CN107254207A - A kind of ultraviolet light solidification super-hydrophobic transparent wear-resistant coating and preparation method thereof - Google Patents

A kind of ultraviolet light solidification super-hydrophobic transparent wear-resistant coating and preparation method thereof Download PDF

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CN107254207A
CN107254207A CN201710464078.2A CN201710464078A CN107254207A CN 107254207 A CN107254207 A CN 107254207A CN 201710464078 A CN201710464078 A CN 201710464078A CN 107254207 A CN107254207 A CN 107254207A
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resistant coating
ultraviolet light
hydrophobic
preparation
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CN107254207B (en
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郑咏梅
周蕾
李吉彤
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Beihang University
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    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/002Pretreatement
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065After-treatment
    • B05D3/067Curing or cross-linking the coating
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/1006Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate

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Abstract

The invention discloses a kind of ultraviolet light solidification super-hydrophobic transparent wear-resistant coating and preparation method thereof, belong to photocureable coating technical field.The preparation method includes transparent base activating pretreatment, the dispersion liquid containing reactive nanoparticles and prepared;Active fluorine monomer, reactive diluent and light trigger are added in the dispersion liquid containing reactive nanoparticles, then homogenous application is on the transparent base after first step activating pretreatment, and in the case where obtaining UV energy effect, solidification obtains super-hydrophobic transparent wear-resistant coating.The features such as preparation method has efficient, wide adaptability, economy, energy-conservation and is environment-friendly, the features such as ultraviolet light solidification super-hydrophobic transparent wear-resistant coating prepare simultaneously obtained by has self-cleaning surface, surface anticorrosion, hydrophobic, anti-fog properties, freezing, with there is good adhesive force to base material.

Description

A kind of ultraviolet light solidification super-hydrophobic transparent wear-resistant coating and preparation method thereof
Technical field
The invention belongs to photocureable coating technical field, and in particular to it is a kind of be adapted to use on glass have it is high durable Property, water droplet wash away, super-hydrophobic automatic cleaning nanometer transparent coating and preparation method thereof.
Background technology
The coating material solidified first part of patent of ultraviolet light (UV) was born in nineteen forty-seven, by the development of over half a century, ultraviolet light (UV) it is coating material solidified to have become more ripe technology, in particular with the raising of people's environmental consciousness, production and research people Member is important to note that the coating material solidified development and application of UV.The end of the sixties in last century, Beyer Co., Ltd is based on unsaturated-resin and rested in peace Fragrant system development works out a kind of ultraviolet-curing paint of environment-friendly energy-saving.In recent years, with people to using energy source with And in terms of environmental protection problem continuous attention, countries in the world are all serious to traditional volatile organic compound VOC emission Solvent based coating limited and improved, more pay attention to based on environmental protection theory coating technology exploitation.At present, China Develop into after the U.S., Japan, the global the third-largest radiation-curable products place of production, among these and with photocureable coating yield most Greatly.In the past few years, ultraviolet light (UV) is coating material solidified in fibre coating, laser disc (CD) coating, digitized video light Suffered from disk (DVD) adhesive, credit card, timber, beverage can, packaging for foodstuff, journal surface, medicine equipment and automobile industry Very rapidly development.
Because the unique surface characteristic of hydrophobic and super hydrophobic surface makes it in self-cleaning surface, microfluid system and biofacies Potential application is there is in terms of capacitive, there are extensive market prospects in national defence, daily life and numerous industrial circles, it is existing Turn into the study hotspot of major industry companies.Disclosed in publication number CN103587185A patent document with nano particle with Super-hydrophobic coat prepared by mixed with resin, although the super-hydrophobic coat possesses certain Scratch Resistance energy, but can not realize coating Translucency.A kind of optical clear of suitable glass baseplate is disclosed in the A of publication number CN 104987520 patent document super thin Water coating, but effective hardness of the coating on glass can not be ensured, limit the commercialized application of its coating.Current material Surface hydrophobicity technology still fails to realize large-scale application, traces it to its cause and is there is substantial amounts of low-surface-energy in super-hydrophobic coat Nano particle can not cause strength of coating while super-hydrophobic effect is ensured not high enough with Bulk coat chemically reactive, logical The coating material often applied in glass baseplate has also been proposed higher requirement to translucency.How super-hydrophobic coat is being ensured On the premise of energy, the high light transmittance of coating is realized, higher requirement is proposed to research staff.
The content of the invention
For problems of the prior art, the present invention provide a kind of ultraviolet light solidification super-hydrophobic transparent wear-resistant coating and Its preparation method, the features such as preparation method has efficient, wide adaptability, economy, energy-conservation and be environment-friendly, while preparing institute Obtained ultraviolet light solidification super-hydrophobic transparent wear-resistant coating has self-cleaning surface, surface anticorrosion, hydrophobic, anti-fog properties, freezing The features such as, with there is good adhesive force to base material.
The ultraviolet light that the present invention is provided solidifies the preparation method of super-hydrophobic transparent wear-resistant coating, comprises the following steps that:
The first step, transparent base activating pretreatment:After transparent substrate surface has been pre-processed, by the silicon of 1~5% mass concentration Alkane coupling agent is added in the first organic solvent, is then wherein activated transparent base immersion, in transparent substrate surface The active group of reaction is may participate in grafting;Described active group is the acryloyl-oxy based structures containing unsaturated functional group.
Second step, according to percentage by weight, second is added to by 0.5~10% nano particle and 2~6% silane couplers Plant in organic solvent, reaction is hydrolyzed in the environment of pH 3~9, generate the dispersion liquid containing reactive nanoparticles.
3rd step, adds active fluorine monomer, reactive diluent and light-initiated in the dispersion liquid containing reactive nanoparticles Agent, then homogenous application is solid in the case where obtaining UV energy effect on the transparent base after first step activating pretreatment Change obtains super-hydrophobic transparent wear-resistant coating.
Compared with prior art, the advantage of the invention is that:
(1) reactive diluent in the present invention, reactive nanoparticles, formed altogether by the reaction that crosses one another between siloxanes Valence link, effectively improves the wearability and hardness of super-hydrophobic coat, overcome traditional super-hydrophobic coat method be sprayed directly into it is transparent After base material, because nano particle is after by external impacts, come off from coating surface, cause the problem of super-hydrophobic effect fails.
(2) micro-nano structure that the present invention is constructed is due to being free of macromolecular resin composition in coating system, and obtained film layer is thick Degree can be controlled effectively, it is ensured that the optical transparence of coating.
(3) present invention research and the UV solidification super-hydrophobic transparent wear-resistant coatings prepared promote super-hydrophobic coat in application road Paces, wide market are strided forward on road.
Brief description of the drawings
The super-hydrophobic transparent wear-resistant coating structural representation that Fig. 1 is prepared for the present invention, reactive grafting is passed through in glass surface Siloxanes chemical group and nano particle.
Fig. 2 is spherical to observe that water droplet (3 μ L) shows on super-hydrophobic transparent wear-resistant coating under an optical microscope.
Fig. 3 is the super-hydrophobic transparent wear-resistant coating of the preparation of the embodiment of the present invention 1 at visible region (390nm~780nm) Light transmittance curve.
Fig. 4 A and Fig. 4 B be respectively embodiment 1 and comparative example 1 obtained by coating measured respectively by contact angle measurement Contact angle.
Embodiment
For the ease of the understanding of those skilled in the art, present invention work is further retouched with reference to the accompanying drawings and examples State.
The present invention provides the preparation method that a kind of ultraviolet light solidifies super-hydrophobic transparent wear-resistant coating, comprises the following steps that:
The first step, transparent base activating pretreatment.
To the transparent base that uses, there is no particular limitation in the present invention, can (light transmittance is big from existing optical transparent properties Select to use in material 80%).The transparent base used in the present invention can (indium tin be aoxidized for glass, crystalline ceramics, ITO Thing transparent conductive semiconductor film), PET, polybutylene terephthalate and poly (ethylene naphthalate), Polyethylene, polypropylene, glassine paper, diacetyl cellulose, tri acetyl cellulose, butyric acid acetylcellulose, polyvinyl chloride, Vingon, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, makrolon, polymethylpentene, polysulfones, Any one in polyether-ether-ketone, PEI, polyimides, fluororesin or polyamide, preferably uses glass baseplate.
The transparent base used in the present invention, can be pre-processed when needing to use to the surface of transparent base, so as to The reaction bonded power of intensified response group and transparent substrate surface.For example using Corona discharge Treatment, plasma (plasma) Processing, it is sharp using the processing for heating air, or in the presence of ozone using the processing of flame using the processing (wet method) of chromic acid Handled with ultraviolet irradiation, using Piranha solution, (piranha solution, 98% concentrated sulfuric acid and 30% hydrogen peroxide are with volume Than for 7:3 mixed liquor) cleaning.Surface preparation carries out appropriate selection according to the species of transparent base, generally from effect and Operability considers.
Preferably, described pretreatment can be plasma (plasma) processing, secondary to elect Piranha solution as (piranha solution) is cleaned.
After having pre-processed, by the silane coupler of 1~5% mass concentration be added to the first organic solvent (herein for One kind in the absolute methanol of 99% concentration, ethanol, normal propyl alcohol, isopropanol) in, then transparent base immersion is wherein lived Change, the active group of reaction is may participate in transparent substrate surface grafting.Described active group is to contain unsaturated functional group Acryloyl-oxy based structures.
Second step, according to percentage by weight, second is added to by 0.5~10% nano particle and 2~6% silane couplers Plant in organic solvent, reaction is hydrolyzed in the environment of pH 3~9, generate the dispersion liquid containing reactive nanoparticles.
Nano particle of the present invention includes sapphire, silicon nitride, white carbon, carborundum, silica, aluminum oxide, oxygen Change zirconium, titanium oxide, frit, silica glass, receive lime glass, single element or multielement oxide, such as Al2O3、ITO、 SnO2、SiO2、TiO2、ZrO2、ZnO、Bi2O3、V2O5, ZnS, CoO, CoFeO, MnFeO or BaFeO.Any one is more kinds of The composition of nano particle all alterables, and do not require that all nano particles are constituted including identical.Nano particle, which can have, appoints Shape of anticipating and surface texture.The structure and aggregation pattern alterable of nano particle, and the geometrical morphology and/or structure of the present invention, Pattern can be spherical, oval, polyhedron, sheet, it is many it is empty, crystal class formation is presented, nano grain surface can be smooth , it is coarse, orderly, unordered or patterning.Nano particle can be of different sizes or be distributed, or for one kind Size or distribution, the average diameter of nano particle is 5 nanometers~10000 nanometers, preferably 10~100nm.
The addition of described nano particle is preferably 1~8%.
Silane R of the present invention1nSi(OR2)4-n, wherein n=0~2;R1Can be CnH2n-1The alkane of (n=1~18) Base, preferably be selected from tetraethoxysilane, MTMS, propyl trimethoxy silicane, octadecyl trimethoxysilane, 3- methyl allyl acyloxypropyl trimethoxysilanes, 3- methacryloxypropyls triethoxysilane, 3- methacryloxypropyls Hydroxypropyl methyl dimethoxysilane, 3- methacryloxypropyls methyldiethoxysilane, VTES, second Alkenyl trimethoxy silane, vinyl three-(2- methoxyethoxies)-silane, 3- aminopropyl triethoxysilanes, 3- aminopropyls three Methoxy silane, N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, N- (2- aminoethyls) -3- aminopropyl-triethoxy silicon Alkane, 3- aminopropyltriethoxies dimethoxysilane, N- normal-butyl -3- aminopropyl trimethoxysilanes, N- normal-butyl -3- aminopropyls three Ethoxysilane, 3- ureas propyl trimethoxy silicane, 3- diethylin propyl trimethoxy silicane, 3- (oxygen of 2,3- epoxies third) third Base trimethoxy silane, 3- (oxygen of 2,3- epoxies third) propyl-triethoxysilicane, 3- (oxygen of 2,3- epoxies third) hydroxypropyl methyl diformazan One or more in TMOS, 3- (oxygen of 2,3- epoxies third) hydroxypropyl methyl diethoxy silane.
Described silane is a kind of silane containing acryloxy, preferably γ-(methacryloxypropyl) propyl trimethoxy Silane (the entitled KH570 of business) or 3- methacryloxypropyls methyl dimethoxysilane (the entitled KH572 of business) conduct The coupling agent of photocuring, effect of the silane coupler in this reaction system is extremely important, nano particle and transparent base, Connecting bridge beam action is played between reactive diluent, active fluorine monomer.
Second of organic solvent of the present invention, including benzene,toluene,xylene, styrene, butyl toluene, vinyl Toluene, carbon disulfide, tricresyl phosphate orthoresol, pentane, hexane, octane, normal hexane, hexamethylene, gasoline, kerosene, positive hexanone, hexamethylene Ketone, toluene cyclohexanone, chlorobenzene, chloroform, dichloro-benzenes, dichloromethane, chloroform, perchloromethane, dichloroethylene, trichloro ethylene, Perchloroethylene, methanol, ethanol, normal propyl alcohol, isopropanol, N, N- DMAAs, ether, expoxy propane, methyl formate, first Acetoacetic ester, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetic acid penta Ester, acetone, butanone, espeleton, methylisobutylketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethene Glycol ether, furans, acetonitrile, pyridine, phenol etc..
3rd step, adds active fluorine monomer, reactive diluent and light-initiated in the dispersion liquid containing reactive nanoparticles Agent, then homogenous application is solid in the case where obtaining UV energy effect on the transparent base after first step activating pretreatment Change obtains super-hydrophobic transparent wear-resistant coating.
By more than three step schemes transparent substrate surface obtain transparent hydrophobic structure as shown in figure 1, the superiors be containing Fluorine low-surface-energy layer, centre is nanoparticle structure layer, and orlop is that siloxanes base material is grafted layer.
The manner of application that the present invention is used includes:Dip-coating, spin coating, blade coating, spraying, physical vapour deposition (PVD), chemical vapor deposition Product, vacuum filter, evaporation, flame-spraying, electron spray, sprayed deposit, growth in situ, Microwave Irradiation Assisted Chemical vapour deposition process.
Described UV energy can be obtained from high-pressure sodium lamp, be generally used for the uv agent amount of irradiation 200~ 400mj/cm2In the range of.
Described active fluorine monomer is high activity, fluorinated volume is high and has in relatively low surface-active fluorine monomer, film forming procedure It can be enriched with coating surface, form fine and close, stable hydrophobic protection film layer.
Specifically, described active fluorine monomer, including perfluoroalkyl ethanol APEO, perfluoroalkyl ethanol polyoxy second Alkene ether, hexafluorobutyl acrylate, trifluoroethyl methacrylate, dodecafluoroheptyl methacrylate, hexafluoropropylene trimer, six Fluoropropene dimer, 4,4 '-(hexafluoroisopropylidenyl) diphenol, 4,4- (hexafluoro isopropyl alkene) two anhydride phthalic acids, ten difluoro enanthol, perfluor N-hexane, full-fluorine octyl sulfuryl fluoride, perfluoro-cyclicether, 2- (trifluoromethyl) acrylic acid, perfluorooctanol acrylate, perfluoro butyl second Base iodine, perfluor (2- methyl -3- oxa-s hexyl) fluoride, perfluorooctylethyl group acrylate, 1- iodine perfluoro decane, 2,5- are double The fluoro nonanoyl fluorine of (trifluoromethyl) -3,6- dioxas 11,2- (the iodo- tetrafluoro ethyoxyls of 2-) four fluoro ethyl vikanes, 2- perfluors Octyl group ethyl alcohol, perfluoro hexyl ethyl alcohol, PERFLUBRON, perfluoro caprylic acid, perfluor caproic acid, PFHB, 2- perfluoroalkyls Ethyl alcohol, 2- fluoroacrylic methyl esters, hexafluoroisopropanol, hexafluoro butanol, 3- perfluoro hexyls propyl alcohol, tetrafluoropropanol, 2,2,3,3,4, 4,5,5- octafluoro -1- amylalcohols, the fluoro- 1- propyl alcohol of 2,2,3,3,3- five, 2- (perfluoro capryl) ethylmethyl acrylate, 2- (perfluors Hexyl) ethylmethyl acrylate, perfluoro butyl ethyl propylene acid esters, 1H, 1H, 2H- perfluor -1- decene, triethoxy -1H, The fluoro- N- octyl groups silane of 1H, 2H, 2H- 13, perfluorobutylethyl alcohol, perfluorobutyl ethylene, Potassium Hexafluorophosphate, perfluor iodo fourth Alkane, 2- perfluor alkyl ethyl acrylates, perfluoro-hexyl iodide alkane, perfluoromethylcyclohexane (PFMCH), perfluor iodo-octane, 2- (perfluoro butyl) Ethylmethyl acrylate, perfluorooctylethyl group iodine, perfluorohexyl ethylene, perfluoro hexyl ethyl iodide.
Described active fluorine monomer preferably comprise functionality acryloxy perfluorinated monomers any one or it is a variety of.Especially Explanation, the compound containing acryloxy functionality can cause radical crosslinking to react by ultraviolet lighting, the freedom of activation Base reacts with the component for playing cross-linking reaction that can undergo free radical initiation.
It according to percentage by weight is 0.01~5% that the addition of described active fluorine monomer, which is, the amount of being preferably added to is 0.1~ 3%.
Described reactive diluent is the monomer that a class contains acryloxy functionality, can contain acryloxy, first Any one or a variety of functional groups of base acryloxy, vinyl and pi-allyl, participate in the coating UV film-forming later stages Cross-linking reaction, improves the performance such as intensity, adhesive force, weatherability of film layer after solidification.On the other hand, the acryloyl-oxy of low molecule amount The monomer of base functional group assigns UV solidifying film layers good translucency.
Reactive diluent of the present invention is neopentylglycol diacrylate, trimethylolpropane trimethacrylate, season Penta tetrol triacrylate, methyl methacrylate, methyl acrylate, two contracting 3 the third two liquor-saturated diacrylate, dipentaerythritol Six acrylate, hexanediyl ester, the propylene diluted acid ester of diethylene glycol phthalate two, neopentylglycol diacrylate, Pentaerythritol triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, different ice Piece acrylate, isobornyl methacrylate, DPG dipropyl acid esters, propoxylation trimethylolpropane tris acrylic acid In ester, season amylalcohol tetraacrylate, 1,3 butyleneglycol diacrylate any one or it is a variety of.
The addition of described reactive diluent is weight percentage 0.001~5%.
Reactive diluent of the present invention is being light-cured into the active group that is played in membrane process on connection glass baseplate, living Property nano grain surface is with perfluorinated monomers containing acryloxy into cross-linked network structure, and described reactive diluent content is preferably 0.05~5%, further preferred content is 0.1~3%.
Light trigger of the present invention is the key component in this reaction, and it plays decisive work to laser curing velocity With, it can be excited after UV energy is absorbed and cause photochemical transformations, reactive intermediate of the generation with initiation polymerizing power.
Light trigger of the present invention be 2- hydroxy-2-methyl -1- phenylacetones, 1- hydroxycyclohexyl phenyl ketones, 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone, the oxidation of 2,4,6- trimethylbenzoy-diphenies Phosphine, 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl esters, 2- dimethylamino -2- benzyls -1- [4- (4- morpholinyls) phenyl] -1- It is any one in butanone, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -1- acetone, methyl benzoylformate Kind.
The percentage by weight of the addition of described light trigger is 0.001~2%, preferably 0.01~1%.
Embodiment 1
Glass baseplate is immersed in Piranha washing lotion and cleaned, the organic solvent of remained on surface is removed, drying is continued to employ.Take 10 Part silane coupler is added in 100 parts of methanol, and clean glass baseplate is soaked wherein and 10h, alkyl is kept at room temperature Activate glass substrate surface structure.
5 parts of gas phase nano aluminum oxide are taken, size is distributed in 50~80nm, be added in 100 parts of methanol;Regulation in addition Solution ph is stirring reaction 12h under 3~4,30~45 DEG C of water bath conditions, finally gives the dispersion liquid of reactive nanoparticles.
50 parts of dispersion liquids are taken, 0.5 part of 2- perfluorooctylethyl group methacrylate, 1.5 parts of trimethylolpropane tris is added Acrylate, 0.25 part of 1- hydroxycyclohexyl phenyl ketone, is uniformly mixed, and coating fluid is made.
Made coating fluid is sprayed on the clear glass substrate surface activated in advance, to formation between 60~80 DEG C After coating is dried 10 minutes, with 300mj/cm2Ultraviolet irradiating dose dry coating is solidified, formed ultraviolet light Solidify super-hydrophobic transparent wear-resistant coating, coating transparent is as shown in Figure 3.
Embodiment 2
By glass baseplate alcohol solvent cleaning, drying, progress plasma in plasma washing machine is then placed in pre- Handle glass-faced construction.Take 10 parts of silane couplers to be added in 100 parts of ethanol, pretreated sheet glass is soaked at room temperature Steep 10h, alkyl activation glass sheet surface structure.
5 parts of nano-ZnO powder are taken, size is distributed in 20~40nm, be added in 100 parts of normal propyl alcohols, adjust in addition molten Liquid pH value is stirring reaction 24h under 3~4,40~50 DEG C of water bath conditions, finally gives the dispersion liquid of reactive nanoparticles.
50 parts of dispersion liquids are taken, 0.5 part of perfluoro butyl ethyl propylene acid esters, 1.5 parts of methyl methacrylates, 0.25 part is added 2- hydroxy-2-methyl -1- phenylacetones, are uniformly mixed, and coating fluid is made.
Made coating fluid is sprayed on the clear glass of alkylation, 10 are dried to the coating of formation between 60~80 DEG C After minute, with 300mj/cm2Ultraviolet irradiating dose dry coating is solidified, formed ultraviolet light solidification it is super-hydrophobic Transparent wear-resistant coating.
Embodiment 3
By glass baseplate alcohol solvent cleaning, drying, progress plasma in plasma washing machine is then placed in pre- Handle glass-faced construction.Take 10 parts of silane couplers to be added in 100 parts of methanol, clean sheet glass is soaked at room temperature 8h, alkyl activation glass sheet surface structure.
Take 5 parts of Nano-meter SiO_2s2Powder, size is distributed in 10~30nm, is added in 100 parts of ethyl acetates, adjusts in addition Solution ph is stirring reaction 12h under 4~5,40~50 DEG C of water bath conditions, finally gives the dispersion liquid of reactive nanoparticles.
Take 50 parts of dispersion liquids, add 0.5 part of 2- fluoroacrylic methyl ester, 1 part of dipentaerythritol acrylate, 0.5 part 2, 4,6- trimethylbenzoy-dipheny phosphine oxides, are uniformly mixed, and coating fluid is made.
The clear glass activated in advance is impregnated into coating fluid and soaked 10 minutes, then presss from both sides out right between 60~80 DEG C After the coating of formation is dried 5 minutes, with 300mj/cm2Ultraviolet irradiating dose dry coating is solidified, and shape Solidify super-hydrophobic transparent wear-resistant coating into ultraviolet light.
Embodiment 4
Sheet glass is immersed in Piranha washing lotion and cleaned, the organic solvent of remained on surface is removed, drying is continued to employ.Take 10 parts Silane coupler is added in 100 parts of methanol, and clean sheet glass is soaked into 10h, alkyl activation glass sheet surface knot at room temperature Structure.
6 parts of nanometer tin indium oxide powders are taken, size is distributed in 80~100nm, be added in 100 parts of isopropanols, in addition It is stirring reaction 18h under 8~9,40~50 DEG C of water bath conditions to adjust solution ph, finally gives the scattered of reactive nanoparticles Liquid.
Take 50 parts of dispersion liquids, add 1 part of 2- (perfluoro capryl) ethylmethyl acrylate, the liquor-saturated dipropyl of 1 part of two contracting 3 the third two Olefin(e) acid ester, 0.5 part of methyl benzoylformate, is uniformly mixed, and coating fluid is made.
The clear glass activated in advance is impregnated into coating fluid and soaked 10 minutes, then presss from both sides out right between 60~80 DEG C After the coating of formation is dried 5 minutes, with 300mj/cm2Ultraviolet irradiating dose dry coating is solidified, and shape Solidify super-hydrophobic transparent wear-resistant coating into ultraviolet light.
Embodiment 5
Sheet glass is immersed in Piranha washing lotion and cleaned, the organic solvent of remained on surface is removed, drying is continued to employ.Take 10 parts Silane coupler is added in 100 parts of methanol solutions, and clean sheet glass is soaked into 10h, alkyl activation sheet glass table at room temperature Face structure.
Take 6 parts of nanometer ZrO2Particle, size is distributed in 40~50nm, is added in 100 parts of ethanol, adjusts in addition molten Liquid pH value is stirring reaction 20h under 8~9,40~50 DEG C of water bath conditions, finally gives the dispersion liquid of reactive nanoparticles.
Take 50 parts of dispersion liquids, add 1 part of dodecafluoroheptyl methacrylate, 1.5 parts of dipentaerythritol acrylates, 0.5 part of 2- hydroxy-2-methyl -1- phenylacetone, is uniformly mixed, and coating fluid is made.
The clear glass activated in advance is impregnated into coating fluid and soaked 10 minutes, then presss from both sides out right between 60~80 DEG C After the coating of formation is dried 1 minute, with 300mj/cm2Ultraviolet irradiating dose dry coating is solidified, and shape Solidify super-hydrophobic transparent wear-resistant coating into ultraviolet light.Super-hydrophobic transparent is solidified to the ultraviolet light provided in above-described embodiment 1~5 Wear-resistant coating carries out performance test, as a result see the table below 1, the requirement of following technical indicator can be reached after tested.
The ultraviolet light of table 1 solidifies the performance test results of super-hydrophobic transparent wear-resistant coating
Project Testing standard Test result
Pencil hardness GB/T6739-2006 More than 1H
Adhesive force GB9286-98 0 grade
Contact angle GB/T 26490-2011 >150°
Roll angle GB/T 30447-2013 <5°
Translucency GB/T 2680-1994 >90%
Comparative example 1
The component selected by ultraviolet light solidification super-hydrophobic transparent wear-resistant coating described in this comparative example and institute in embodiment 1 The raw material components provided are identical, and it is differed only in is operated according to each step of scheme of embodiment 1, but in final step Take and the content of monomer of 2- fluoroacrylic methyl esters is kept to 0 part, other conditions keep constant.By this comparative example equally carry out 60~ 80 DEG C of heat drying, then carry out ultraviolet light curing reaction.As optical photograph it is easily observed that obtained by sample, as a result such as Fig. 4 institutes Show, the coating does not have ultra-hydrophobicity after ultraviolet light solidification process.
Comparative example 2
The component selected by ultraviolet light solidification super-hydrophobic transparent wear-resistant coating described in this comparative example and institute in embodiment 1 The raw material components provided are identical, and it is differed only in is carried out after equally operating according to the scheme of embodiment 1, to the activity in system It (is that a class is post-processed by hydrophilic aerosil through HMDS that nano particle, which changes Degussa R812s products into, Hydrophobic type fumed silica) after, same comparative example carries out carrying out ultraviolet light solidification after 60~80 DEG C of heat drying anti- Should.
Hardness of paint film is tested with pencil method to embodiment 1 and comparative example 2 according to national standard GB/T6739-2006.The test side Method is the assay method that hardness of film is represented using known hardness label.After tested, coating prepared in comparative example 2 test knot Fruit can not show a candle to the 1H hardness of prepared coating in embodiment 1 for 5B.This test result illustrates that reactive nanoparticles are applied overall Being chemically reacted in material with reactive diluent has obvious effect to lifting strength of coating, and R812s nanometers of gas outer silicon bags Coating hardness can not be effectively improved by wrapping up in the accumulation of one layer of methyl group in the coating of dry solidification only physically.
Obviously, above-described embodiment is only intended to clearly illustrate illustrates with making, and the not restriction to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or Among changing still in the protection domain of the invention.

Claims (8)

1. a kind of ultraviolet light solidifies the preparation method of super-hydrophobic transparent wear-resistant coating, it is characterised in that:Specific steps such as,
The first step, transparent base activating pretreatment:Transparent base is activated with silane-containing solution, can in transparent substrate surface grafting Participate in the active group of reaction;
Second step, according to percentage by weight, 0.5~10% nano particle and 2~6% silane couplers are added into second has In machine solvent, reaction is hydrolyzed in the environment of pH 3~9, the dispersion liquid containing reactive nanoparticles is generated;
3rd step, adds active fluorine monomer, reactive diluent and light trigger, so in the dispersion liquid containing reactive nanoparticles Homogenous application solidifies in the case where obtaining UV energy effect and obtained on the transparent base after first step activating pretreatment afterwards Super-hydrophobic transparent wear-resistant coating.
2. a kind of ultraviolet light according to claim 1 solidifies the preparation method of super-hydrophobic transparent wear-resistant coating, its feature exists In:Described activating pretreatment specifically,
Using plasma processing or Piranha solution cleaning transparent substrate surface;It is after having pre-processed, 1~5% mass is dense The silane coupler of degree is added in the first organic solvent, is then wherein activated transparent base immersion, in transparent base The active group of reaction is may participate on material surface grafting;Described active group is the acryloxy containing unsaturated functional group Structure.
3. a kind of ultraviolet light according to claim 2 solidifies the preparation method of super-hydrophobic transparent wear-resistant coating, its feature exists In:The first described organic solvent is in absolute methanol, ethanol, normal propyl alcohol or the isopropanol of 99% weight percent concentration It is a kind of.
4. a kind of ultraviolet light according to claim 1 solidifies the preparation method of super-hydrophobic transparent wear-resistant coating, its feature exists In:Nano particle described in second step includes sapphire, silicon nitride, white carbon, carborundum, silica, aluminum oxide, oxidation Zirconium, titanium oxide, frit, silica glass, receive lime glass, single element or multielement oxide, the average diameter of nano particle It it is 5 nanometers~10000 nanometers, the addition of described nano particle is 1~8%.
5. a kind of ultraviolet light according to claim 1 solidifies the preparation method of super-hydrophobic transparent wear-resistant coating, its feature exists In:Described UV energy is obtained from high-pressure sodium lamp, and uv agent amount is in 200~400mj/cm2In the range of.
6. a kind of ultraviolet light according to claim 1 solidifies the preparation method of super-hydrophobic transparent wear-resistant coating, its feature exists In:It according to percentage by weight is 0.01~5% that the addition of described active fluorine monomer, which is,;The addition of described reactive diluent Measure as weight percentage 0.001~5%;The percentage by weight of the addition of described light trigger is 0.001~2%.
7. a kind of ultraviolet light according to claim 1 or 6 solidifies the preparation method of super-hydrophobic transparent wear-resistant coating, its feature It is:It according to percentage by weight is 0.1~3% that the addition of described active fluorine monomer, which is,;The reactive diluent content is 0.05~5%;The percentage by weight of the addition of described light trigger is 0.01~1%.
8. a kind of ultraviolet light solidifies super-hydrophobic transparent wear-resistant coating, it is characterised in that:The superiors of the coating are fluorine-containing low table Face ergosphere, centre is nanoparticle structure layer, and orlop is that siloxanes base material is grafted layer.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109013233A (en) * 2018-08-03 2018-12-18 武汉理工大学 A method of quaternary ammonium salt coating is prepared in metal surface using self assembly
CN109097984A (en) * 2018-08-22 2018-12-28 安徽利思达网业有限公司 A kind of preparation method of the super-hydrophobic polyester cloth of water-oil separating
CN109851738A (en) * 2018-12-04 2019-06-07 广州市金铂尔化工有限公司 A kind of preparation method of fluorinated silicone modified urea-based compound
CN110511415A (en) * 2019-08-30 2019-11-29 华南理工大学 Using epoxy soybean oil acrylate as waterproof starch film of coating and preparation method thereof
CN112038421A (en) * 2020-08-19 2020-12-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of photo-induced solar cell surface self-cleaning coating
EP3771734A3 (en) * 2019-08-01 2021-04-14 The Boeing Company Transparent hydrophobic and icephobic compositions, coatings, and methods
CN112812611A (en) * 2020-12-30 2021-05-18 中科院长春应化所黄埔先进材料研究院 Preparation method of conductive coating
CN113980501A (en) * 2021-11-19 2022-01-28 国网江苏省电力有限公司电力科学研究院 Photo-induced front-line polymerized graphene super-hydrophobic anticorrosive coating and preparation method thereof
CN114634725A (en) * 2022-03-24 2022-06-17 九牧厨卫股份有限公司 Preparation method of stainless steel antifouling film and 8K mirror surface antifouling stainless steel plate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1820058A (en) * 2003-05-20 2006-08-16 帝斯曼知识产权资产管理有限公司 Hydrophobic coatings comprising reactive nano-particles
CN101250340A (en) * 2008-04-03 2008-08-27 惠州市长润发涂料有限公司 Ultraviolet light curing fingerprint resistant paint
CN102911530A (en) * 2012-11-07 2013-02-06 北京化工大学 Preparation method capable of realizing chemical blending of modified nano silicon dioxide particles in acrylate monomer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1820058A (en) * 2003-05-20 2006-08-16 帝斯曼知识产权资产管理有限公司 Hydrophobic coatings comprising reactive nano-particles
CN101250340A (en) * 2008-04-03 2008-08-27 惠州市长润发涂料有限公司 Ultraviolet light curing fingerprint resistant paint
CN102911530A (en) * 2012-11-07 2013-02-06 北京化工大学 Preparation method capable of realizing chemical blending of modified nano silicon dioxide particles in acrylate monomer

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
山边正显 等: "《含氟材料的研究开发》", 30 June 2003, 华东理工大学出版社 *
朱万强: "《涂料基础教程》", 30 June 2012, 西南交通大学出版社 *
章基凯: "《有机硅材料》", 31 October 1999, 中国物资出版社 *
翟庆洲: "《纳米技术》", 31 March 2006, 兵器工业出版社 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109013233A (en) * 2018-08-03 2018-12-18 武汉理工大学 A method of quaternary ammonium salt coating is prepared in metal surface using self assembly
CN109097984A (en) * 2018-08-22 2018-12-28 安徽利思达网业有限公司 A kind of preparation method of the super-hydrophobic polyester cloth of water-oil separating
CN109097984B (en) * 2018-08-22 2020-11-24 安徽利思达网业有限公司 Preparation method of super-hydrophobic polyester filter cloth for oil-water separation
CN109851738A (en) * 2018-12-04 2019-06-07 广州市金铂尔化工有限公司 A kind of preparation method of fluorinated silicone modified urea-based compound
CN109851738B (en) * 2018-12-04 2021-03-26 广东坚派新材料有限公司 Preparation method of fluorine-silicon modified carbamido compound
EP3771734A3 (en) * 2019-08-01 2021-04-14 The Boeing Company Transparent hydrophobic and icephobic compositions, coatings, and methods
EP4303278A3 (en) * 2019-08-01 2024-04-10 The Boeing Company Transparent hydrophobic and icephobic compositions, coatings, and methods
CN110511415A (en) * 2019-08-30 2019-11-29 华南理工大学 Using epoxy soybean oil acrylate as waterproof starch film of coating and preparation method thereof
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CN112812611A (en) * 2020-12-30 2021-05-18 中科院长春应化所黄埔先进材料研究院 Preparation method of conductive coating
CN113980501A (en) * 2021-11-19 2022-01-28 国网江苏省电力有限公司电力科学研究院 Photo-induced front-line polymerized graphene super-hydrophobic anticorrosive coating and preparation method thereof
CN114634725A (en) * 2022-03-24 2022-06-17 九牧厨卫股份有限公司 Preparation method of stainless steel antifouling film and 8K mirror surface antifouling stainless steel plate

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