CN103360807A - Fluorine-containing light-cured waterborne coating and preparation method thereof - Google Patents
Fluorine-containing light-cured waterborne coating and preparation method thereof Download PDFInfo
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- CN103360807A CN103360807A CN2013102726827A CN201310272682A CN103360807A CN 103360807 A CN103360807 A CN 103360807A CN 2013102726827 A CN2013102726827 A CN 2013102726827A CN 201310272682 A CN201310272682 A CN 201310272682A CN 103360807 A CN103360807 A CN 103360807A
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Abstract
The invention discloses a fluorine-containing light-cured waterborne coating and a preparation method thereof. The light-cured waterborne coating is prepared from the components in parts by weight: 100 parts of solvent (a), 1-69 parts of light-cured fluorine-containing resin (b) and 0.05-3.45 parts of cross-linking agent (c), wherein the light-cured fluorine-containing resin (b) is prepared by virtue of copolymerization of fluorine monomers, N-vinyl pyrrolidone and monomers containing light active groups. The fluorine-containing light-cured waterborne coating has the excellent performances of short curing time, strong hydrophilicity and high lubricity.
Description
Technical field
The present invention relates to technical field of coatings, relate in particular to a kind of fluorine-containing UV curable waterborne coatings and preparation method thereof.
Background technology
Along with the development of science and technology and the people attention to environmental issue, exploitation high-performance, pollution-free, environmentally friendly coating have become a trend of paint field.The luminous energy of utilizing the photocuring coatings volatile organic compounds causes low molecule performed polymer in the coating or oligomer and obtains the paint film that hardens as the polymerization between the monomer molecule of reactive thinner and crosslinking reaction, its advantage is: capacity usage ratio is high, curing speed is fast, and production efficiency is high.Water-borne coatings is with water as solvent, and its advantage is: only adopt a small amount of hypotoxicity alcohol ethers as organic solvent, Environmental Safety; Can directly apply construction in wet surface and wet environment, good to material surface adaptability, coating adhesion is strong.
UV curable waterborne coatings combines the advantage of water-borne coatings and photocuring coatings volatile organic compounds, is rapidly developed in recent years.UV curable waterborne coatings has solved the intrinsic soft of water-borne coatings, and energy consumption is high, requires the shortcomings such as high to reaching the material surface degree of cleaning in the construction process; Solved the photocuring coatings volatile organic compounds dangerous, the problems such as cure shrinkage have realized aqueous, environmental protective, cost degradation and high-level efficiency application.Along with further developing of photocuring hydrophilic coating research, the range of application of photocuring hydrophilic coating is increasingly extensive, on the base materials such as metal, woodenware, plastics, leather, glass, pottery, all can apply, thereby fully develop talents in fields such as optical fiber, printed circuit board (PCB), battery, medicine equipment, windshield glass, rearview mirror of means of transportation, wall paints.
Although UV curable waterborne coatings makes some progress in production technology and Application Areas, solve that production efficiency is low, solidification value is higher and the problem such as paint film mechanical property aspect still make little progress.At this on the one hand, application number is that 86101022 Chinese patent discloses a kind of water wetted material for offset printing forme, this invention applies one deck at aluminium base and comprises the support that acrylamide iso-butylene phosphoric acid hydrophilic coating forms preparation press plate photoactive substance, but this hydrophilic coating could apply after base material is through complicated processing, process time is longer, and its application has larger restriction.It is a kind of for the stable hydrophilic coating on the carbon-based material of fuel cell that application number is that 101685864 Chinese patent discloses, but this coating need to obtain active surface through ozone or Cement Composite Treated by Plasma, complex process, and the process time is longer.Application number provides a kind of hydrophilic coated aluminum foil use protective system for 101798479 Chinese patent, satisfies the erosion resistance requirement to coating, but this water-borne coatings needs hot setting when applying, be not suitable for the coating of some thermo-sensitivity base materials.Application number has solved the poor problem of the anti-contamination of exterior coating for 102911581 Chinese patent provides a kind of super hydrophilic and compound hydrophilic coating of the significant organic-inorganic of automatically cleaning effect, but its mechanical property and lasting hydrophilic power are not quite desirable.
Summary of the invention
For problems of the prior art, main purpose of the present invention is to provide a kind of fluorine-containing UV curable waterborne coatings, this fluorine-containing UV curable waterborne coatings at normal temperatures set time short, and wetting ability is strong, oilness is high.Another object of the present invention is to provide a kind of method for preparing above-mentioned fluorine-containing UV curable waterborne coatings.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of UV curable waterborne coatings is characterized in that comprising:
(a) solvent;
(b) photo-cured fluorine-containing resin; And
(c) linking agent;
Wherein in 100 parts by weight of component (a), the content of described component (b) is 1～69 weight part, and the content of component (c) is 0.05～3.45 weight part.
In a preferred embodiment, in 100 parts by weight of component (a), the content of component (b) is 5～34.5 weight parts.
In a preferred embodiment, in 100 parts by weight of component (a), the content of component (c) is 1～1.72 weight part.
In a preferred embodiment, component (a) is the mixture of isopropyl alcohol and water, and the volume ratio of isopropyl alcohol and water is 1:1～1.5:1.
In a preferred embodiment, component (b) is formed by fluorine monomer, NVP, the monomer copolymerization that contains optical active group.By the reaction of the polymer copolymerization between the monomer, fluorine monomer and the NVP monomer that contain optical active group, synthesized a kind of wetting ability light-cured resin, use it for UV curable waterborne coatings.This fluorine-containing UV curable waterborne coatings passes through ultraviolet irradiation after being coated in substrate surface, can solidify rapidly, has greatly reduced the time of naturally drying or solidifying in vacuum drying oven with respect to traditional hydrophilic coating.
Preferably, fluorine monomer is fluoro-acrylate monomer.
Preferably, the monomer that contains optical active group is the reactive monomer that contains benzophenone structural.
In a preferred embodiment, the monomer that contains optical active group is N-[3-(4-benzoyl benzamido) propyl group] Methacrylamide, N-[3-(4-benzoyl benzamido) propyl group] concrete preparation method is as follows for Methacrylamide:
1) with the N-(3-aminopropyl) methacrylamide hydrochloride and 4-benzophenone formyl chloride in molar ratio 1:1.2 be dissolved in the chloroform;
2) adding and N-(3-aminopropyl under condition of ice bath) the methacrylamide hydrochloride mol ratio is the triethylamine of 1:1.2, ice bath reaction 2 hours;
3) room temperature reaction is 2 hours, and behind the removal solvent, the reaction product volume ratio is that the toluene of 3:1 and the mixed solvent recrystallization of chloroform are purified, and namely obtains N-[3-(4-benzoyl benzamido) propyl group] Methacrylamide.
The invention also discloses a kind of method for preparing the photo-cured fluorine-containing resin, it is characterized in that, may further comprise the steps:
The monomer that 1) will contain optical active group is dissolved in the organic solvent;
2) in the solution of step 1) gained, add NVP, fluorine monomer, photosensitizers;
3) with step 2) solution of gained is to heat 12～48 hours under 50 ℃～70 ℃ the condition in nitrogen atmosphere, temperature;
4) make solution precipitation with ether after the heating, filter out throw out, drying obtains the photo-cured fluorine-containing resin;
Wherein fluorine monomer, NVP, the monomer molar ratio that contains optical active group are 1～3:40～60:0.2～0.8.
The invention also discloses a kind of using method of UV curable waterborne coatings, it is characterized in that, may further comprise the steps:
1) photo-cured fluorine-containing resin and linking agent are dissolved in form solution in the solvent;
2) base material is invaded in the solution 1～2 minute;
3) room temperature is dried;
4) at 0.5-2mw/cm
2Solidified under the UV-light 1～10 minute, and formed fluorine-containing light solidifying coating at substrate surface.
A kind of UV curable waterborne coatings of the present invention comprises fluorine resin, fluorine resin is owing to having replaced the position of hydrogen atom in the molecule with the strongest fluorine of electronegativity, and electronics is adsorbed on around the fluorine atom nuclear tightly, is difficult for polarization, shield nucleus, thereby greatly reduced the surface free energy of coating.The radius of fluorine atom is again little, the polarizability of C-F key is low, both combined action cause its intramolecule compact structure, therefore show the special surface propertys such as outstanding resistance to soiling, hydrophobic, oleophobic after the coating film forming prepared therefrom, and have good chemical stability, thermostability and biocompatibility, also further increased the Hydrophilic lubrication of coating.
Embodiment
Various raw material of the present invention all can obtain by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Because the characteristic of fluorine atom and fluorine carbon bond, fluorine-containing light-cured resin has thermostability, ageing resistance, and frictional coefficient is little, and surface tension is little, and wetting property is good, the characteristics that cohesive strength is high, so the photo-cured coating among the present invention is selected fluorine-containing light-cured resin.Linking agent of the present invention can be selected the art linking agent commonly used, can require to select according to the difference of coating the linking agent of different qualities, is preferably commercially available N,N methylene bis acrylamide.Solvent can be common varsol or oxo solvent, is preferably the mixture of isopropyl alcohol and water, because water and isopropanol mixture safety non-toxic not only, and it is fast to send out speed, can shorten the set time of photo-cured coating.
The monomer polymerization that the present invention adopts fluorine monomer, NVP monomer and contains optical active group becomes light-cured resin, and this light-cured resin has the excellent properties of fluorine resin, and preparation technology's simple possible.The NVP monomer is made an addition in the prescription of photo-cured coating, can make coating form pliable and tough and hard film.The monomer that contains optical active group used in the present invention is preferably the optical active group with benzophenone structural, because benzophenone itself is light trigger, need to not add in addition light trigger in reaction again.Fluorine monomer is preferable over fluoro-acrylate monomer, and it is such as but not limited to being selected from trifluoroethyl methacrylate, tetrafluoropropyl propyl ester, Hexafluorobutyl mathacrylate, vinylformic acid seven fluorine butyl esters, the group that methacrylic acid octafluoro pentyl ester and composition thereof forms.
The contriver is through research; self synthesized a kind of reactive monomer; be called N-[3-(4-benzoyl benzamido) propyl group] Methacrylamide; the preparation method of this reactive monomer is as follows: with the N-(3-aminopropyl) methacrylamide hydrochloride and 4-benzophenone formyl chloride in molar ratio 1:1.2 be dissolved in the chloroform; again adding and N-(3-aminopropyl under condition of ice bath) the methacrylamide hydrochloride mol ratio is the triethylamine of 1:1.2; the ice bath reaction is after 2 hours; in room temperature reaction 2 hours; after removing solvent, the product volume ratio is that the toluene of 3:1 and the mixed solvent recrystallization of chloroform are purified.Its reaction equation is as follows:
Wherein, the concrete preparation method of 4-benzophenone formyl chloride is as follows:
1) taking by weighing 1 gram 4-benzoylbenzoic acid is dissolved in the 30ml toluene;
2) add sulfur oxychloride 0.7ml(1.05 gram, with the mol ratio of 4-benzoylbenzoic acid be 1:2), add again two to three catalyzer dimethyl formamides (DMF);
3) be heated to about 45 ℃, refluxed 3 hours;
4) after the cooling, revolve the steaming desolventizing, use normal hexane: toluene (volume ratio is 4:1) mixed solution recrystallization reaction product obtains white solid and is 4-benzophenone formyl chloride.
The present invention prepares the photosensitizers that adds in the fluorine resin method, there is no particular restriction, is can produce free radical after rayed, and sees through the transmission initiated polymerization person of free radical, is preferably Diisopropyl azodicarboxylate.In addition, can optionally use two or more photosensitizers.The consumption of photosensitizers is adjusted according to kind and the consumption thereof of optional reactive monomer and fluorine monomer also without particular restriction.
Fluorine-containing photocuring hydrophilic coating of the present invention also can comprise one or more the technical field of the invention and have the additive usually known known to the knowledgeable as component (d).Can be used for additive of the present invention and there is no particular restriction, such as but not limited to the group that free wetting agent, smooth dose, defoamer, dispersion agent and combination thereof form, its consumption also determines according to different demands for the persond having ordinary knowledge in the technical field of the present invention.
The base material that fluorine-containing photocuring hydrophilic coating of the present invention is suitable for there is no particular restriction, such as can be ceramic tile, timber, leather, stone material, glass, metal, alloy, paper, plastics, fiber, cotton goods etc., be preferably glass, metal, plastics or composite base material.
Fluorine-containing photocuring hydrophilic coating of the present invention can be coated on the surface of base material by any persond having ordinary knowledge in the technical field of the present invention mode known.For example, can be used via the method that comprises following steps:
(1) synthetic fluorine resin and the linking agent of selecting are added in the solvent, mix;
(2) be adjusted to suitable viscosity;
(3) the liquid polymerisable compound of step (2) gained is coated by rights on the base material and to be done the surface and process, form a coating or directly base material is invaded in the liquid polymerisable compound 1～2 minute;
(4) at room temperature dry base material;
(5) the irradiation energy ray is so that this coating curing.
The coating curing step of step (5) is to solidify energy-ray by irradiation ultraviolet radiation to produce photopolymerization reaction and carry out, exposure intensity and irradiation time determine according to the factors such as thickness of base material and coating, irradiation time is preferably 1～10 minute, and exposure intensity is preferably 0.5～2mw/cm
2
For the purpose, technical solutions and advantages of the present invention better are described, the invention will be further described below in conjunction with specific embodiment.
Embodiment 1: with synthesizing of photoactive fluorine-containing (trifluoroethyl methacrylate) hydrophilic resin
Take by weighing vinyl pyrrolidone 5.55g(50mmol), trifluoroethyl methacrylate 0.5g (2.9mmol) places three-necked flask; add again N-[3-(the 4-benzoyl benzamido) propyl group that is dissolved in the 10ml dimethyl sulfoxide (DMSO)] Methacrylamide 0.18g(0.52mmol); in flask, pass into nitrogen to remove air; add again Diisopropyl azodicarboxylate 0.1g (0.6mmol); be full of nitrogen rear enclosed container on the liquid level, 55 ℃ were heated 12 hours.Reaction makes solution precipitation with ether after finishing, and filters out throw out, is put in drying in the baking oven, obtains the 5g white solid.The optical active group benzophenone is 0.1mmol/g after testing.
Embodiment 2: with synthesizing of photoactive fluorine-containing (tetrafluoropropyl propyl ester) hydrophilic resin
Take by weighing vinyl pyrrolidone 5.55g(50mmol), tetrafluoropropyl propyl ester 0.5g (2.5mmol) places three-necked flask; add again N-[3-(the 4-benzoyl benzamido) propyl group that is dissolved in the 10ml dimethyl sulfoxide (DMSO)] Methacrylamide 0.18g(0.52mmol); in flask, pass into nitrogen to remove air; add Diisopropyl azodicarboxylate 0.1g (0.6mmol); be full of nitrogen rear enclosed container on the liquid level, 70 ℃ degrees centigrade were heated 30 hours.Reaction makes solution precipitation with ether after finishing, and filters out throw out, is put in drying in the baking oven, obtains the 5g white solid.The optical active group benzophenone is 0.1mmol/g after testing.
Embodiment 3: with synthesizing of photoactive fluorine-containing (Hexafluorobutyl mathacrylate) hydrophilic resin
Take by weighing vinyl pyrrolidone 5.55g(50mmol), Hexafluorobutyl mathacrylate 0.5g (2mmol) places three-necked flask; add again N-[3-(the 4-benzoyl benzamido) propyl group that is dissolved in the 10ml dimethyl sulfoxide (DMSO)] Methacrylamide 0.18g(0.52mmol); in flask, pass into nitrogen to remove air; add again Diisopropyl azodicarboxylate 0.1g (0.6mmol); be full of nitrogen rear enclosed container on the liquid level, 50 ℃ were heated 48 hours.Reaction makes solution precipitation with ether after finishing, and filters out throw out, is put in drying in the baking oven, obtains the 5g white solid.The optical active group benzophenone is 1mmol/g after testing.
Embodiment 4: the preparation of fluorine-containing UV curable waterborne coatings (A1)
Fluorine-containing hydrophilic resin prepared among the 5g embodiment 1 and 0.2g linking agent N,N methylene bis acrylamide are joined in the solvent that is comprised of 30ml Virahol and 20ml pure water, behind ultrasonic dissolution, form coating solution.
Embodiment 5: the preparation of fluorine-containing UV curable waterborne coatings (A2)
Fluorine-containing hydrophilic resin prepared among the 6g embodiment 2 and 0.25g linking agent N,N methylene bis acrylamide are joined in the solvent that is comprised of 30ml Virahol and 30ml pure water, behind ultrasonic dissolution, form coating solution.
Embodiment 7: the preparation of fluorine-containing UV curable waterborne coatings (A3)
Fluorine-containing hydrophilic resin prepared among the 7g embodiment 3 and 0.3g linking agent N,N methylene bis acrylamide are joined in the solvent that is comprised of 30ml Virahol and 25ml pure water, behind ultrasonic dissolution, form coating solution.
Embodiment 8: the preparation of not fluorine-containing UV curable waterborne coatings (B1)
Take by weighing vinyl pyrrolidone 5.55g(50mmol) place three-necked flask; add again N-[3-(the 4-benzoyl benzamido) propyl group that is dissolved in the 10ml dimethyl sulfoxide (DMSO)] Methacrylamide 0.18g(0.52mmol); in flask, pass into nitrogen to remove air; add Diisopropyl azodicarboxylate 0.1g (0.6mmol); Tetramethyl Ethylene Diamine 0.006ml (0.042mmol); be full of nitrogen rear enclosed container on the liquid level, 55 ℃ were heated 12 hours.Reaction makes solution precipitation with ether after finishing, and filters out throw out, is put in drying in the baking oven, obtains the 5g white solid.The optical active group benzophenone is 1mmol/g after testing.
Not fluorine-containing hydrophilic resin and the 0.3g linking agent N,N methylene bis acrylamide of 7g preparation are joined in the solvent that is comprised of 30ml Virahol and 25ml pure water, behind ultrasonic dissolution, form coating solution.
Performance test:
1, test set time
Polyurethane base material behind the cleaning-drying is in advance immersed respectively in A1, A2, A3, the B1 coating solution, take out after 2 minutes, at room temperature dry, the base material that is coated with coating solution is solidified under UV-irradiation obtain coating, UV-irradiation intensity is 2mw/cm
2, write down each coating curing time completely.
2, sticking power test
Draw 100 1 millimeter * 1 millimeter square lattice at coatingsurface with drawing the lattice device, then be bonded on the grid with scotch tape is smooth, do not stay a space, then uncover rapidly adhesive tape with 60 degree angles, whether the cut edge of observing paint film has depainting.
As being 5B without any depainting, the depainting amount is 4B between 0-5 area %, and the depainting amount is 3B between 5-15 area %, and the depainting amount is 2B between 15-35 area %, and the depainting amount is 1B between 35-65 area %, and the depainting amount is 0B more than 65 area %.
3, water resistance test
Coating is placed in the water respectively soaks, write down each coating from time that base material begins to come off.
4, PVvalue testing
With the PVvalue testing instrument frictional coefficient of each coating is measured.
Table 1
| Numbering | Set time | Sticking power | Water tolerance | Frictional coefficient |
| A1 | 5min | 5B | 30 days | 0.08 |
| A2 | 4.5min | 4B | 32 days | 0.08 |
| A3 | 5min | 5B | 28 days | 0.08 |
| B1 | 9min | 4B | 15 days | 0.1 |
Can find out from the data of table 1, the coating that fluorine-containing photo-cured coating provided by the invention forms is suitable with not fluorine-containing photo-cured coating to the sticking power of matrix, but the fluorine-containing photo-cured coating coating curing time is shorter than not fluorine-containing photo-cured coating, and water tolerance is apparently higher than not fluorine-containing photo-cured coating, and oilness is also more superior.
Above disclosed is preferred embodiment of the present invention only, and for one of ordinary skill in the art, the thought according to content of the present invention all will change in specific embodiments and applications.In sum, this description should not be construed as limitation of the present invention, and all any changes of doing according to design philosophy of the present invention are all within protection scope of the present invention.
Claims (10)
1. UV curable waterborne coatings is characterized in that comprising:
(a) solvent;
(b) photo-cured fluorine-containing resin; And
(c) linking agent;
Wherein in 100 parts by weight of component (a), the content of described component (b) is 1～69 weight part, and the content of component (c) is 0.05～3.45 weight part.
2. UV curable waterborne coatings as claimed in claim 1, it is characterized in that: wherein in 100 parts by weight of component (a), the content of component (b) is 5～34.5 weight parts.
3. UV curable waterborne coatings as claimed in claim 1, it is characterized in that: wherein in 100 parts by weight of component (a), the content of component (c) is 1～1.72 weight part.
4. UV curable waterborne coatings as claimed in claim 1, it is characterized in that: described component (a) is the mixture of isopropyl alcohol and water, the volume ratio of isopropyl alcohol and water is 1:1～1.5:1.
5. UV curable waterborne coatings as claimed in claim 1 is characterized in that: described component (b) is formed by fluorine monomer, NVP, the monomer copolymerization that contains optical active group.
6. UV curable waterborne coatings as claimed in claim 5, it is characterized in that: described fluorine monomer is fluoro-acrylate monomer.
7. UV curable waterborne coatings as claimed in claim 5, it is characterized in that: the described monomer that contains optical active group is the reactive monomer that contains benzophenone structural.
8. UV curable waterborne coatings as claimed in claim 5; it is characterized in that: the described monomer that contains optical active group is N-[3-(4-benzoyl benzamido) propyl group] Methacrylamide, described N-[3-(4-benzoyl benzamido) propyl group] concrete preparation method is as follows for Methacrylamide:
1) with the N-(3-aminopropyl) methacrylamide hydrochloride and 4-benzophenone formyl chloride in molar ratio 1:1.2 be dissolved in the chloroform;
2) adding and N-(3-aminopropyl under condition of ice bath) the methacrylamide hydrochloride mol ratio is the triethylamine of 1:1.2, ice bath reaction 2 hours;
3) room temperature reaction is 2 hours, and behind the removal solvent, the reaction product volume ratio is that the toluene of 3:1 and the mixed solvent recrystallization of chloroform are purified, and namely obtains described N-[3-(4-benzoyl benzamido) propyl group] Methacrylamide.
9. a method for preparing the photo-cured fluorine-containing resin is characterized in that, may further comprise the steps:
The monomer that 1) will contain optical active group is dissolved in the organic solvent;
2) in the solution of step 1) gained, add NVP, fluorine monomer, photosensitizers;
3) with step 2) solution of gained is to heat 12～48 hours under 50 ℃～70 ℃ the condition in nitrogen atmosphere, temperature;
4) make solution precipitation with ether after the heating, filter out throw out, drying obtains fluorine-containing light-cured resin;
Wherein fluorine monomer, NVP, the molar ratio that contains the monomer of optical active group are 1～3:40～60:0.2～0.8.
10. the using method of a UV curable waterborne coatings is characterized in that, may further comprise the steps:
1) photo-cured fluorine-containing resin and linking agent are dissolved in form solution in the solvent;
2) base material is invaded in the solution 1～2 minute;
3) room temperature is dried;
4) at 0.5-2mw/cm
2UV-light under solidified 1～10 minute, form fluorine-containing light solidifying coating at substrate surface.
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| CN106125510A (en) * | 2016-08-30 | 2016-11-16 | Tcl集团股份有限公司 | A kind of negativity photoresistance thin film and preparation method and application |
| CN112745705A (en) * | 2020-12-14 | 2021-05-04 | 安徽庆润新材料技术有限公司 | Fluoropolymer nanoparticle modified photocuring fluorocarbon coating and preparation method thereof |
| CN115894767A (en) * | 2022-12-05 | 2023-04-04 | 陕西希泰兴邦材料科技有限公司 | Light-cured fluororubber, synthetic method, composite sealing gasket and application |
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| CN115894767A (en) * | 2022-12-05 | 2023-04-04 | 陕西希泰兴邦材料科技有限公司 | Light-cured fluororubber, synthetic method, composite sealing gasket and application |
| CN115894767B (en) * | 2022-12-05 | 2024-02-13 | 陕西希泰兴邦材料科技有限公司 | Photo-curing fluororubber, synthesis method, composite sealing gasket and application |
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