CN104529185B - Anti-fogging coating and preparation method thereof - Google Patents
Anti-fogging coating and preparation method thereof Download PDFInfo
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- CN104529185B CN104529185B CN201510018381.0A CN201510018381A CN104529185B CN 104529185 B CN104529185 B CN 104529185B CN 201510018381 A CN201510018381 A CN 201510018381A CN 104529185 B CN104529185 B CN 104529185B
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Abstract
The invention provides an anti-fogging coating and a preparation method of the anti-fogging coating. The anti-fogging coating is composed of a polyethylene maleic anhydride copolymer layer and a photo-curing crosslinking layer, wherein the polyethylene maleic anhydride copolymer layer and the photo-curing crosslinking layer are sequentially stacked on the surface of a base body. The surface of the base body is connected with the polyethylene maleic anhydride copolymer layer through generated first chemical bond force, and the photo-curing crosslinking layer is connected with the polyethylene maleic anhydride copolymer layer through generated second chemical bond force. Resin used in the photo-curing crosslinking layer is UV-curing cellulose ester resin of JS-113 or JS-116 or JS-126. The anti-fogging coating can be used for surface anti-fogging treatment of glass used for a mobile phone window, an automobile and a bathroom mirror, and has permanent use stability.
Description
Technical field
The present invention relates to glass art, especially, is related to the preparation method of a kind of antifogging coating and the coating.
Background technology
In daily life, as glass both sides have the obvious temperature difference and psychrometric difference.In the air of the higher side of temperature
Gasifying liquid glass surface can be condensed in when running into glass form the poor droplet of mobility, make glass surface produce mist
Gas.The droplet of glass surface can make light produce irregular scattering, reflection and diffraction, so as to significantly affects the saturating of light
Penetrate ability.
Haze to reduce glass, in prior art, there are various methods being improved for glass surface.It is anti-at present
The method of mist mainly includes：(1) surfactant directly penetrates into glass method；(2) surfactant directly painting method；(3) high score
Sub- cladding process.But first two method lasting stability is low, Jing is needed often repeatedly to process glass surface using activating agent.The third method
The good antifogging effect of gained glass, and anti-fog effect is persistently wear-resisting, and it is wide concerned.The antifog principle of polymer coating method is
Using the hydrophilic of coating of high molecular polymer, the film with highly-hydrophilic effect is formed in glass surface, make glass to water
Contact angle diminishes.Drop forms very thin moisture film, plays anti-fog effect in glass surface easily wetting and spreading.However, macromolecule material
Material is difficult to be attached to glass surface, and after life-time service, the polymeric coating layer meeting unstability of glass surface comes off.And for example, when coating is subject to
After pollution, if after using conventional cleaning method such as wiping, can come off more than antifogging coating.
The content of the invention
Present invention aim at the preparation method of a kind of antifogging coating and the coating is provided, it is antifog in prior art to solve
Coating holds caducous technical problem.
For achieving the above object, according to an aspect of the invention, there is provided a kind of antifogging coating, antifogging coating is by sequentially
The polyethylene maleic anhydride copolymer layer being stacked and placed on matrix surface and photocured cross-linked layer composition, matrix surface and polyethylene horse
To be connected by there is the first chemical bond force between anhydride copolymers nitride layer, photocured cross-linked layer and polyethylene maleic anhydride copolymerization
It is connected by there is the second chemical bond force between nitride layer；In the photocured cross-linked layer, resin used is that uV curable is fine
The plain ester resin of dimension, comprising unsaturated fiber element in the resin, viscosity is 3200～60000cps；Matrix surface is provided with amino
Layer.
Further, the first chemical bond force is served as reasons the generation of-NH-CO- chemical bonds, and the second chemical bond force is served as reasons-COO- ester bonds
Produce；Photocured cross-linked layer is that uV curable cellulose ester resin occurs ultraviolet light with -2 methyl propane sulfonic acid of 2- acrylamides
The cross-linked network structure layer that curing reaction is formed.
Further, matrix is display screen, glass or mirror.
Further, it is more than 600 times that the RCA of antifogging coating is wear-resisting, and antifogging coating is more than 5B to the adhesive force of glass,
The pencil hardness of antifogging coating is more than H, and the water contact angle of antifogging coating is less than 7 °.
Additionally provide a kind of method of the antifogging coating for preparing any of the above-described according to a further aspect in the invention, including with
Lower step：1) hydroxylating matrix surface；2) hydroxyl of matrix surface is converted into into amino, obtains amino matrix；3) in amino base
Body surface face coating polyethylene copolymer-maleic anhydride, and there is ring-opening reaction, obtain with polyethylene maleic anhydride copolymer layer
Open loop matrix；4) uV curable cellulose ester resin is coated in open loop matrix surface, and make uV curable fiber
Plain ester resin is occurred after amide reaction with open loop matrix, then carries out curing reaction, obtains the antifog painting with photocured cross-linked layer
Layer.
Further, step 1) in comprise the following steps：Under the conditions of ultrasonic Treatment, matrix is sequentially carried out cleaning,
Immerse hydroxylating solution and clean again, afterwards gained matrix is dried；Step 2) it is in microwave plasma reactor
In carry out, ventilated body is the mixed gas of hydrogen and nitrogen；Step 3) in polyethylene maleic anhydride copolymer be dissolved in acetone and
Polyethylene maleic anhydride solution is formed in the mixed solution of tetrahydrofuran, polyethylene maleic anhydride solution is coated on into amino base
On body；Ring-opening reaction condition is under conditions of vacuum is 665 handkerchiefs to be heated to 90～100 DEG C of constant temperature 8～12 hours, makes matrix
There is open loop chemical reaction with the maleic anhydride in polyethylene maleic anhydride copolymer molecule chain in the amino on surface.
Further, it is 1 by the volume ratio of hydrogen and nitrogen that mixed gas are:1 mixing, 2) step is in microwave plasma
The process time of reactor according is 400～800 seconds；The concentration of polyethylene maleic anhydride solution is 0.1～0.5%；Polyethylene horse
The molecular weight for carrying out acid anhydride copolymer is 100000～500000；Acetone is pressed with tetrahydrofuran with acetone in tetrahydrofuran mixed solution
Volume ratio is 1：2 mixing.
Further, in hydroxylating matrix surface step scavenging period and scavenging period is 10 minutes again；Hydroxyl
Change solution for by volume 3:7 mixing hydrogen peroxide are obtained with concentrated sulphuric acid.
Further, step 4) in comprise the following steps：A) uV curable cellulose ester resin is dissolved in into acetic acid second
After ester, then quality is added in resulting solution for the p-methyl benzenesulfonic acid of uV curable cellulose ester resin quality 0.03%,
Hybrid resin is obtained, hybrid resin is coated on open loop matrix surface with 4000rmp, be 665 handkerchiefs in vacuum, be heated to
At 120～140 DEG C, constant temperature carried out amide reaction under the conditions of 5～10 hours, obtained resin matrix；B) by light trigger and 2- propylene
- 2 methyl propane sulfonic acid of amide obtains causing solution in being dissolved in ethyl acetate solution, and solution will be caused to be coated on resin matrix surface simultaneously
55 DEG C of constant temperature are heated to after 5 minutes, curing reaction occurs under ultraviolet light.
Further, the concentration of the uV curable cellulose ester resin in hybrid resin is 1～3%；Light trigger
Concentration in solution is caused is that concentration of -2 methyl propane sulfonic acid of 0.02～0.15%, 2- acrylamides in solution is caused is
0.2～1.0%, the exposure energy of ultraviolet light is 600～1000mJ/cm2。
The invention has the advantages that：
The antifogging coating that the present invention is provided includes the polyethylene maleic anhydride copolymer layer being connected with each other by chemical bond force
With photocured cross-linked layer, in photocured cross-linked layer, resin used is fine for the uV curable of JS-113, JS-116 or JS-126
The plain ester resin of dimension, the resin formation on the polyethylene maleic anhydride copolymer layer the two be connected by chemical bond, be connected firmly,
Anti- fog effect lasting stability, can be used for the antifog process of the glass surfaces such as handset viewing window, automobile and bathroom mirror, and has enduringly
Stability in use energy.Gained coating surface RCA is wear-resisting up to 600 times, and to the adhesive force of glass up to 5B, pencil hardness is up to H.
The anti-fog effect of gained coating is more excellent simultaneously, and drop is only 7 ° in the water contact angle of coating surface.It is easily formed liquid stream to flow away, it is difficult
It is atomized with forming moisture film attachment thereon.
The preparation method of the antifogging coating that the present invention is provided, by carrying out hydroxylating first to matrix surface and turning ammonia
Change, form uniform amino surface, be beneficial to the adhesion of follow-up polyethylene maleic anhydride copolymer layer Yu matrix, improve institute
Obtain the adhesion and persistency of coating.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
The present invention is further detailed explanation below.
Description of the drawings
The accompanying drawing for constituting the part of the application is used for providing a further understanding of the present invention, the schematic reality of the present invention
Apply example and its illustrate, for explaining the present invention, not constituting inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is the antifog Contrast on effect schematic diagram of preferred embodiment of the present invention antifogging coating.
Specific embodiment
The present invention is described in detail with reference to embodiments, but the present invention can be defined by the claims and cover
Multitude of different ways implement.
If not specializing, the conventional meanses that technological means used are well known to those skilled in the art in embodiment.
The percentage sign " % " being referred to herein, if not specified, refers to mass percent；But the percentage ratio of solution,
Unless otherwise specified, contain some grams of solute in referring to solution 100m1；Percentage ratio between liquid, refers to the capacity at 20 DEG C
Ratio.
Matrix is referred to smooth surface and needs antifog all kinds of polymer surfaces, such as display screen, glass herein
Glass, instrument and meter card or mirror, wherein display screen refer to the screen such as mobile phone screen, LED/LCD TVs of all kinds of electronic devices
Screen or curtain wall screen etc..
The antifogging coating that the present invention is provided by the polyethylene maleic anhydride copolymer layer that is sequentially stacked and placed on matrix surface and
Photocured cross-linked layer composition, is connected by there is the first chemical bond force between matrix surface and polyethylene maleic anhydride copolymer layer
Connecing, being connected by there is the second chemical bond force between photocured cross-linked layer and polyethylene maleic anhydride copolymer layer.Photocuring
In cross-linked layer, resin used is uV curable cellulose ester resin, and comprising unsaturated fiber element in the resin, viscosity is
3200～60000cps.As resin is macromolecule mixture, wherein it is various to there is the grafting comprising the monomer structure, copolymerization etc.
The polymer substance of connected mode.Matrix surface is provided with amino layer.Body with amino layer can be obtained by conventional method.
UV curable cellulose ester resin can be purchased from middle mountain outstanding person thing up to Fine Chemical Co., Ltd JS-113,
Obtain after the uV curable cellulose ester resin mixing of JS-116 and/or JS-126.JS-113, JS-116 and JS-126 tri-
The corresponding viscosity of resin of kind of different model be respectively 25 DEG C at 3200cps, 42500cps and 55 DEG C at 55 DEG C at 60000cps.
The viscosity determining procedure of three kinds of resins is：Corresponding resin addition BAC (butyl acetate) solution is configured to containing 30wt.%BAC
Solution after, viscosimetric analysis are carried out to the solution.Measure instrument is NDJ-1 viscosity apparatuss.
The viscosity of uV curable cellulose ester resin is 3200～60000cps, and test condition is at 25 DEG C or 55 DEG C
Under by above-mentioned steps test obtain.
The first chemical bond force in the antifogging coating that the present invention is provided, refers to matrix surface and polyethylene maleic anhydride copolymerization
The connection that polyethylene maleic anhydride copolymer occurs chemical bond is fixed in nitride layer.It is preferred that first chemistry it is bonded can be in matrix
Surface forms amino layer, and amino ring-opening reaction occurs with polyethylene maleic anhydride copolymer afterwards.Form-NH-CO- chemical bonds
As the first chemical bond force.The chemical bonded refractory is made a concerted effort relatively by force, can prevent polyethylene maleic anhydride copolymer layer from using with matrix
During come off when being rubbed.
Photocured cross-linked layer is that uV curable cellulose ester resin is being formed by ultraviolet light solidify afterwards.Should
Contain cellulose group in resin, part of hydroxyl OH in cellulose group reacts to form ester with acrylic acid or acryloyl chloride
Key, C=C double bonds are grafted on cellulose, so as to uV curable cellulose ester resin.It is found through experiments, with fibre
The water contact angle of the formed film layer of UV-cured resin of the plain group of dimension is less so that coating is attached to drop or dust granule
Ability less, serve preferable anti-fog effect.
When the first chemical bond force is to be provided by ring-opening reaction, the polyethylene maleic anhydride copolymer layer surface for being formed is also
- COOH carboxyls are formed, the hydroxyl in uV curable cellulose ester resin occurs polycondensation reaction with the carboxyl.Formation-COO-
The chemical binding force of ester bond is used as the second chemical bond force.During the chemical bond force is enough to ensure that use, polyethylene maleic anhydride is common
Polymers layer is reacted with the above-mentioned resin in photocured cross-linked layer ,-COO- the ester bonds of formation, and the key has stronger adhesion
Power, during preventing use, photocured cross-linked layer is separated with polyethylene maleic anhydride copolymer layer.Prevent photocured cross-linked layer
Coming off causes the forfeiture of anti-fog effect.
Photocured cross-linked layer can directly occur ultraviolet light polymerization reaction by uV curable cellulose ester resin and obtain.
In the curing process, the coating containing light trigger can be set outside uV curable cellulose ester resin.In follow-up Jing
Make uV curable cellulose ester resin produce cross-linking and curing reaction when crossing ultraviolet light and obtain photocured cross-linked layer.Due to
In the resin for obtaining containing cellulose group thus after ultraviolet light polymerization, surface has preferable wearability.
It is preferred that uV curable cellulose ester resin and -2 methyl propane sulfonic acid of 2- acrylamides during ultraviolet light polymerization
There is ultraviolet light polymerization and react the cross-linked network structure layer to be formed.C=C double bonds in uV curable cellulose ester resin with
There is the free radical of C=C double bonds under light trigger and illumination in the C=C double bonds in -2 methyl propane sulfonic acid molecule of 2- acrylamides
Additive reaction, forms network cross-linked structure.There is network cross-linked structure in the photocured cross-linked layer of gained, the wear-resisting of coating is can guarantee that
Property.Avoid causing coating shedding when face is wiped, cause antifog failure.
The persistency of matrix surface anti-fog layer, on the one hand, relevant with the adhesive force stability of antifogging coating and matrix surface,
Adhesive force is more stable, and anti-fog performance is stronger；On the other hand, relevant with the surface abrasion resistance of antifogging coating, surface abrasion resistance is stronger,
During then hydrophilic group hydroxyl and sulfonic group more stable can be embedded in coating and surface, forms endurance anti-fog function.
Hydrophilic molecules segment with anti-fog function is connect by the anti-fog coating composition that the present invention is provided by chemical method
Branch arrives glass surface, and adhesion is higher, and stability is more preferable.Coating forms cross-linked structure through ultraviolet light polymerization, improves anti-
The case hardness and wearability of mist coating, increased the long-acting stability in use of coating.Steam or water droplet can moisten in coating surface
Wet-laying exhibition, with excellent anti-fog function.
Gained antifogging coating is arranged on the matrix surface such as glass, it is more than 600 times that the RCA of the coating is wear-resisting, is prevented
Mist coating is more than 5B to the adhesive force of glass, and the pencil hardness of antifogging coating is more than H, and the water contact angle of antifogging coating is 7 °
Below.
Antifog effect testing method is hot mist method of testing：Product coating face is statically placed in 60 points in 80 DEG C of saturated steam
Take out after clock, the transparent situation of coating product is observed under the room temperature condition of 50% humidity.It is by the present invention referring to the b in Fig. 1
The coating that provider's method is prepared be attached on glass after antifog design sketch.A in Fig. 1 provides painting to be not provided with the present invention
The glass surface of layer.After a and b in contrast Fig. 1 is it is obvious that arrange the coating that the present invention is provided, glass it is anti-
Substantially, in b, no misty liquid droplets are formed fog effect.In a, glass surface has formed very thin drop layer.It follows that this
The coating of bright offer has preferably anti-fog effect.
Therefore, in the present invention, polyethylene maleic anhydride copolymer layer plays bridging action, and bonding has anti-fog function
Resin solidification coating and matrix surface.And UV-curable cellulose ester resin contains a large amount of hydrophilic hydroxyls, and 2- propylene
- 2 methyl propane sulfonic acid of amide contains the sulfonic acid group of hydrophilic functionality, it is possible to provide the anti-fog function of coating；Pass through photocuring simultaneously
Cross-linked structure, hydrophilic group firmly can be embedded in coating surface and coating, it is ensured that the lasting stability of anti-fog function.
Another aspect of the present invention additionally provides a kind of preparation method of above-mentioned coating, comprises the following steps：
1) hydroxylating matrix surface；
2) hydroxyl of matrix surface is converted into into amino, obtains amino matrix；
3) in amino matrix surface coating polyethylene copolymer-maleic anhydride, and there is ring-opening reaction, obtain with poly- second
The open loop matrix of alkene copolymer-maleic anhydride layer；
4) uV curable cellulose ester resin is coated in open loop matrix surface, and make uV curable cellulose esters
Resin is occurred after amide reaction with open loop matrix, then carries out curing reaction, obtains the antifogging coating with photocured cross-linked layer.
Above steps is carried out according to a conventional method, and aforementioned antifogging coating is obtained.
The present invention is to solve the problems, such as that the method is first by matrix with the functional coating of hydrophilic antifogging and matrix adhesive force
Surface carries out hydroxylating, then gained hydroxyl is converted to amino.Matrix surface amination is processed to produce amino group；Adopt again
There is ring-opening reaction, shape under heat effect with maleic anhydride units in polyethylene maleic anhydride copolymer molecule structure and amino
Into-NH-CO- acid amides chemical bond adhesions, and production-COOH carboxylic groups；Then uV curable cellulose esters are utilized
In resinous molecular structure there is condensation reaction formation-O-CO- ester bonds with carboxyl in hydroxyl, make uV curable cellulose ester resin
Molecule forms firm chemical bonded refractory with polyethylene maleic anhydride copolymer molecule and makes a concerted effort；Under the conditions of last ultraviolet photoetching, light
Acrylate carbon-carbon double bond and uV curable cellulose in -2 methyl propane sulfonic acid molecule of initiator initiation 2- acrylamides
There is radical reaction in the acrylate carbon-carbon double bond in ester molecular resin, form stable cross-linked structure, increase coating
The hardness and anti-wear performance on surface.Therefore, in the present invention, polyethylene maleic anhydride copolymer plays bridging action, to provide
To the coating with anti-fog function and the adhesion of matrix surface；And uV curable cellulose ester resin contain it is a large amount of hydrophilic
The hydroxyl of property, and -2 methyl propane sulfonic acid of 2- acrylamides contains the sulfonic acid group of hydrophilic functionality, it is possible to provide coating it is antifog
Function；Simultaneously by the cross-linked structure of photocuring, hydrophilic group firmly can be embedded in coating surface and coating, it is ensured that antifog work(
The lasting stability of energy.
The coating that the method is prepared is wear-resisting, stronger with the adhesion of matrix, even if after in use, coating is polluted,
It is not easy to come off through conventional cleaning.Extend the service life of coating.
It is preferred that 1) comprise the following steps in step：Under the conditions of ultrasonic Treatment, matrix is sequentially carried out cleaning, immerses hydroxyl
Base solution and clean again, afterwards gained matrix is dried.The dust Impurity removal of matrix surface can be subtracted by cleaning
The impact that few impurity adheres to follow-up coating.Carry out reducing the damage to matrix under Ultrasonic Conditions, only to matrix surface
Play cleaning action.It is preferred that hydroxylating solution used is by volume 3 in hydroxylation procedures:7 mixing hydrogen peroxide are obtained with concentrated sulphuric acid
Arrive.Now the solution is optimal to the hydroxylating effect of matrix.It is in order to by hydroxylating to carry out cleaning after hydroxylating to matrix
Solution is removed from matrix surface.In hydroxylation procedures, scavenging period is 10 minutes twice.Now cleaning performance is optimal.
Preferred 2) step is to carry out in microwave plasma reactor, and ventilated body is the gaseous mixture of hydrogen and nitrogen
Body.Can now see that the hydroxyl of matrix surface is fully converted to amino.Preferred mixed gas are the volume by hydrogen with nitrogen
Ratio is 1:1 mixing, the power of microwave plasma reactor is 300 watts, 2.45GHZ, and 2) step is anti-in microwave plasma
The process time for answering device is 400～800 seconds.Again under the conditions of this, the amino for being formed can be with poly- second effectively with follow-up addition
Alkene copolymer-maleic anhydride reacts, and improves the adhesion of gained coating.
Preferably, 3) in step, polyethylene maleic anhydride copolymer is dissolved in shape in acetone and the mixed solution of tetrahydrofuran
Into polyethylene maleic anhydride solution, polyethylene maleic anhydride solution is coated on amino matrix.By by polyethylene maleic acid
Anhydride copolymer is dissolved in mixed solution minute, can improve polyethylene maleic anhydride copolymer uniform in spreading for amino matrix surface
Property, improve the adhesion of gained coating.More preferably the concentration of polyethylene maleic anhydride solution is 0.1～0.5%；Polyethylene Malaysia
The molecular weight of acid anhydride copolymer is 100000～500000；Acetone presses body with acetone in tetrahydrofuran mixed solution and tetrahydrofuran
Product is than being 1：2 mixing.Now the viscosity of gained polyethylene maleic anhydride solution is optimal, most beneficial in amino matrix surface
The uniformity of the polyethylene maleic anhydride copolymer layer of formation, pore and shrinkage cavity are minimum, so as to be conducive to obtaining with optimum viscous
The coating of attached power and anti-wear performance.
The mode of being preferably coated with can be spin coating or spraying or dip-coating.When for spin coating when polyethylene maleic anhydride solution coating
Speed is 2000rpm.Now the applying coating of polyethylene maleic anhydride solution is uniform, and smooth, air blister defect is less.
Preferred ring-opening reaction condition is that under conditions of vacuum is 665 handkerchiefs to be heated to 90～100 DEG C of constant temperature 8～12 little
When, there is open loop chemical reaction in the amino and the maleic anhydride in polyethylene maleic anhydride copolymer molecule chain for making matrix surface.
Now ring-opening reaction reaches maximum in the-NH-CO- chemical bond quantity that amino matrix surface is formed, so as to visible gained coating
Adhesion is improved to higher.
Preferred step 4) in comprise the following steps：
A) uV curable cellulose ester resin is dissolved in after ethyl acetate, then quality is added in resulting solution for can
The p-methyl benzenesulfonic acid of ultraviolet light polymerization cellulose ester resin quality 0.03%, obtains hybrid resin, hybrid resin is coated on out
On ring base surface, it is 665 handkerchiefs in vacuum, being heated to constant temperature at 120～140 DEG C, to carry out amide under the conditions of 5～10 hours anti-
Should, obtain resin matrix；
B) light trigger and -2 methyl propane sulfonic acid of 2- acrylamides are dissolved in ethyl acetate solution and obtain causing solution, with
After 4000rpm will cause solution to be coated on resin matrix surface and be heated to 55 DEG C of constant temperature 5 minutes, there is solidification under ultraviolet light
Reaction.
Carry out step 4 under this condition) obtained by hybrid resin uV curable cellulose ester resin can fully be dissolved,
Reduce its viscosity and improve its levelling ability.Spread ability of the resin in open loop matrix surface can be improved, is obtained after improving subsequent cure
The uniformity of the coating for arriving, after preventing film, caused by heterogeneity, adhesion is reduced.More preferably in hybrid resin can UV-curing
The concentration of cellulose ester resin is 1～3%.Now the viscosity of hybrid resin is optimal.
Amide reaction condition, can guarantee that in hybrid resin can reactive group fully react, reduce not anti-in coating
Answer harmful effect of the quantity of group to film layer adhesion.
It is preferred that the coating speed of the spin coating of hybrid resin is that now resin smears most uniform to 4000rmp.
Concentration of the preferred photoinitiator in solution is caused exists for -2 methyl propane sulfonic acid of 0.02～0.15%, 2- acrylamides
Concentration in initiation solution is 0.2～1.0%, and the exposure energy of ultraviolet light is 600～1000mJ/cm2.2- acryloyls used
- 2 methyl propane sulfonic acid main purpose of amine is that solidification is participated in uV curable cellulose ester resin solidification process.While in order to
The adequacy for adding excessive -2 methyl propane sulfonic acid of 2- acrylamides to affect curing reaction is prevented, it is unreacted in the residual coating of reduction
The amount of material, mixing light trigger and -2 methyl propane sulfonic acid of 2- acrylamides in this ratio can make the residual in gained coating not anti-
Material and group is answered to minimize so that the coating adhesion for obtaining is optimal.The exposure energy of ultraviolet light be 600～
1000mJ/cm2.Curing reaction now in photocured cross-linked layer is most abundant.
Antifog effect testing method is hot mist method of testing：Product coating face is statically placed in 60 points in 80 DEG C of saturated steam
After clock take out, indoors humidity be 50% room temperature condition under observe coating product transparent situation.Referring to the b in Fig. 1 be by
The coating that the method provided by the present invention is prepared be attached on glass after antifog design sketch.A in Fig. 1 is to be not provided with the present invention
The glass surface of coating is provided.After a and b in contrast Fig. 1 is it is obvious that arrange the coating that the present invention is provided, glass
Substantially, in b, no misty liquid droplets are formed the anti-fog effect of glass.In a, glass surface has formed very thin drop layer.Thus may be used
Know, the coating that the present invention is provided has preferably anti-fog effect.
Therefore, in the present invention, polyethylene maleic anhydride copolymer plays bridging action, tree of the bonding with anti-fog function
Fat solidify coating and matrix surface.And UV-curable cellulose ester resin contains a large amount of hydrophilic hydroxyls, and 2- acryloyls
- 2 methyl propane sulfonic acid of amine contains the sulfonic acid group of hydrophilic functionality, it is possible to provide the anti-fog function of coating；Simultaneously by photocuring
Cross-linked structure, hydrophilic group firmly can be embedded in coating surface and coating, it is ensured that the lasting stability of anti-fog function.
Embodiment
Embodiment 1
The present invention provides ultraviolet light and can be provided by uviol lamp, and the LT-1602 types of such as blue sky Te Deng Development Co., Ltds are ultraviolet
Line curing；Microwave plasma reactor is produced for Plasmionique companies of Canada.
UV-curable cellulose ester resin, reaches JS-113, JS- of Fine Chemical Co., Ltd of company purchased from Zhongshan city's outstanding person's thing
116、JS-126。
Polyethylene maleic anhydride copolymer, purchased from Canadian Sigma-Aldrich companies.
In light trigger Alpha-hydroxy phenylcyclohexyl ketone model Irgacure 184 be purchased from Ciba companies of Switzerland, 2,4,6-
Trimethyl benzoyl diphenyl base phosphine oxide model Darocur TPO is purchased from Ciba companies of Switzerland.
Embodiment 1
Clear glass is placed in deionized water carries out ultrasound wave cleaning 10 minutes, then under conditions of ultrasonic Treatment
Volume ratio is placed in for 3:In 7 hydrogen peroxide and the mixed solution of concentrated sulphuric acid；Deionized water ultrasonic glass cleaning table is adopted finally
Face 10 minutes, and dried 30 minutes, to realize that the hydroxylating to glass surface is processed.By the glass of Jing surface hydroxylations process
Glass is placed in the microwave plasma reactor of logical highly purified hydrogen and nitrogen mixed gas and processes 400 seconds, makes glass surface
Hydroxyl be converted into amino.Acetone and tetrahydrofuran mixed solution (1 will be dissolved in:2) the polyethylene maleic anhydride copolymer in is (dense
0.1%) degree is spun on amidized glass surface with 2000rpm speed, and lower 90 DEG C of 665 handkerchief vacuum conditions are heated 8 hours, made
There is open loop chemical reaction with the maleic anhydride in polyethylene maleic anhydride copolymer molecule chain in amino.By UV-curable cellulose
Ester resin is dissolved in ethyl acetate (concentration 1%), and dissolves in quality for the right of UV-curable cellulose ester resin quality 0.03%
Toluenesulfonic acid, is spun on the coating surface for producing ring-opening reaction, the lower 120 DEG C of heating 5 of 665 handkerchief vacuums with 4000rmp speed
Hour.Light trigger (concentration 0.02%) and -2 methyl propane sulfonic acid of 2- acrylamides (concentration 0.2%) are dissolved in into ethyl acetate molten
In liquid, above-mentioned coating surface is spun on 4000rpm speed, 55 DEG C are heated 5 minutes.Most after intensity be 1000mJ/cm2Purple
Exposure curing under outer light.
UV curable cellulose ester resin is JS-113.The BAC solution of JS-113 30wt.% at 25 DEG C, viscosity
For 3200cps.
Embodiment 2
Clear glass is placed in deionized water carries out ultrasound wave cleaning 10 minutes, then under conditions of ultrasonic Treatment
Volume ratio is placed in for 3:In 7 hydrogen peroxide and the mixed solution of concentrated sulphuric acid；Deionized water ultrasonic glass cleaning table is adopted finally
Face 10 minutes, and dried 30 minutes, to realize that the hydroxylating to glass surface is processed.By the glass of Jing surface hydroxylations process
Glass is placed in the microwave plasma reactor of logical highly purified hydrogen and nitrogen mixed gas and processes 800 seconds, makes glass surface
Hydroxyl be converted into amino.Acetone and tetrahydrofuran mixed solution (1 will be dissolved in:2) the polyethylene maleic anhydride copolymer in is (dense
0.5%) degree is spun on amidized glass surface with 2000rpm speed, and the lower 100 DEG C of heating 12 of 665 handkerchief vacuum degree conditions are little
When, make amino that open loop chemical reaction occur with the maleic anhydride in polyethylene maleic anhydride copolymer molecule chain.By UV-curable
Cellulose ester resin is dissolved in ethyl acetate (concentration 3%), and dissolves in quality for UV-curable cellulose ester resin quality
0.03% p-methyl benzenesulfonic acid, is spun on the coating surface for producing ring-opening reaction, under 665 handkerchief vacuums with 4000rmp speed
130 DEG C are heated 7 hours.Light trigger (concentration 0.1%) and -2 methyl propane sulfonic acid of 2- acrylamides (concentration 1%) are dissolved in into acetic acid
In ethyl ester solution, above-mentioned coating surface is spun on 4000rpm speed, 55 DEG C are heated 5 minutes.Most after intensity be 600mJ/
cm2Exposed under UV light solidification.
UV curable cellulose ester resin is JS-116.The BAC solution of JS-116 30wt.% at 55 DEG C, viscosity
For 42500cps.
Embodiment 3
Clear glass is placed in deionized water carries out ultrasound wave cleaning 10 minutes, then under conditions of ultrasonic Treatment
Volume ratio is placed in for 3:In 7 hydrogen peroxide and the mixed solution of concentrated sulphuric acid；Deionized water ultrasonic glass cleaning table is adopted finally
Face 10 minutes, and dried 30 minutes, to realize that the hydroxylating to glass surface is processed.By the glass of Jing surface hydroxylations process
Glass is placed in the microwave plasma reactor of logical highly purified hydrogen and nitrogen mixed gas and processes 600 seconds, makes glass surface
Hydroxyl be converted into amino.Acetone and tetrahydrofuran mixed solution (1 will be dissolved in:2) the polyethylene maleic anhydride copolymer in is (dense
0.2%) degree is spun on amidized glass surface with 2000rpm speed, and the lower 95 DEG C of heating 10 of 665 handkerchief vacuum degree conditions are little
When, make amino that open loop chemical reaction occur with the maleic anhydride in polyethylene maleic anhydride copolymer molecule chain.By UV-curable
Cellulose ester resin is dissolved in ethyl acetate (concentration 1.5%), and dissolves in quality for UV-curable cellulose ester resin quality
0.03% p-methyl benzenesulfonic acid, is spun on the coating surface for producing ring-opening reaction, under 665 handkerchief vacuums with 4000rmp speed
140 DEG C are heated 10 hours.Light trigger (concentration 0.1%) and -2 methyl propane sulfonic acid of 2- acrylamides (concentration 0.5%) are dissolved in
In ethyl acetate solution, above-mentioned coating surface is spun on 4000rpm speed, 55 DEG C are heated 5 minutes.Most after intensity it is
800mJ/cm2Exposed under UV light solidification.
UV curable cellulose ester resin is JS-126.The BAC solution of JS-126 30wt.% at 55 DEG C, viscosity
For 60000cps.
Embodiment 4
Clear glass is placed in deionized water carries out ultrasound wave cleaning 10 minutes, then under conditions of ultrasonic Treatment
Volume ratio is placed in for 3:In 7 hydrogen peroxide and the mixed solution of concentrated sulphuric acid；Deionized water ultrasonic glass cleaning table is adopted finally
Face 10 minutes, and dried 30 minutes, to realize that the hydroxylating to glass surface is processed.By the glass of Jing surface hydroxylations process
Glass is placed in the microwave plasma reactor of logical highly purified hydrogen and nitrogen mixed gas and processes 500 seconds, makes glass surface
Hydroxyl be converted into amino.Acetone and tetrahydrofuran mixed solution (1 will be dissolved in:2) the polyethylene maleic anhydride copolymer in is (dense
0.3%) degree is spun on amidized glass surface with 2000rpm speed, and the lower 90 DEG C of heating 12 of 665 handkerchief vacuum degree conditions are little
When, make amino that open loop chemical reaction occur with the maleic anhydride in polyethylene maleic anhydride copolymer molecule chain.By UV-curable
Cellulose ester resin is dissolved in ethyl acetate (concentration 2%), and dissolves in quality for UV-curable cellulose ester resin quality
0.03% p-methyl benzenesulfonic acid, is spun on the coating surface for producing ring-opening reaction, under 665 handkerchief vacuums with 4000rmp speed
140 DEG C are heated 8 hours.Light trigger (concentration 0.1%) and -2 methyl propane sulfonic acid of 2- acrylamides (concentration 0.8%) are dissolved in into second
In acetate solution, above-mentioned coating surface is spun on 4000rpm speed, 55 DEG C are heated 5 minutes.Most after intensity be 900mJ/
cm2Exposed under UV light solidification.
UV curable cellulose ester resin is the BAC solution of 30wt.% at 25 DEG C containing unsaturated fiber element, is glued
Spend the resin for 40000cps.
Embodiment 5
Clear glass is placed in deionized water carries out ultrasound wave cleaning 10 minutes, then under conditions of ultrasonic Treatment
Volume ratio is placed in for 3:In 7 hydrogen peroxide and the mixed solution of concentrated sulphuric acid；Deionized water ultrasonic glass cleaning table is adopted finally
Face 10 minutes, and dried 30 minutes, to realize that the hydroxylating to glass surface is processed.By the glass of Jing surface hydroxylations process
Glass is placed in the microwave plasma reactor of logical highly purified hydrogen and nitrogen mixed gas and processes 700 seconds, makes glass surface
Hydroxyl be converted into amino.Acetone and tetrahydrofuran mixed solution (1 will be dissolved in:2) the polyethylene maleic anhydride copolymer in is (dense
0.4%) degree is spun on amidized glass surface with 2000rpm speed, and lower 90 DEG C of 665 handkerchief vacuum degree conditions are heated 8 hours,
Make amino that open loop chemical reaction occur with the maleic anhydride in polyethylene maleic anhydride copolymer molecule chain.By UV-curable fiber
Plain ester resin is dissolved in ethyl acetate (concentration 2.5%), and dissolves in quality for UV-curable cellulose ester resin quality 0.03%
P-methyl benzenesulfonic acid, be spun on the coating surface for producing ring-opening reaction with 4000rmp speed, 665 handkerchief vacuums it is lower 130 DEG C plus
Heat 8 hours.Light trigger (concentration 0.15%) and -2 methyl propane sulfonic acid of 2- acrylamides (concentration 0.4%) are dissolved in into ethyl acetate
In solution, above-mentioned coating surface is spun on 4000rpm speed, 55 DEG C are heated 5 minutes.Most after intensity be 700mJ/cm2's
Exposed under UV light solidifies.
UV curable cellulose ester resin is the BAC solution of 30wt.% at 25 DEG C containing unsaturated fiber element, is glued
Spend the resin for 50000cps.Embodiment 6
Difference with embodiment 1 is：- 2 methyl propane sulfonic acid of 2- acrylamides, direct ultraviolet photocuring are not added.
Embodiment 7
Difference with embodiment 1 is：Using hydroxyl in molecular structure, the polyvinyl alcohol of non-carbon-carbon double bonds is substituted
UV-curable cellulose ester resin, does not add -2 methyl propane sulfonic acid of 2- acrylamides, does not adopt ultraviolet light polymerization and make coating
Compositionss there is no the free radical addition chemical reaction of carbon-carbon double bond.
The solidify coating of embodiment 1～7 is carried out into the detection of adhesive force, wearability, hardness, water contact angle and anti-fog performance,
Testing result is listed in Table 1 below.
Adhesive force is according to GB9286-1998 standard testings.
RCA wear-resisting tests method is routine RCA wear-resisting test methods, and using Norman RCA wear-resistant testers, paint film is born
Weight 175g.
Pencil hardness test presses GB/T 6739-2006 standard testings, heavy burden 1000g；GB 9286- are pressed in adhesive force test
1998 standard testings.
GB/T 23764-2009 standard testings are pressed in water contact angle test.
Anti-fog performance test is estimated using two methods of harl and hot mist：Harl method of testing is by containing solidify coating
Glass product is taken out after preserving 30 minutes at being statically placed in -15 DEG C, and the saturating of coating product is observed under the room temperature condition of 50% humidity
Obviously condition.Hot mist method of testing is taken out after being statically placed in 60 minutes in 80 DEG C of saturated steam for product coating face, in 50% humidity
Room temperature condition under observe coating product transparent situation.Transparency levels are represented using 1 to 5 successively, wherein 5 represent completely thoroughly
It is bright, 1 represent it is muddy opaque.
1 embodiment 1～7 of table prepares the performance test results table of antifogging coating
From table 1, the coating being coated on glass of embodiment 1～7, good adhesive force, wearability are shown
Energy, pencil hardness, water contact angle and anti-fog performance.The combination property of the solidify coating for wherein preparing in embodiment 3 is optimum,
For optimum embodiment of the present invention.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (9)
1. a kind of antifogging coating, it is characterised in that the antifogging coating is by the polyethylene Malaysia being sequentially stacked and placed on matrix surface
Anhydride copolymers nitride layer and photocured cross-linked layer composition, lead between described matrix surface and the polyethylene maleic anhydride copolymer layer
Cross the first chemical bond force of generation to be connected, pass through between the photocured cross-linked layer and the polyethylene maleic anhydride copolymer layer
There is the second chemical bond force to be connected；
In the photocured cross-linked layer, resin used is uV curable cellulose ester resin, comprising unsaturated fine in the resin
Dimension element, viscosity are 3200～60000cps；The uV curable cellulose ester resin includes acrylate carbon-carbon double bond；
Described matrix surface is provided with amino layer；
First chemical bond force serve as reasons-NH-CO- chemical bonds generation, second chemical bond force serve as reasons-COO- ester bonds generation；
The photocured cross-linked layer is that uV curable cellulose ester resin occurs purple with -2 methyl propane sulfonic acid of 2- acrylamides
The cross-linked network structure layer that outer photocuring reaction is formed.
2. antifogging coating according to claim 1, it is characterised in that described matrix is display screen, glass or mirror.
3. antifogging coating according to claim 2, it is characterised in that the RCA of the antifogging coating is wear-resisting be 600 times with
On, the antifogging coating is more than 5B to the adhesive force of glass, and the pencil hardness of the antifogging coating is more than H, described antifog
The water contact angle of coating is less than 7 °.
4. a kind of method of the antifogging coating prepared any one of claims 1 to 3, it is characterised in that including following step
Suddenly：
1) hydroxylating matrix surface；
2) hydroxyl on described matrix surface is converted into into amino, obtains amino matrix；
3) in the amino matrix surface coating polyethylene copolymer-maleic anhydride, and there is ring-opening reaction, obtain with poly- second
The open loop matrix of alkene copolymer-maleic anhydride layer；
4) uV curable cellulose ester resin is coated in the open loop matrix surface, and make the uV curable fiber
Plain ester resin is occurred after amide reaction with the open loop matrix, then carries out curing reaction, obtains the institute with photocured cross-linked layer
State antifogging coating.
5. method according to claim 4, it is characterised in that the step 1) in comprise the following steps：At ultrasound wave
Under the conditions of reason, described matrix is sequentially carried out cleaning, immerse hydroxylating solution and cleaning again, afterwards gained matrix is done
It is dry；
The step 2) it is to carry out in microwave plasma reactor, ventilated body is the mixed gas of hydrogen and nitrogen；
The step 3) described in polyethylene maleic anhydride copolymer be dissolved in acetone and the mixed solution of tetrahydrofuran and being formed
Polyethylene maleic anhydride solution, the polyethylene maleic anhydride solution is coated on the amino matrix；
The ring-opening reaction condition is under conditions of vacuum is 665 handkerchiefs to be heated to 90～100 DEG C of constant temperature 8～12 hours, is made
There is open loop chemistry instead with the maleic anhydride in the polyethylene maleic anhydride copolymer molecule chain in the amino on described matrix surface
Should.
6. method according to claim 5, it is characterised in that
It is 1 by the volume ratio of hydrogen and nitrogen that the mixed gas are:1 mixing, the 2) step is in the microwave plasma
The process time of reactor according is 400～800 seconds；
The mass concentration of the polyethylene maleic anhydride solution is 0.1～0.5%；The polyethylene maleic anhydride copolymer point
Son amount is 100000～500000；The acetone presses volume with the tetrahydrofuran with acetone described in tetrahydrofuran mixed solution
Than for 1：2 mixing.
7. method according to claim 5, it is characterised in that during the cleaning in the hydroxylating matrix surface step
Between and the scavenging period again be 10 minutes；
The hydroxylating solution is by volume 3:7 mixing hydrogen peroxide are obtained with concentrated sulphuric acid.
8. method according to claim 5, it is characterised in that the step 4) in comprise the following steps：
A) the uV curable cellulose ester resin is dissolved in after ethyl acetate, then in resulting solution, adds quality to be institute
The p-methyl benzenesulfonic acid of uV curable cellulose ester resin quality 0.03% is stated, hybrid resin is obtained, by the hybrid resin
It is coated on the open loop matrix surface with 4000rmp, is 665 handkerchiefs in vacuum, is heated to constant temperature 5～10 at 120～140 DEG C
The amide reaction is carried out under the conditions of hour, resin matrix is obtained；
B) light trigger and -2 methyl propane sulfonic acid of 2- acrylamides are dissolved in ethyl acetate solution and obtain causing solution, will be described
Cause solution to be coated on the resin matrix surface and 55 DEG C of constant temperature are heated to after 5 minutes, curing reaction occurs under ultraviolet light.
9. method according to claim 8, it is characterised in that
The mass concentration of the uV curable cellulose ester resin in the hybrid resin is 1～3%；
Mass concentration of the light trigger in the initiation solution is 0.02～0.15%, -2 methyl of 2- acrylamides
Propane sulfonic acid is 0.2～1.0% in the mass concentration caused in solution, the exposure energy of the ultraviolet light is 600～
1000mJ/cm2。
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| CN108948895B (en) * | 2018-06-05 | 2020-08-28 | 武汉工程大学 | Preparation method of anti-fog self-repairing coating |
| SE545002C2 (en) * | 2020-07-24 | 2023-02-21 | Cuptronic Tech Ltd | Method for surface treatment prior to metallization |
| CN113667393B (en) * | 2021-08-31 | 2022-07-29 | 武汉中科先进材料科技有限公司 | Anti-glare organic-inorganic hybrid antifogging coating and preparation thereof |
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| WO2007056856A1 (en) * | 2005-11-16 | 2007-05-24 | UNIVERSITé LAVAL | Process for producing anto-fog coating |
| EP2650127B1 (en) * | 2010-12-07 | 2017-11-15 | Asahi Glass Company, Limited | Anti-fogging article and method for producing same |
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Address after: 410600 No. 777 East Third Ring Road, Ningxiang Economic and Technological Development Zone, Changsha City, Hunan Province Patentee after: Hunan Matsui new materials Limited by Share Ltd Address before: 410600 No. 777 East Third Ring Road, Ningxiang Economic and Technological Development Zone, Changsha City, Hunan Province Patentee before: Hu'nan Sokan New Material Co., Ltd. |