CN106189642B - Ultraviolet light curing anti fogging coating composite - Google Patents
Ultraviolet light curing anti fogging coating composite Download PDFInfo
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- CN106189642B CN106189642B CN201610607744.9A CN201610607744A CN106189642B CN 106189642 B CN106189642 B CN 106189642B CN 201610607744 A CN201610607744 A CN 201610607744A CN 106189642 B CN106189642 B CN 106189642B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention provides a kind of ultraviolet light curing anti fogging coating composites；The composition includes each component of following parts by weight: 40~80 parts of hydrophily light-cured resin；15~45 parts of hydrophobicity light-cured resin；5~15 parts of hydrophily photo-curing monomer；1~5 part of photoinitiator；0.01-0.05 parts of auxiliary agent；The composition further includes solvent, and the weight of solvent is 2-4 times of other component weights.Ultraviolet anti-fog coating provided by the invention is after ultraviolet light solidifies, water-resistance property of coating can improve, while have lasting anti-fog performance, and hardness of film is high, resistance to wiping is good, it is highly suitable to be applied for the field with antifog requirement, such as car light, windshield, bathroom mirror, optical lens material.
Description
Technical field
The invention belongs to field of photo-curing coatings, and in particular to a kind of cured anti fogging coating composite of ultraviolet light.
Background technique
Vapor in air will condense into small drop and mist formation when temperature is lower than dew point.It is this undesirable
Influence frequently occurs in window, bathroom mirror, glasses, swimming and Lunettes, windshield, optical instrument camera lens, car light, refers to
Showing lamp, agricultural film etc., these live on the transparent material being closely related with us.Transparent material surface water droplet atomization as a result, not only
Light transmittance decline influences vision, generates harm sometimes, such as when droplet condenses in such as infrared optics microscope rigorous analysis
When on the lens surface of instrument, the accuracy of analysis can be reduced.And when droplet condenses on solar battery light-transmitting plate, it causes
Make the reduction of solar absorption efficiency, so that being unfavorable for solar cell device gives full play to due effect.
In order to solve these problems, can generally hydrophobic or hydrophilic treated be carried out to material surface.Hydrophobic common perfluorinated resin
Class, one side price is higher, and on the other hand the resinoid is generally softer, wears no resistance, while its hydrophobic property also leads to its table
Face easily adsorbs greasy dirt and dust, the effect not reached requirement instead.And organic hydrophilic coating price itself is inexpensively, it can also
Its wearability is improved by some modifications.Using organic hydrophilic coating compared to hydrophobic coating processing method not only construction party
Just, and it is cheap.
It is concentrated mainly on super hydrophilic research both at home and abroad now, as coating surface introducing can form the group such as carboxylic of hydrogen bond
Base, amino, sulfydryl, hydroxyl or some ionic groups: carboxylate radical, sulfonate radical, ammonium root, phosphate radical etc., when these groups of introducing
Or when ion, the surface of coating reaches super hydrophilic state, sprawls after moisture condensation in substrate surface height, forms one layer
Even moisture film eliminates tiny drops of water and achievees the purpose that antifog to the diffusing reflection of light.Super hydrophilic approach master is prepared at present
If passing through physical blending, Chemical modification, chemical bond connection.Anti-fog coating currently on the market continue anti-fog performance with it is resistance to
Mill performance can not balance, and after a period of use, anti-fog performance just declines obviously.
Domestic patent CN 102795791A discloses a kind of wear-resisting super hydrophilic antireflecting coating, and the coating by depositing repeatedly
Diallyl dimethyl ammoniumchloride and kayexalate prepare 5~20 layers of double-layer structure, then poly- by deposition repeatedly
Diallyldimethylammonium chloride and the SiO for being 10~40nm containing partial size2The suspension of nano spherical particle prepares 3~8 layers
Double-layer structure, then 100~300s system is quenched by 100~140 DEG C of hydro-thermal process and in 600~800 DEG C of Muffle furnace
Coating needed for obtaining.Although coating made from this method can reach the high rigidity of 5H and water contact angle also very little, step is complicated,
Lasting anti-fog properties general, energy consumption is high, only has the user of special high request suitable performance.
Domestic patent CN102086348A discloses a kind of preparation side of urethane cures acrylate anti-fog coating
Method, the coating is by hydrophilic acrylic resin, enclosed type polyethers isocyanate curing agent and catalyst dibutyltin dilaurylate
Composition.The coating hardness is greater than 2H, and wear-resisting property is good, but lasting anti-fog performance is general, and solidification process needs the time longer, and needs
Stage curing (50 DEG C~120 DEG C), the process is more complicated.
If anti-fog coating protracted hydrophilicity on the market can be excellent, wear-resisting property just not can guarantee；It is wear-resisting in hardness on the contrary
While excellent, persistently anti-fog effect is general.To overcome traditional anti-fog coating on the market to continue anti-fog performance and wear-resisting property
Contradiction, urgent need, which is developed, a kind of has both hydrophily and wear-resisting anti-fog coating.
Summary of the invention
For the defects in the prior art, the object of the present invention is to provide a kind of ultraviolet lights to solidify hydrophilic antifogging coating.It should
Gained coating after coating photocuring, the splendid and lasting anti-fog performance of hydrophily is outstanding, while will not lose wear-resisting property, therefore gram
The some drawbacks for having taken anti-fog coating on the market, are highly suitable to be applied for the field with antifog requirement, and such as car light, keep out the wind glass
Glass, bathroom mirror, optical lens material etc..
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention provides a kind of ultraviolet light curing anti fogging coating composite, the composition include as each component:
The composition further includes solvent, and the weight of solvent is 2-4 times of other component weights.
If hydrophily light-cured resin is crossed higher than 80 parts, when hydrophobicity light-cured resin is lower than 15 parts, hydrophily photocuring
When monomer is higher than 15 parts, gained film hydrophily is very good after the final photocuring of gained, and it is poor to will lead to final water-resistance property of coating, continues
Anti-fog properties difference；If hydrophily light-cured resin is lower than 40 parts, hydrophobicity light-cured resin is higher than 45 parts, hydrophily photo-curing monomer
When lower than 5 parts, it will lead to that final film hydrophily is too poor, and initial water contact is larger, not anti-fog properties.
If photoinitiator is higher than 5 parts, a large amount of free radicals can be generated under ultraviolet lighting, are formed after leading to gained paint solidification
Final three-dimensional network polymer molecular weight it is low, cause film more crisp, adhesive force can be deteriorated, while can also improve coating cost；
It if photoinitiator is lower than 1 part, can generate free radicals under ultraviolet lighting insufficient, lead to the resin and monomer of the not no photopolymerization of residual
Content is more, causes final film surface drying bad, tacky, cannot use at all.If auxiliary agent, the present invention refers to polymerization inhibitor, is lower than
At 0.01 part, the poor storage stability of coating；When higher than 0.05 part, needing to improve ultraviolet ray intensity can just be such that coating reaches completely
To photocuring, under common luminous intensity, there is the danger that cannot be fully cured.
When the amount of solvent is higher than monomer and 4 times of total resin weight, coating is too dilute, and coating thickness is too low, leads to final film
Hardness it is too low, wear-resisting variation.If the amount of solvent is lower than monomer and 2 times of total resin weight, viscosity of the coating is too big, is easy to cause
Film levelling is bad, and coating thickness is too thick, also brings along the incomplete problem of solidification.
Preferably, the hydrophily light-cured resin is pure acrylic resin.
Preferably, the pure acrylic resin is the acrylate that side chain contains unsaturated double-bond.
Preferably, the preparation method of the pure acrylic resin includes the following steps:
S1, in a solvent, is added monomer and initiator is reacted；
S2, add glycidyl methacrylate (GMA), catalyst and polymerization inhibitor reaction to get.
Preferably, in step S1, the monomer includes that molar ratio is single shown in 2~5:2~4:0~3:2~3 formula (I)
Monomer II shown in body I, formula (II), hy-droxybutyl (HBA), acrylic acid (AA)；
The monomer I is the allyl ether of the nonionic surfactant containing terminal hydroxy group, and monomer II is containing end methoxy
The methacrylate of the nonionic surfactant of base.
Preferably, the molar ratio of the monomer and glycidyl methacrylate is 1:1.
Preferably, the solvent is glycol monoethyl ether；The initiator is azodiisobutyronitrile；The catalyst is benzyl
Base trimethyl ammonium chloride；The polymerization inhibitor is p-hydroxyanisole.
Preferably, the weight ratio of the monomer and solvent is 1:2, and the additional amount of initiator is the 1% of total monomer weight.
Preferably, the dosage of the catalyst is the 0.1% of monomer and GMA total weight, the dosage of polymerization inhibitor be monomer and
The 0.3% of GMA total weight.
Preferably, in step S1, the reaction temperature is 80-85 DEG C；In step S2, the reaction temperature is 90-95 DEG C,
React 2h.
It is highly preferred that the preparation method of the pure acrylic resin specifically: at room temperature, in glycol monoethyl ether solvent
In, the 20% of monomer (monomer I, monomer II, HBA, AA) and initiator azodiisobutyronitrile (AIBN) is put into, increases temperature extremely
80-85 degree reacts 0.5 hour.Then the mixture of remaining monomer and initiator is added dropwise in 2 hours, after dripping, continues anti-
It answers 3 hours.GMA, benzyltrimethylammonium chloride catalyst and a small amount of polymerization inhibitor p-hydroxyanisole are finally added, temperature is increased
Reaction 2 hours is carried out to 90-95 degree, is cooled to room temperature.
The double bond unsaturated group of the hydrophily photocuring pure acrylic resin prepared using the above method is in side chain, therefore
Under ultraviolet light, hydrophobic network easily is formed very much with hydrophobicity light-cured resin crosslinking curing.It can repel equally in side chain
Hydrophilic parts be gathered in film coated surface, therefore the good hydrophilic property on surface, the network structure partially hydrophobic inside film is good.
There is excellent hydrophilicity so as to cause film, the condensation vapor in air can be made to be formed on its surface moisture film rather than water
Drop has good anti-fog performance.In addition there is enough hydrophobic networks inside film, water or vapor will not be caused to make film
Bubble falls, so, have protracted hydrophilicity good, has and continue anti-fog performance.
Preferably, the hydrophobicity light-cured resin includes urethane acrylate of the degree of functionality higher than 6, is more than or equal to 2
At least one of the polyester acrylate of epoxy acrylate, degree of functionality higher than 4.
Preferably, the hydrophily photo-curing monomer is polymerisable surfactant, is selected from 3- propyl sulfonic acid metering system
Sour potassium, methacrylic acid hydroxypropyl sulfonic acid sodium, methacrylic acid trimethyl ammonium chloride, methacrylic acid polyoxyethylene sodium phosphate,
One of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether ammonium sulfate
Or several combination.Such component can substantially reduce water contact angle, and may participate in photocuring reaction, have splendid lasting parent
Water effect.
Preferably, the photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- propyl ketone, 1- [4- (2- hydroxy ethoxy) -
Phenylene]-2- hydroxyl-2 ', 2 '-dimethyl ethyl ketones, 1- hydroxycyclohexyl phenyl ketone, 2- methyl-1-(4- methyl mercapto phenyl)-
At least one of 2- morpholine -1- acetone.
Preferably, the auxiliary agent is at least one of levelling agent, polymerization inhibitor；The solvent is ethyl acetate, acetic acid fourth
Ester, isopropanol, n-butanol, glycol monoethyl ether, butyl glycol ether, propylene glycol monomethyl ether, in propylene glycol methyl ether acetate at least
It is a kind of.
It is highly preferred that the solvent is ethyl acetate, butyl acetate and isopropanol, three's weight ratio is 2:3:1.
The present invention also provides a kind of preparation methods of ultraviolet light curing anti fogging coating composite, and the method includes following
Step:
Accurately weigh each component, by hydrophily light-cured resin, hydrophobicity light-cured resin, hydrophily photo-curing monomer and
Solvent mixing；Photoinitiator and auxiliary agent are added, mixing obtains.
The prior art is compared, the present invention have it is following the utility model has the advantages that
1, the present invention is because using the excellent hyperbranched type light-cured resin (pure acrylic resin) of hydrophily and polymerizable table
Face activating agent cooperates the hydrophobicity light-cured resin of high-ranking official, and formation hydrophily and hydrophobic parts are crosslinked netted after photocuring
Structure.Wherein hydrophilic segment has excellent hydrophilicity, and water droplet is caused easily to sprawl to form moisture film without hazing on coating.
Hydrophobic part plays the role of anchor point in the coating, and crosslink density increases, and guarantees that coating will not be because when encountering a large amount of water
It is swollen and dissolves, not only can guarantee lasting anti-fog performance but also wear-resisting property can be improved.
2, ultraviolet light curing anti fogging coating composite prepared by the present invention is coated on plastic basis material surface, after photocuring,
The initial stage water contact angle of gained film is less than 10 degree, and after water impregnates 48 hours, water contact angle is less than 35 degree.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Ultraviolet light curing anti fogging coating composite described in following embodiment and comparative examples the preparation method is as follows:
Accurately weigh each component, by hydrophily light-cured resin, hydrophobicity light-cured resin, hydrophily photo-curing monomer and
Solvent mixes 30 minutes；Photoinitiator and auxiliary agent are added, mixes 10 minutes, obtains.
Solvent described in following embodiment and comparative examples is ethyl acetate, butyl acetate and isopropanol, and three's weight ratio is
2:3:1.The weight of solvent is 3 times of other components total weight in embodiment and comparative example, is omitted here other in 2-4 times
Range.
Embodiment 1
Present embodiments provide a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.
The synthetic method of pure acrylic resin described in the present embodiment is as follows:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added glycol monoethyl ether
(20 grams), first the monomer, initiator A IBN (0.21 gram) of addition 20% and the mixture of glycol monoethyl ether (40 grams), increase
Temperature is reacted 0.5 hour to 80-85 degree.Then the mixed of remaining monomer, initiator and glycol monoethyl ether is added dropwise in 2 hours
Object is closed, after dripping, the reaction was continued 3 hours.The monomer include: monomer I (9.7 grams, 12.5mmol), monomer II (8.9 grams,
8.3mmol), HBA (1.2 grams, 8.3mmmol), AA (0.9 gram, 12.5mmol).
Finally add GMA (9.3 grams, 12.5mmol), benzyltrimethylammonium chloride catalyst (0.03 gram) and polymerization inhibitor
P-hydroxyanisole (0.09 gram) increases temperature to 90-95 degree and carries out reaction 2 hours, is cooled to room temperature and obtains thick pale yellow
Liquid.Then it is precipitated with n-hexane, then is dried in vacuo through 50 degree and obtains within 12 hours gained hydrophily ultraviolet light solidification pure C
Olefin(e) acid resin.
Embodiment 2
Present embodiments provide a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.
The synthetic method of pure acrylic resin described in the present embodiment is as follows:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added glycol monoethyl ether
(20 grams), first the monomer, initiator A IBN (0.24 gram) of addition 20% and the mixture of glycol monoethyl ether (40 grams), increase
Temperature is reacted 0.5 hour to 80-85 degree.Then the mixed of remaining monomer, initiator and glycol monoethyl ether is added dropwise in 2 hours
Object is closed, after dripping, the reaction was continued 3 hours.The monomer include: monomer I (12.9 grams, 16.6mmol), monomer II (8.9 grams,
8.3mmol), HBA (1.2 grams, 8.3mmmol), AA (0.6 gram, 8.3mmol).
Finally add GMA (6.2 grams, 16.6mmol), benzyltrimethylammonium chloride catalyst (0.03 gram) and polymerization inhibitor
P-hydroxyanisole (0.09 gram) increases temperature to 90-95 degree and carries out reaction 2 hours, is cooled to room temperature and obtains thick pale yellow
Liquid.Then it is precipitated with n-hexane, then is dried in vacuo through 50 degree and obtains within 12 hours gained hydrophily ultraviolet light solidification pure C
Olefin(e) acid resin.
Embodiment 3
Present embodiments provide a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.
The synthetic method of pure acrylic resin described in the present embodiment is as follows:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added glycol monoethyl ether
(25 grams), first the monomer, initiator A IBN (0.26 gram) of addition 20% and the mixture of glycol monoethyl ether (40 grams), increase
Temperature is reacted 0.5 hour to 80-85 degree.Then the mixed of remaining monomer, initiator and glycol monoethyl ether is added dropwise in 2 hours
Object is closed, after dripping, the reaction was continued 3 hours.The monomer are as follows: monomer I (6.4 grams, 8.3mmol), II (17.8 grams,
16.6mmol), HBA (1.2 grams, 8.3mmmol), AA (0.6 gram, 8.3mmol).
Finally add GMA (6.1 grams, 8.3mmol), benzyltrimethylammonium chloride catalyst (0.032 gram) and polymerization inhibitor
P-hydroxyanisole (0.096 gram) increases temperature to 90-95 degree and carries out reaction 2 hours, is cooled to room temperature and obtains thick pale yellow
Liquid.Then it is precipitated with n-hexane, then is dried in vacuo through 50 degree and obtains within 12 hours gained hydrophily ultraviolet light solidification pure C
Olefin(e) acid resin.
Embodiment 4
Present embodiments provide a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.
The synthetic method of pure acrylic resin described in the present embodiment is as follows:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added glycol monoethyl ether
(35 grams), first the monomer, initiator A IBN (0.36 gram) of addition 20% and the mixture of glycol monoethyl ether (50 grams), increase
Temperature is reacted 0.5 hour to 80-85 degree.Then the mixed of remaining monomer, initiator and glycol monoethyl ether is added dropwise in 2 hours
Object is closed, after dripping, the reaction was continued 3 hours.The monomer are as follows: monomer I (16.1 grams, 20.8mmol), monomer II (13.4 grams,
12.4mmol), AA (0.6 gram, 8.3mmol).
Finally add GMA (6.1 grams, 8.3mmol), benzyltrimethylammonium chloride catalyst (0.042 gram) and polymerization inhibitor
P-hydroxyanisole (0.13 gram) increases temperature to 90-95 degree and carries out reaction 2 hours, is cooled to room temperature and obtains thick pale yellow
Liquid.Then it is precipitated with n-hexane, then is dried in vacuo through 50 degree and obtains within 12 hours gained hydrophily ultraviolet light solidification pure C
Olefin(e) acid resin.
Embodiment 5
Present embodiments provide a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.
The synthetic method of pure acrylic resin described in the present embodiment is as follows:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added glycol monoethyl ether
(40 grams), first the monomer, initiator A IBN (0.42 gram) of addition 20% and the mixture of glycol monoethyl ether (70 grams), increase
Temperature is reacted 0.5 hour to 80-85 degree.Then the mixed of remaining monomer, initiator and glycol monoethyl ether is added dropwise in 2 hours
Object is closed, after dripping, the reaction was continued 3 hours.The monomer are as follows: monomer I (19.3 grams, 24.9mmol), monomer II (17.8 grams,
16.6mmol), HBA (3.6 grams, 24.9mmol) AA (1.2 grams, 16.6mmol).
Finally add GMA (12.2 grams, 16.6mmol), benzyltrimethylammonium chloride catalyst (0.054 gram) and polymerization inhibitor
Agent p-hydroxyanisole (0.16 gram) increases temperature to 90-95 degree and carries out reaction 2 hours, is cooled to room temperature and obtains light yellow glue
Thick liquid.Then it is precipitated with n-hexane, then is dried in vacuo through 50 degree that obtain within 12 hours gained hydrophily ultraviolet light solidification pure
Acrylic resin.
Embodiment 6
Present embodiments provide a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.
The synthetic method of pure acrylic resin described in the present embodiment is as follows:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added glycol monoethyl ether
(40 grams), first the monomer, initiator A IBN (0.23 gram) of addition 20% and the mixture of glycol monoethyl ether (60 grams), increase
Temperature is reacted 0.5 hour to 80-85 degree.Then the mixed of remaining monomer, initiator and glycol monoethyl ether is added dropwise in 2 hours
Object is closed, after dripping, the reaction was continued 3 hours.The monomer are as follows: monomer I (12.9 grams, 16.6mmol), monomer II (8.9 grams,
8.3mmol), HBA (0.6 gram, 4.15mmmol), AA (0.9 gram, 12.5mmol).
Finally add GMA (9.3 grams, 12.5mmol), benzyltrimethylammonium chloride catalyst (0.033 gram) and polymerization inhibitor
P-hydroxyanisole (0.099 gram) increases temperature to 90-95 degree and carries out reaction 2 hours, is cooled to room temperature and obtains thick pale yellow
Liquid.Then it is precipitated with n-hexane, then is dried in vacuo through 50 degree and obtains within 12 hours gained hydrophily ultraviolet light solidification pure C
Olefin(e) acid resin.
Comparative example 1
This comparative example provides a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.
The synthetic method of pure acrylic resin described in this comparative example is as follows:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added glycol monoethyl ether
(32 grams), first the monomer, initiator A IBN (0.34 gram) of addition 20% and the mixture of glycol monoethyl ether (40 grams), are added
Monomer I (3.2 grams, 4.2mmol), II (30.1 grams, 10.4mmol), HBA (0.6 gram, 4.2mmmol), AA (0.15 gram,
2.1mmol), temperature is increased to 80-85 degree, is reacted 0.5 hour.Then remaining monomer, initiator and second two are added dropwise in 2 hours
The mixture of alcohol monomethyl ether, after dripping, the reaction was continued 3 hours.Finally add GMA (1.6 grams, 2.1mmol), benzyl front three
Ammonium chloride catalyst (0.035 gram) and polymerization inhibitor p-hydroxyanisole (0.11 gram) increase temperature to 90-95 degree and are reacted
It 2 hours, is cooled to room temperature and obtains pale yellow viscous liquid.Then it is precipitated with n-hexane, then small through 50 degree of vacuum drying 12
When obtain gained hydrophily ultraviolet light solidification pure acrylic resin.
Comparative example 2
This comparative example provides a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.
The synthetic method of pure acrylic resin described in this comparative example is as follows:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added glycol monoethyl ether
(35 grams), first the monomer, initiator A IBN (0.50 gram) of addition 20% and the mixture of glycol monoethyl ether (58 grams), increase
Temperature is reacted 0.5 hour to 80-85 degree.Then the mixed of remaining monomer, initiator and glycol monoethyl ether is added dropwise in 2 hours
Object is closed, after dripping, the reaction was continued 3 hours.The monomer be monomer I (16.3 grams, 21.0mmol), monomer II (12.0 grams,
4.2mmol), AA (1.2 grams, 16.6mmol).
Finally add GMA (12.2 grams, 16.6mmol), benzyltrimethylammonium chloride catalyst (0.042 gram) and polymerization inhibitor
Agent p-hydroxyanisole (0.13 gram) increases temperature to 90-95 degree and carries out reaction 2 hours, is cooled to room temperature and obtains light yellow glue
Thick liquid.Then it is precipitated with n-hexane, then is dried in vacuo through 50 degree that obtain within 12 hours gained hydrophily ultraviolet light solidification pure
Acrylic resin.
Comparative example 3
This comparative example provides a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.
The synthetic method of pure acrylic resin described in this comparative example is as follows:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added glycol monoethyl ether
(43 grams), first the monomer, initiator A IBN (0.45 gram) of addition 20% and the mixture of glycol monoethyl ether (60 grams), increase
Temperature is reacted 0.5 hour to 80-85 degree.Then the mixed of remaining monomer, initiator and glycol monoethyl ether is added dropwise in 2 hours
Object is closed, after dripping, the reaction was continued 3 hours.The monomer be monomer I (19.3 grams, 24.9mmol), monomer II (24.1 grams,
4.15mmol), HBA (0.6 gram, 4.15mmmol), AA (0.6 gram, 8.3mmol).
Finally add GMA (6.1 grams, 8.3mmol), benzyltrimethylammonium chloride catalyst (0.051 gram) and polymerization inhibitor
P-hydroxyanisole (0.15 gram) increases temperature to 90-95 degree and carries out reaction 2 hours, is cooled to room temperature and obtains thick pale yellow
Liquid.Then it is precipitated with n-hexane, then is dried in vacuo through 50 degree and obtains within 12 hours gained hydrophily ultraviolet light solidification pure C
Olefin(e) acid resin.
Comparative example 4
This comparative example provides a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.
The synthetic method of pure acrylic resin described in this comparative example is as follows:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added glycol monoethyl ether
(20 grams), first the monomer, initiator A IBN (0.23 gram) of addition 20% and the mixture of glycol monoethyl ether (45 grams), increase
Temperature is reacted 0.5 hour to 80-85 degree.Then the mixed of remaining monomer, initiator and glycol monoethyl ether is added dropwise in 2 hours
Object is closed, after dripping, the reaction was continued 3 hours.The monomer are as follows: monomer I (3.2 grams, 4.15mmol), monomer II (17.8 grams,
16.6mmol), HBA (1.2 grams, 8.3mmmol), AA (0.9 gram, 12.5mmol).
Finally add GMA (9.3 grams, 12.5mmol), benzyltrimethylammonium chloride catalyst (0.032 gram) and polymerization inhibitor
P-hydroxyanisole (0.096 gram) increases temperature to 90-95 degree and carries out reaction 2 hours, is cooled to room temperature and obtains thick pale yellow
Liquid.Then it is precipitated with n-hexane, then is dried in vacuo through 50 degree and obtains within 12 hours gained hydrophily ultraviolet light solidification pure C
Olefin(e) acid resin.
Comparative example 5
This comparative example provides a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.The synthetic method of pure acrylic resin described in this comparative example is same as Example 2.
Comparative example 6
This comparative example provides a kind of ultraviolet light curing anti fogging coating composite, each component and its weight of the composition
Number is as shown in table 1.The synthetic method of pure acrylic resin described in this comparative example is same as Example 2.
Performance test
Using PET as substrate, coating (30% contains admittedly) prepared by embodiment and comparative example is coated on it with No. 10 line stick
Surface is put into 60 DEG C of baking oven 1min, passes through ultra-violet curing, energy 500mJ/cm later2。
Performance detection is carried out to coating made from Examples 1 to 6 and comparative example 1~6 respectively, measures the attachment of coating
Power, pencil hardness, wearability, initial stage water contact angle and sustained water contact angle performance.Concrete outcome is listed in Table 1 below.
Specific performance detection project and corresponding method are as follows:
One, adhesive force
Using baige method, specimen page adhesive force is tested with 3M Pressure sensitive adhesive tape.
Appraisal procedure:
5B- scribing edge is smooth, at the edge and intersection of scribing line without peeling paint；
4B- has the peeling paint of small pieces in the intersection of scribing line, and the gross area that falls off is less than 5%；
3B- has the peeling paint of small pieces at the edge and intersection of scribing line, and fall off the gross area 5~15% it
Between；
2B- has sheet of peeling paint at the edge and intersection of scribing line, and fall off the gross area 15~35% it
Between；
1B- has sheet of peeling paint at the edge and intersection of scribing line, and fall off the gross area 35~65% it
Between；
0B- has sheet of peeling paint at the edge and intersection of scribing line, and the gross area that falls off is greater than 65%.
Two, pencil hardness
Referring to standard GB/T/T6739 " hardness of paint film pencil measuring method ".
Three, wear-resisting property
Using 0000# steel wool, 300g power, one is denoted as once back and forth, and the number scratched occurs in recording surface.
Appraisal procedure: after the friction of certain number, whether observation coating has scratch, is resistant to when recording without scratch
Most Rubbing numbers.
Four, initial stage hydrophilic angle
4 μ L deionized waters are dripped in the specimen surface being cured, are measured within the scope of 20~25 DEG C with contact angle tester.
Five, continue hydrophilic angle
The sample being cured is put into deionized water and is impregnated for 24 hours, is measured after drying with contact angle measurement.
By the test result of Examples 1 to 5 and comparative example 1~5, including attachment, pencil hardness, wear-resisting, initial stage hydrophilic angle
Persistently hydrophilic angle
Six: anti-fog properties: the test board that surface temperature is 25 degree being horizontally placed above 80 DEG C of the water surface at 10cm, sample is observed
The time that plate hazes.
X hazes in 1 second
Δ: it hazes after 10 seconds
It hazes after zero: 30 second
◎: it does not haze
Table 1
Note: 1000 acrylate of methoxy poly (ethylene glycol) refers to that ethylene glycol weight average molecular weight is the 1000 poly- second two of methoxyl group
Alcohol acrylate.
As can be seen from Table 1, Examples 1 to 6 has preferable anti-fog performance.Initial water contact is below 10 degree, and 24
Water contact angle after hour immersion is below 35 degree, and anti-fog performance is excellent.Comparative example 1 and comparative example 3 compared with Example 2, by
When hydrophily pure acrylic acid ester type light-cured resin used synthesis, the amount using hydrophilic monomer II and I is more, therefore gained
Final resin pure acrylic acid ester type light-cured resin hydrophily is preferable, cause the initial water contact of coating after coating photocuring compared with
It is low, so having a little anti-fog properties.But after its 100 degree are impregnated, hydrophily is greatly reduced.This is because hydrophilic resin used
Hydrophily it is very good, cause final coating made due to water-swellable hydrophilic segment network from substrate surface be detached from, cause in coating
Hydrophobic part is in the great majority, and substantially reduces hydrophily.Comparative example 2 compared with Example 2, due to hydrophily pure C alkene used
It is more using the amount of acrylic monomers when acid esters type light-cured resin synthesizes, then reacted through GMA with carboxyl, lead to hydrophobic part
Increase, therefore the final resin pure acrylic acid ester type light-cured resin hydrophily of gained is poor.Additionally, due to unsaturated double-bond also phase
It should increase, so cross-linked network is finer and close when photocuring.These two aspects reason causes the hydrophily of coating poor, because anti-without having
Mist performance.Comparative example 4 compared with Example 2, due to hydrophily pure acrylic acid ester type light-cured resin used synthesis when, using parent
The amount of aqueous monomers I is very low, therefore the final resin pure acrylic acid ester type light-cured resin hydrophily of gained is poor.So as to cause painting
The hydrophily of layer is poor, because without having anti-fog performance.Comparative example 5 is lower than 6 compared with Example 2, due to joined degree of functionality
Hydrophobicity light-cured resin, although initial stage water contact angle within 10 degree, since final coating network is not fine and close, leads to it
When contact vapor and water impregnate for a long time, hydrophilic segment network is detached from from substrate surface, and reduces hydrophily, so antifog
Performance is poor, and protracted hydrophilicity is poor.Comparative example 4 compared with Example 3, uses non-ionic photocuring hydrophilic monomer, due to
Its hydrophily is lower than ionic comonomer, therefore its initial water contact is higher, does not have anti-fog performance.
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention.More than it should be pointed out that
Embodiment is merely to illustrate the present invention, and the protection scope being not intended to restrict the invention.For the common skill of the art
For art personnel, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as this hair
Bright protection scope.
Claims (5)
1. a kind of ultraviolet light curing anti fogging coating composite, which is characterized in that the composition include as each component:
The composition further includes solvent, and the weight of solvent is 2-4 times of other component weights；The solvent is acetic acid second
Ester, butyl acetate and isopropanol；
The hydrophily light-cured resin is pure acrylic resin；The pure acrylic resin is that side chain contains unsaturated double-bond
Acrylic resin；
The preparation method of the pure acrylic resin includes the following steps:
S1, in a solvent, is added monomer and initiator is reacted；
S2, add glycidyl methacrylate, catalyst and polymerization inhibitor reaction to get；
In step S1, the monomer includes molar ratio for monomer I shown in 2~5:2~4:0~3:2~3 formula (I), formula (II) institute
Show monomer II, hy-droxybutyl, acrylic acid；
The molar ratio of the monomer and glycidyl methacrylate is 1:1.
2. ultraviolet light curing anti fogging coating composite as described in claim 1, which is characterized in that the solvent is ethylene glycol list
Methyl ether；The initiator is azodiisobutyronitrile；The catalyst is benzyltrimethylammonium chloride；The polymerization inhibitor is to hydroxyl
Methyl phenyl ethers anisole.
3. ultraviolet light curing anti fogging coating composite according to claim 1, which is characterized in that the hydrophobicity photocuring
Resin includes urethane acrylate of the degree of functionality higher than 6, the polyester of the epoxy acrylate more than or equal to 2, degree of functionality higher than 4
At least one of acrylate.
4. ultraviolet light curing anti fogging coating composite according to claim 1, which is characterized in that the hydrophily photocuring
Monomer is selected from 3- propyl sulfonic acid methacrylic acid potassium, methacrylic acid trimethyl ammonium chloride, allyloxy Nonyl pheno
The combination of one or more of ether, allyloxy nonylphenol polyoxyethylene ether ammonium sulfate.
5. ultraviolet light curing anti fogging coating composite according to claim 1, which is characterized in that the photoinitiator is 2-
Hydroxy-2-methyl -1- phenyl -1- propyl ketone, 1- [4- (2- hydroxy ethoxy)-phenylene] -2- hydroxyl -2 ', 2 '-dimethyl second
Ketone, 1- hydroxycyclohexyl phenyl ketone, at least one of 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholine-1- acetone.
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| CN110361873A (en) * | 2019-07-12 | 2019-10-22 | 漳州东利光学科技有限公司 | A kind of discoloration antifogging type sunglasses lenses and its manufacturing process |
| CN110903754A (en) * | 2019-11-08 | 2020-03-24 | 上海翰飞新材料科技有限公司 | Anti-fog polyurethane acrylate coating and preparation and use methods thereof |
| CN112574667A (en) * | 2020-11-23 | 2021-03-30 | 山东亿博润新材料科技有限公司 | One-step method for preparing antistatic material, photocureable coating and application |
| CN112409915A (en) * | 2020-12-21 | 2021-02-26 | 广州市奈森化工有限公司 | Hydrophilic oleophobic antifogging photocureable coating and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1845141A1 (en) * | 2006-03-13 | 2007-10-17 | Mitsubishi Gas Chemical Company, Inc. | Antifogging coating composition |
| CN101602913A (en) * | 2009-06-26 | 2009-12-16 | 广州慧谷化学有限公司 | A kind of ultraviolet light curing anti fogging coating composite and compound method thereof |
| CN102911582A (en) * | 2012-10-30 | 2013-02-06 | 中国海洋石油总公司 | Ultraviolet light cured antifogging coating |
| CN105482067A (en) * | 2015-12-03 | 2016-04-13 | 佛山佛塑科技集团股份有限公司 | Fluorine-containing surface active oligomer, and preparation method and ultraviolet light cured anti-fogging coating thereof |
-
2016
- 2016-07-28 CN CN201610607744.9A patent/CN106189642B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1845141A1 (en) * | 2006-03-13 | 2007-10-17 | Mitsubishi Gas Chemical Company, Inc. | Antifogging coating composition |
| CN101602913A (en) * | 2009-06-26 | 2009-12-16 | 广州慧谷化学有限公司 | A kind of ultraviolet light curing anti fogging coating composite and compound method thereof |
| CN102911582A (en) * | 2012-10-30 | 2013-02-06 | 中国海洋石油总公司 | Ultraviolet light cured antifogging coating |
| CN105482067A (en) * | 2015-12-03 | 2016-04-13 | 佛山佛塑科技集团股份有限公司 | Fluorine-containing surface active oligomer, and preparation method and ultraviolet light cured anti-fogging coating thereof |
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