrolidone, N, dinethylformamide, acetone, tetrahydrofuran (THF) etc.
One of advantage of the present invention is the excellent performances such as water tolerance, solvent resistance, weathering resistance, resistance to crocking of the fluorine-containing aqueous polyurethane acrylate of preparation.
Two of advantage of the present invention is to utilize the characteristics of urethane acrylate macromonomer self-emulsifying, fluorochemical monomer is introduced in the aqueous polyurethane acrylate resin system, here the urethane acrylate macromole had both been made reaction monomers, make emulsifying agent again, avoided adding the influence of emulsifying agent resin property.
Three of advantage of the present invention is after adding fluorochemical monomer, and the ratio of regulating fluorochemical monomer and urethane acrylate can make the dispersiveness of compound resin in water better than the dispersiveness of aqueous polyurethane acrylate in water.
Four of advantage of the present invention is that the content of fluorochemical in the resin can be regulated in very wide concentration range, therefore, can prepare the different soft and hard degree according to different requirements, and the urethane acrylate of different fluorine content is filmed.
Embodiment
The invention will be further described below in conjunction with embodiment, and subject area involved in the present invention is not limited only to this two examples.
Embodiment 1
Take by weighing polyoxyethylene glycol (molecular weight 1000) 40.0 grams, isophorone diisocyanate 5.0 grams, dimethylol propionic acid 4.5g renders in 40.0 gram N-methyl-pyrrolidone, and heated and stirred makes it dissolving.Dissolving finishes, and feeds nitrogen, stirs 15 minutes, is warming up to 90 ℃ of also stirring reactions 6 hours.Be cooled to 50 ℃, add hydroxyethyl methylacrylate 3.0 grams, continued stirring reaction 7 hours.Be cooled to room temperature, add triethylamine 0.5g, stirred 1 hour, make the aqueous polyurethane acrylate macromonomer.
Adding distil water 60.0g in above-mentioned reaction flask, restir 1 hour.Methylate methyl acrylate 1.5g stirred 0.5 hour.Add vinylformic acid hexafluoro butyl ester 5.0g, room temperature vigorous stirring 1.5 hours.Get this composite emulsion 10.0g, add light trigger (Irgacure 2959) 0.12g, stirred film-forming under UV-light 0.5 hour.
Embodiment 2
Take by weighing polypropylene oxide glycol (molecular weight 2000) 50.0 grams, tolylene diisocyanate 3.0 grams, dihydroxymethyl valeric acid 4.8g renders to 45.0 gram N, and in the dinethylformamide, heated and stirred makes it dissolving.Dissolving finishes, and feeds nitrogen, stirs 15 minutes, is warming up to 90 ℃ of also stirring reactions 6 hours.Be cooled to 50 ℃, add Hydroxyethyl acrylate 2.0 grams, continued stirring reaction 7 hours.Be cooled to room temperature, add triethylamine 0.3g, stirred 1 hour, make the aqueous polyurethane acrylate macromonomer.
Adding distil water 70.0g in above-mentioned reaction flask, restir 1 hour.Add methyl acrylate 1.2g, stirred 0.5 hour.Add Perfluorocaprylic Acid methacryloxy ethyl ester 6.0g, room temperature vigorous stirring 1.5 hours.Get this composite emulsion 10.0g, add light trigger (Irgacure 2959) 0.1g, stirred film-forming under UV-light 0.5 hour.
Claims (10)
1. ultraviolet-cured fluorine-containing aqueous urethane acrylate and preparation method thereof is characterized in that its proportioning is:
A fluorine-containing (methyl) acrylic ester monomer 0.5-50wt%
B aqueous polyurethane acrylate macromonomer 10-80wt%
C (methyl) acrylic ester monomer 0-20wt%
D light trigger 0.01-1.5wt%
E water 15-80wt%.
2. a kind of ultraviolet-cured fluorine-containing aqueous urethane acrylate according to claim 1 and preparation method thereof; it is characterized in that its preparation method is: under the room temperature condition; aqueous polyurethane acrylate macromonomer, water are added mixing in the reaction flask; under nitrogen protection; vigorous stirring 0.5-2 hour; add (methyl) acrylic ester monomer; stirred 0.5-2 hour; add fluorine-containing (methyl) acrylic ester monomer; continued vigorous stirring 0.5-3 hour; add light trigger, stirred 0.5-1 hour, then film-forming under UV-irradiation.
3. a kind of ultraviolet-cured fluorine-containing aqueous urethane acrylate according to claim 1 and preparation method thereof is characterized in that the A monomer selects at least a C for use
2-C
18Fluorine-containing (methyl) acrylic ester monomer, preferred C
5-C
16Fluorine-containing (methyl) acrylic ester monomer.
4. a kind of ultraviolet-cured fluorine-containing aqueous urethane acrylate according to claim 1 and preparation method thereof is characterized in that C selects at least a acrylic monomer or methyl acrylic ester monomer for use.
5. a kind of ultraviolet-cured fluorine-containing aqueous urethane acrylate according to claim 1 and preparation method thereof, it is characterized in that light trigger D selects at least a oil soluble light trigger or water-soluble light trigger for use, Irgacure2959[2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl phenyl ketone].
6. a kind of ultraviolet-cured fluorine-containing aqueous urethane acrylate according to claim 1 and preparation method thereof, the preparation method who it is characterized in that the aqueous polyurethane acrylate macromonomer is: in reaction flask, add solvent, polyisocyanates monomer, polyalcohols monomer, the polyvalent alcohol that contains carboxyl or tertiary amine groups or polynary amine monomer, logical nitrogen 30 minutes, be warmed up to 65-90 ℃, reacted 5-8 hour; Cool to 50 ℃, drip (methyl) acrylic acid hydroxy alkyl ester class monomer, reacted 6-10 hour, make the aqueous polyurethane acrylate macromonomer of the two keys of terminal band.
7. a kind of ultraviolet-cured fluorine-containing aqueous urethane acrylate according to claim 6 and preparation method thereof is characterized in that the polyisocyanates monomer, selects at least a aliphatic polyisocyante or aromatic polyisocyanate for use; The polyalcohols monomer is selected at least a polyether glycol, polyester polyol or small molecules polyvalent alcohol for use; The monomeric amount ratio of polyisocynate monomer and polyalcohols is looked required soft durometer of filming and is regulated.
8. a kind of ultraviolet-cured fluorine-containing aqueous urethane acrylate according to claim 6 and preparation method thereof, it is characterized in that introducing the polyvalent alcohol or the polyamine compound that contain carboxyl or uncle's amino, to improve the wetting ability of urethane acrylate macromonomer; Preferred carboxylic multicomponent alcoholics compound, as: dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid or 2,3-dimethylolpropionic acid.
9. a kind of ultraviolet-cured fluorine-containing aqueous urethane acrylate according to claim 6 and preparation method thereof, it is characterized in that selecting for use (methyl) acrylic acid hydroxy alkyl ester class monomer that the polyurethane macromolecular monomer is carried out end-blocking, to introduce two keys at the macromole end; As: hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate or Propylene glycol monoacrylate.
10. a kind of ultraviolet-cured fluorine-containing aqueous urethane acrylate according to claim 6 and preparation method thereof, it is characterized in that its solvent selects the solvent that dissolves each other with water for use, as: N-Methyl pyrrolidone, N, dinethylformamide, acetone or tetrahydrofuran (THF).
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| CN200910135090A CN101870756A (en) | 2009-04-23 | 2009-04-23 | Ultraviolet-cured fluorine-containing aqueous urethane acrylate and preparation method thereof |
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| CN200910135090A CN101870756A (en) | 2009-04-23 | 2009-04-23 | Ultraviolet-cured fluorine-containing aqueous urethane acrylate and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153929A (en) * | 2011-02-28 | 2011-08-17 | 上虞市佑谦特种材料有限公司 | Ultraviolet (UV) curable aqueous spraying paint and construction process thereof |
| CN103360807A (en) * | 2013-07-01 | 2013-10-23 | 恒昌涂料（惠阳）有限公司 | Fluorine-containing light-cured waterborne coating and preparation method thereof |
| CN106519755A (en) * | 2016-11-16 | 2017-03-22 | 成都市创斯德机电设备有限公司 | Wear-resistant ultraviolet-cured coating for optical fiber and preparation method thereof |
| CN109135551A (en) * | 2018-08-09 | 2019-01-04 | 深圳市前海奇迹新材料有限公司 | A kind of high-flexibility waterborne UV coating |
| CN109468120A (en) * | 2018-11-13 | 2019-03-15 | 上海仁速新材料有限公司 | UV adhesive of high pressure resistant boiling and preparation method thereof |
| CN114958179A (en) * | 2022-07-19 | 2022-08-30 | 湖南松井新材料股份有限公司 | High-adhesion stain-resistant water-based paint and preparation method and application thereof |
| CN115634818A (en) * | 2021-07-20 | 2023-01-24 | 李萍 | Automobile minimally invasive repair paint repairing method |
-
2009
- 2009-04-23 CN CN200910135090A patent/CN101870756A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153929A (en) * | 2011-02-28 | 2011-08-17 | 上虞市佑谦特种材料有限公司 | Ultraviolet (UV) curable aqueous spraying paint and construction process thereof |
| CN102153929B (en) * | 2011-02-28 | 2013-04-24 | 上虞市佑谦特种材料有限公司 | Ultraviolet (UV) curable aqueous spraying paint and construction process thereof |
| CN103360807A (en) * | 2013-07-01 | 2013-10-23 | 恒昌涂料（惠阳）有限公司 | Fluorine-containing light-cured waterborne coating and preparation method thereof |
| CN106519755A (en) * | 2016-11-16 | 2017-03-22 | 成都市创斯德机电设备有限公司 | Wear-resistant ultraviolet-cured coating for optical fiber and preparation method thereof |
| CN109135551A (en) * | 2018-08-09 | 2019-01-04 | 深圳市前海奇迹新材料有限公司 | A kind of high-flexibility waterborne UV coating |
| CN109135551B (en) * | 2018-08-09 | 2020-11-20 | 深圳市前海奇迹新材料有限公司 | High-flexibility water-based UV coating |
| CN109468120A (en) * | 2018-11-13 | 2019-03-15 | 上海仁速新材料有限公司 | UV adhesive of high pressure resistant boiling and preparation method thereof |
| CN115634818A (en) * | 2021-07-20 | 2023-01-24 | 李萍 | Automobile minimally invasive repair paint repairing method |
| CN114958179A (en) * | 2022-07-19 | 2022-08-30 | 湖南松井新材料股份有限公司 | High-adhesion stain-resistant water-based paint and preparation method and application thereof |
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Open date: 20101027 |