CN106146868A - A kind of multi-functional antifogging coating and preparation method thereof - Google Patents
A kind of multi-functional antifogging coating and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of multi-functional antifogging coating and preparation method thereof.Described multi-functional antifogging coating includes at least one of which functional coat being coated on suprabasil at least one of which antifogging coating and being coated on antifogging coating；Described antifogging coating has hygroscopicity；Described functional coat can make water pass through.Multi-functional antifogging coating prepared by the present invention is in addition to having the anti-fog performance of excellence, by changing the composition of the functional coat outside anti-fog layer, it is possible to obtain not only have outside coating performance but also have the coating of anti-fog performance.This result has overthrown the traditional theory of " anti-fog layer must be at outermost ", and will advance the design of multifunctional material significantly, makes various component material present multiformity and motility on spatial arrangement.The preparation method safety of the present invention, simple, wide application；Gained coating is applicable to unorganic glass, polymer plate or thin film, organo-mineral complexing sheet material, cable and airplane skin etc..
Description
Technical field
The present invention relates to Material Field.More particularly, to a kind of multi-functional antifogging coating and preparation side thereof
Method.
Background technology
Mist can cause the distortion of image, reduces the transmitance of light.In actual applications, there is antireflective merit
Can (hereinafter referred to as anti-reflection) have again simultaneously the coating of anti-fog function glasses, protective eye lens, lens, point
Application in analysis and medical optics device has good prospect.Super-hydrophilic coating, with water in 0.5 second
Contact angle is less than 5 °, makes water can sprawl rapidly on surface and present excellent performance.But it is super hydrophilic
The preparation of coating typically requires the step of complexity, even if coating of titanium dioxide, is required for the most greatly ultraviolet light
Lower just can present super hydrophilic characteristic.Meanwhile, the anti-fog performance deriving from super hydrophilic character is the longest
Effect, because super hydrophilic character tends to vary with the time and dies.
The most many work are devoted to build multi-function membrane and are allowed to both have anti-fog performance, have again anti-reflection
Deng other performance, including building super hydrophilic inorganic interface, polymer is combined with low-refraction inorganic material,
Build porous or the polymer etc. of moth ocular structure.These work differ from one another but common feature is anti-fog layer
All at outermost." anti-fog layer must be at outermost " this potential traditional idea is multifunctional material design
A big obstacle.Owing to anti-fog layer is designed in outermost, cause other that design must be relied at outermost layer
Could effectively play coating (such as hydrophobic coating, Anti Glare Coatings, the automatic cleaning coating of its functional characteristic
Deng) cannot embody with anti-fog performance simultaneously, if thus can by anti-fog layer design at internal layer, then outer layer
Functional coating selection and build will present the multiformity of structure and the multiformity of function.
Summary of the invention
It is an object of the present invention to provide a kind of multi-functional antifogging coating.
Further object is that the preparation method that a kind of multi-functional antifogging coating is provided.
Different from the antifogging coating utilizing material super hydrophilicity (contact angle is less than 5 °), the applicant's
Current research shows (patent No. 2014072500611940 and number of patent application 2014090200731090):
When the hydrone in the humid air of heat to condense on polymer coating, due to polymer and hydrone
Between interaction of hydrogen bond and Dipolar cycloadition, hydrone is immediately wicked into in polymer, is prevented
Water droplet is formed on the polymer film, and this kind of performance of polymer is referred to as hygroscopicity by us.It is derived from poly-
Hydrophilic and the hygroscopic antifog polymer coating of compound thin film have good anti-fog feature.
On this basis, first the applicant builds has hygroscopic antifogging coating, then at antifogging coating
Upper deposition hollow silica ball coating, obtains the composite coating with antifog anti-reflection in surprise.According to this
Known to applicant, up to now nobody work synthesis coating at anti-fog layer not in outmost situation
Under still present the antifog and reflection preventing ability of excellence.By changing the composition of the coating outside anti-fog layer,
Antifogging self-cleaning coating, antifog Anti Glare Coatings, antifog optical Limiting coating, antifog hydrophobic can also be obtained
Coating.On antifogging coating, i.e. coat other coatings that water can be made to pass through, can obtain and both there is outside
Coating performance has again the coating of anti-fog performance.This result has overthrown " anti-fog layer must be at outermost "
Traditional theory, and the design of multifunctional material will be advanced significantly, make various component material at spatial arrangement
On present multiformity and motility.
For reaching above-mentioned first purpose, the present invention uses following technical proposals:
A kind of multi-functional antifogging coating, described multi-functional antifogging coating includes being coated on suprabasil at least one
Layer antifogging coating and at least one of which functional coat being coated on antifogging coating；Described antifogging coating has
There is hygroscopicity；Described functional coat can make water pass through.
Preferably, described antifogging coating is selected from having hygroscopic polymer coating, polymer and inorganic material
Crosslinking there is hygroscopic coating, polymer has hygroscopic coating with crosslinked polymer or is polymerized
What thing mixed with inorganic material has hygroscopic coating.
Preferably, described functional coat is selected from having the coating of reflection preventing ability, having self-cleaning performance
Coating, there is the coating of anti-dazzle performance, there is the coating of optical limiting properties and there is hydrophobic performance
One or more in coating.
Preferably, the coating described in reflection preventing ability is hollow silica ball coating.
Preferably, described multi-functional antifogging coating is by being coated on suprabasil one layer of antifogging coating and coating
Two-layer hollow silica ball coating composition on antifogging coating.
The present invention creates anti-fog layer first in internal layer and the coating with excellent anti-reflection anti-fog performance, starts
Property ground propose and achieve the structure that anti-fog layer still can have the coating of excellent anti-reflection anti-fog performance at internal layer
Theory and design.
Preferably, described substrate is selected from unorganic glass, polymer plate, thin polymer film, organic-inorganic
Composite board, cable or airplane skin.
For reaching above-mentioned second purpose, the present invention uses following technical proposals:
The preparation method of a kind of multi-functional antifogging coating, comprises the steps:
Substrate coats at least one of which there is hygroscopic antifogging coating；
Antifogging coating coats the functional coat that at least one of which can make water pass through, i.e. obtains multi-functional
Antifogging coating.
Preferably, the mode of coating is lifting, spraying, spin coating, blade coating, roller coating or smears by hand.
Preferably, the preparation method of described antifogging coating is divided into following two:
One. antifogging coating preparation method one:
Referenced patent (number of patent application 2014072500611940), concretely comprises the following steps: 1) by main chain or
The polymer that polymer powder that side chain contains hydroxyl or main chain or side chain contain amino mixes with water (can
Preparing under conditions of heating in water bath and stirring, the temperature such as heating is 80 DEG C～100 DEG C, is preferably
85 DEG C～100 DEG C), being configured to mass concentration is the poly-of 1%～40% (preferred mass concentration is 5%～30%)
Compound aqueous solution；2) by master that mass concentration is 1%～85% (preferred mass concentration is 10%～70%)
Aqueous solutions of polymers that chain or side chain contain carboxyl and step 1) aqueous solutions of polymers that obtains mixes, stirring,
Obtain mixed liquor, wherein, step 1) the aqueous solutions of polymers polymer that contains carboxyl with main chain or side chain
The volume ratio of aqueous solution is 1:1～1:58；3) with acid, alkali or salt, by step 2) mixed liquor that obtains
PH regulator is 1～13 (preferably pH is 1～4) to pH scope, after stirring certain time, and ultrasonic or standing
Deaeration；4) by step 3) solution that obtains after deaeration is coated in solid substrate, then carries out heat treatment,
Obtain crosslinking has the water-fast long-acting antifog frost-resistant of self-healing properties and the big scrubbable high transmission rate of hardness
Polymer coating.The polymer that described main chain or side chain contain hydroxyl is selected from polyvinyl alcohol (PVA), gathers
Ethylene glycol, Polyethylene Glycol block copolymer in one.Described main chain or side chain contain the poly-of amino
Compound is polyvinylamine or polypropylene amine etc..The polymer that described main chain or side chain contain carboxyl is poly-third
Olefin(e) acid (PAA) or polymethylacrylic acid.Described acid is hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid or acetic acid
Deng.Described alkali is sodium hydroxide or potassium hydroxide etc..Described salt be potassium acid sulfate, sodium bisulfate,
Disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate etc..Step 4) described in coating
It is to use lifting, spraying, spin coating, blade coating, roller coating or the manual method smeared.Described solid substrate
It is outside substrate of glass, resistant to elevated temperatures polymer plate, resistant to elevated temperatures thin polymer film, cable or aircraft
Shell etc..The temperature range of described heat treatment is 20 DEG C～150 DEG C, preferably 100 DEG C～140 DEG C.Described
Time of heat treatment be 1 minute～720 hours, preferably 2 minutes～7 hours.
Two. antifogging coating preparation method two:
Referenced patent (number of patent application 2014090200731090), concretely comprises the following steps: 1) by main chain or
The polymer powder that side chain contains hydroxyl mixes with water (can join under conditions of heating in water bath and stirring
System, the temperature such as heating is 80 DEG C～100 DEG C, preferably 85 DEG C～100 DEG C), being configured to mass concentration is
The aqueous solutions of polymers of 1%～40% (preferred mass concentration is 5%～30%)；2) by organosilane reagents
It is added drop-wise to step 1 with the mixed liquor of ethanol) in the aqueous solutions of polymers that obtains, it is 0 DEG C～100 DEG C in temperature
It is stirred under the bath temperature of (preferably 30 DEG C～90 DEG C), adds mineral acid, the pH of regulation solution
Value is 1～7, proceeds stirring, there was added machine silane coupling agent after solution is transparent, and stirring, under room temperature
Standing and defoaming, by the liquid sucking filtration after standing and defoaming crosslinked polymer to remove precipitation；3) by step 2)
The liquid that sucking filtration obtains after removing precipitation is coated in solid substrate, naturally dries or dries in an oven,
Obtain the water-fast long-acting antifog frost-resistant high transmission rate coating with the Controllable cross-linking degree of network structure.Described
Crosslinked polymer, the degree of cross linking (hydroxyl bonding rate) of its polymer is 5%～60%, this degree of cross linking (hydroxyl
Base bonding rate) it is that the polymer being contained hydroxyl by main chain or side chain participates in crosslinking instead in crosslinked polymer
The amount of the material of the hydroxyl answered and crosslinked polymer react before main chain or side chain contain hydroxyl polymer in
The ratio of the amount of the material of hydroxyl determines.This degree of cross linking result in prepared water-fast long-acting antifog frost-resistant height
The degree of cross linking of light transmittance coating is controlled.Step 2) in organosilane reagents and the addition of organo silane coupling agent,
According to step 1) in described main chain or side chain contain in the polymer of hydroxyl the amount of the material of hydroxyl with
The ratio of the amount of the material of organosilane reagents is 5:1～100:1, and described main chain or side chain contain the poly-of hydroxyl
In compound, the amount of the amount of the material of hydroxyl and the material of organo silane coupling agent is than for 5:1～1:0.Step further
Rapid 2) organosilane reagents and the addition of organo silane coupling agent in, preferably according to step 1) in institute
The main chain stated or side chain contain the amount of the material of hydroxyl and described organosilane reagents in the polymer of hydroxyl
The amount of the material total with organo silane coupling agent is than for 5:1～100:1.Described organosilane reagents and ethanol
Mixed liquor in the mass ratio of organosilane reagents and ethanol be 1:10 to 1:0.The time of described stirring
It is 0.2～72 hour, preferably 0.3～7 hour.The time of described standing and defoaming is 0.2～72 hour,
It is preferably 0.3～7 hour.Described coating is to use lifting, spraying, spin coating, blade coating, roller coating or craft
The method smeared.Described drying in an oven, dries temperature in the range of 20 DEG C to 150 DEG C.Described
Main chain or side chain contain the polymer of hydroxyl selected from polyvinyl alcohol, Polyethylene Glycol, Polyethylene Glycol block altogether
One or more in polymers.Described organosilane reagents selected from APTES,
One in chlorosilane, tetramethoxy-silicane, tetraethyl orthosilicate, positive silicic acid propyl ester, positive isopropyl silicate
Or it is several.Described mineral acid one in hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid.Described is organic
Silane coupler shrinks sweet selected from γ-aminopropyl trimethoxysilane, aminopropyl triethoxysilane, 3-
Oil ether epoxide propyl trimethoxy silicane (KH-560), γ-methacryloxypropyl trimethoxy silicon
Alkane, VTES, vinyltrimethoxy silane, vinyl three ('beta '-methoxy second
Epoxide) silane, one or more in N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane.Described
Solid substrate selected from unorganic glass (such as K7105 glass, the artistic glass of 5 millimeters thick, microscope slide etc.),
Polymer plate or thin film are (such as Merlon (PC), polymethyl methacrylate (PMMA), automobile
Sunscreen film, resin lens, polyethylene terephthalate (PET)), cable, airplane skin etc. need
Want the one in antifog frost-resistant antifreeze material etc..
Preferably, the preparation method of described hollow silica ball coating is divided into following two steps:
One. the preparation of the sol solutions containing hollow silica ball nanoparticle:
Referenced patent (number of patent application 201410758433.3), particularly as follows: by 0.1 gram～0.7 gram poly-third
Olefin(e) acid is dissolved in the ammonia of 4.5 milliliters, ultrasonic disperse；Then be added dropwise to be mounted with 90 milliliters anhydrous
In the container of ethanol, stirring obtains mixed liquor；By the tetraethoxysilane of 1 milliliter～4 milliliters with per minute
The speed of 45 microlitres is added drop-wise in this mixed liquor；After completion of dropwise addition, gained solution is at room temperature stirred,
Obtain the sol solutions containing hollow silica ball nanoparticle；
Two. the preparation of hollow silica ball coating:
By containing hollow silica ball nanoparticle sol solutions use lifting, spraying, spin coating, blade coating,
Roller coating or the manual method smeared are coated on antifogging coating.Molten by changing coating silicon dioxide hollow ball
The number of times of glue, it is possible to obtain 1 layer of hollow silica ball/antifogging coating, 2 layers of hollow silica ball/
Antifogging coating, 3 layers of hollow silica ball/antifogging coating.
Beneficial effects of the present invention is as follows:
Multi-functional antifogging coating prepared by the present invention is in addition to having the anti-fog performance of excellence, anti-by changing
The composition of the functional coat outside mist layer, it is also possible to obtain antifogging self-cleaning coating, antifog anti-dazzle is coated with
Layer, antifog optical Limiting coating, antifog hydrophobic coating.I.e. coat it having on hygroscopic antifogging coating
He can make the coating that water passes through, and can obtain and not only have outside coating performance but also have the coating of anti-fog performance.
This result has overthrown the traditional theory of " anti-fog layer must be at outermost ", and will advance many merits significantly
The design of energy material, makes various component material present multiformity and motility on spatial arrangement.This
Bright method safety, simple, wide application；Gained coating is applicable to unorganic glass (such as K7105
Glass, the artistic glass of 5 millimeters thick, microscope slide etc.), polymer plate or thin film (as Merlon (PC),
Polymethyl methacrylate (PMMA), automobile sun film, resin lens, polyethylene terephthalate
(PET)), organo-mineral complexing sheet material, cable, airplane skin.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described in further detail.
Fig. 1 illustrates that the embodiment of the present invention 1 prepares the schematic diagram of antifog anti-reflection coating.
Fig. 2 illustrates antifog anti-reflection coating morphology figure prepared by the embodiment of the present invention 1.Wherein, (a) is 2
The electron scanning micrograph of layer hollow ball/antifogging coating, (b) is the transmitted electron of hollow silica ball
Microphotograph, (c) is the electron scanning micrograph side view of 2 layers of hollow ball/antifogging coating.
Fig. 3 illustrates the embodiment of the present invention 1 empty glass, the hyaloid of 1 layer of hollow ball/anti-fog layer coating
The glass sample that product, 2 layers of hollow ball/glass sample of anti-fog layer coating, 3 layers of hollow ball/anti-fog layer cover
Light transmittance in 300-900nm wave-length coverage.
Fig. 4 illustrates 2 layers of hollow ball in the embodiment of the present invention 1, anti-fog layer and 2 layers of hollow ball/anti-fog layer
The glass sample covered is placed 24 hours at 6 DEG C of refrigerators, the antifog test photo shot at once after taking-up.
Wherein, (a) is the glass sample antifog test comparison figure with blank glass of 2 layers of hollow balls covering, (b)
For the antifog test comparison figure of glass sample and blank glass that anti-fog layer covers, (c) be 2 layers of hollow ball/
The glass sample of anti-fog layer covering and the antifog test comparison figure of blank glass.
Fig. 5 illustrates that in the embodiment of the present invention 1, water is at blank glass (a), the hyaloid that 2 layers of hollow ball covers
The glass sample (d) that the glass sample (c) that product (b), anti-fog layer cover, 2 layers of hollow ball/anti-fog layer cover
On contact angle.
Fig. 6 illustrates that in the embodiment of the present invention 1, water vapour runs into blank glass (a), 2 layers of hollow ball covering
The glass that the glass sample (c) that glass sample (b), anti-fog layer cover, 2 layers of hollow ball/anti-fog layer cover
The behavior schematic diagram of sample (d).
Detailed description of the invention
In order to be illustrated more clearly that the present invention, below in conjunction with preferred embodiments and drawings, the present invention is done into one
The explanation of step.Parts similar in accompanying drawing are indicated with identical reference.Those skilled in the art
Should be appreciated that following specifically described content is illustrative and be not restrictive, should not limit with this
Protection scope of the present invention.
Embodiment 1
Polyvinyl alcohol (PVA) powder is mixed with water, in the heating in water bath that temperature is 85 DEG C and stirring
Under the conditions of be configured to the PVA aqueous solution that mass concentration is 10%, then by 38.20ml～42.17ml mass
Concentration be 10% PVA aqueous solution and 7.83ml～11.80ml mass concentration be the polyacrylic acid of 53%
(PAA) aqueous solution carries out being mixed to get mixed liquor under conditions of being sufficiently stirred for, by hydrochloric acid or hydroxide
The pH of sodium regulation mixed liquor is 1～4, and ultrasonic or standing deaeration in 24 hours after stirring, by gained after deaeration
Liquid coating (using one of lifting, spraying, spin coating, blade coating, roller coating, the manual method smeared) exists
On simple glass, in temperature is 100 DEG C～140 DEG C of high temperature, heat treatment 2 minutes～7 hours, then cools down
To room temperature, obtain crosslinking on the surface of simple glass has the water-fast long-acting antifog and hard of self-healing properties
Spend big scrubbable high transmission rate polymer coating.
0.1 gram～0.7 gram of polyacrylic acid are dissolved in the ammonia of 4.5 milliliters, ultrasonic disperse；The most dropwise add
Entering in the container being mounted with 90 milliliters of dehydrated alcohol, stirring obtains mixed liquor；By 1 milliliter～4 milliliters
Tetraethoxysilane is added drop-wise in this mixed liquor with the speed of 45 microlitres per minute；After completion of dropwise addition, gained
Solution is at room temperature stirred, and obtains the sol solutions containing hollow silica ball nanoparticle；
By obtain the sol solutions containing hollow silica ball nanoparticle use lifting, spraying, spin coating,
Blade coating, roller coating or the manual method smeared are coated on antifogging coating, i.e. obtain anti-reflection antifogging coating.Logical
Cross change coating silicon dioxide hollow ball sol solutions number of times, we obtain 1 layer of hollow ball/anti-fog layer, 2
The glass sample that layer hollow ball/anti-fog layer, 3 layers of hollow ball/anti-fog layer cover.
The forming process of described coating is as shown in Figure 1.We first in substrate coat anti-fog layer, then
Hollow silica ball coating it is coated with on anti-fog layer.By changing coating silicon dioxide hollow ball sol solutions
Number of times, we obtain 1 layer of hollow ball/anti-fog layer, 2 layers of hollow ball/anti-fog layer, 3 layers of hollow ball/anti-
The glass that mist layer covers.Fig. 2 illustrates antifog anti-reflection coating morphology figure prepared by the embodiment of the present invention 1.Its
In, (a) is the electron scanning micrograph of 2 layers of hollow ball/antifogging coating, demonstrates titanium dioxide in figure
Silicon hollow ball dense accumulation on anti-fog layer, has many gaps, hole on hollow silica ball layer and splits
Gap, these spaces provide the passage that hydrone enters the thin polymer film of hydrophilic moisture absorption.B () is dioxy
The transmission electron microscope photo of SiClx hollow ball, it can be seen that the mean outside diameter of hollow silica ball
For 41nm, internal diameter is 19nm.C () is the electron scanning micrograph side of 2 layers of hollow ball/antifogging coating
View, this figure shows that the thickness of the polymer anti-fog layer of internal layer is 7.1 μm.
The optical property of described coating, anti-fog performance are as follows:
Optical property
Blank glass, anti-fog layer, 1 layer of hollow ball/anti-fog layer, 2 layers of hollow ball/anti-fog layer, 3 layers of hollow ball
The light transmittance of the glass sample that/anti-fog layer covers is as shown in Figure 3, it will be apparent that anti-fog layer is to substrate of glass
Light transmittance change less, but deposition hollow ball can significantly change the light transmittance of sample.Therefore coating
Anti-reflection character comes from the hollow silica ball layer of low-refraction.Wherein, 2 layers of hollow ball/anti-fog layer cover
The glass sample of lid has the most excellent anti-fog performance.
Table 1 embodiment of the present invention 1 empty glass, 1 layer of hollow ball/anti-fog layer, 2 layers of hollow ball/anti-
The glass sample that mist layer, 3 layers of hollow ball/anti-fog layer covers in 300-900nm wave-length coverage maximum thoroughly
Light rate and average transmittance
As shown in table 1, in listed sample, the glass sample of 2 layers of hollow ball/anti-fog layer covering exists
There is in 300-900nm wave-length coverage the highest maximum transmission rate 98.9%, and the highest average transmittance
91.9%.
Antifog character
Fig. 4 illustrates 2 layers of hollow ball in the embodiment of the present invention 1, anti-fog layer and 2 layers of hollow ball/anti-fog layer
The glass sample covered is placed 24 hours at 6 DEG C of refrigerators, the antifog test photo shot at once after taking-up.
Wherein, (a) is the glass sample antifog test comparison figure with blank glass of 2 layers of hollow balls covering, (b)
For the antifog test comparison figure of glass sample and blank glass that anti-fog layer covers, (c) be 2 layers of hollow ball/
The glass sample of anti-fog layer covering and the antifog test comparison figure of blank glass.As shown in Figure 4, blank glass
The glass sample of glass part and 2 layers of hollow ball covering hazes, and anti-fog layer, 2 layers of hollow ball/anti-fog layer cover
Cover is antifog, and word below is high-visible.2 layers of hollow ball/anti-fog layer can be drawn the most intuitively
Anti-fog performance not from the hollow silica ball layer of outer layer, and from polymer anti-fog layer, although this
Layer is not at outermost.
Fig. 5 illustrates that in the embodiment of the present invention 1, water is at blank glass (a), the hyaloid that 2 layers of hollow ball covers
The glass sample (d) that the glass sample (c) that product (b), anti-fog layer cover, 2 layers of hollow ball/anti-fog layer cover
On contact angle.Figure shows: blank glass, 2 layers of hollow ball, anti-fog layer, 2 layers of hollow ball/anti-fog layer
The glass covered is respectively 49.4 ° with the contact angle of water, and 18.0 °, 56.8 °, 37.5 °, they are not super hydrophilic
's.
The anti-fog performance of 2 layers of hollow ball/anti-fog layer is not from the super hydrophilic antifog mechanism of traditional idea.I
Probed into the antifog mechanism of polymer coating with QCM.As it was previously stated, at silicon dioxide
Hollow layers of balls has many gaps, hole, crack, it is possible to make hydrone shuttle back and forth in the past, owing to hydrone is with poly-
The interaction of hydrogen bond of compound and Dipolar cycloadition, hydrone can be immediately wicked into polymeric layer
In.In antifog test process, the quality QCM of the water being inhaled into polymeric layer is surveyed
Amount, result shows 6.78 × 10-9The polymer anti-fog layer of g water absorption in antifog test process is
3.69×10-10G, i.e. due to water suction, the quality of coating adds 5.45wt%.In a word, 2 layers of hollow ball/
The anti-fog performance of anti-fog layer is not from the hollow silica ball layer of outer layer, and from polymer anti-fog layer,
Although this layer is not at outermost.
When surface runs into the malaria of heat, mist can be formed, therefore just within former seconds of contact
Stage beginning antifog critically important, because ensuing atomization can be because substrate have adapted to the temperature of environment and wet
Spend and haze and seriously even do not disappear.In antifog test process, water vapour runs into blank glass, 2 layers of sky
The behavior during glass that bulbus cordis, anti-fog layer, 2 layers of hollow ball/anti-fog layer covers as shown in Figure 6, in contact
In former seconds of water vapour, the glass sample of blank glass and 2 layers of hollow ball covering forms water droplet,
But not forming water droplet in anti-fog layer, 2 layers of hollow ball/anti-fog layer coating, hydrone is inhaled into polymerization
In nitride layer, from scanning electron microscope side view, show that the thickness of polymer coating is 7.1 μm, illustrate poly-
Compound coating has enough spaces to accommodate hydrone.The anti-fog performance of 2 layers of hollow ball/anti-fog layer coating
Source: the 1. hygroscopicity of polymer coating provides the driving force of inherence；2. in hollow silica ball layer
Gap, hole, crack provide the path that hydrone shuttles back and forth.2 layers of hollow ball/anti-fog layer coating deposit 10
Still keep good anti-fog performance after Yue, show that this coating anti-fog performance has long-lasting.
Embodiment 2
With reference to embodiment 1, difference is to mix, in temperature polyvinyl alcohol (PVA) powder with water
Be 85 DEG C heating in water bath and stirring under conditions of be configured to the PVA aqueous solution that mass concentration is 10%, so
After by PVA aqueous solution that 38.20ml～42.17ml mass concentration is 10% and 7.83ml～11.80ml mass
Concentration be 53% polyacrylic acid (PAA) aqueous solution carry out being mixed to get mixed under conditions of being sufficiently stirred for
Close liquid, replace with and PVA powder is mixed with water, in the heating in water bath that temperature is 85 DEG C and the condition of stirring
Under be configured to the PVA aqueous solution that mass concentration is 10%, then by 42.18ml～44.49ml mass concentration
Be 10% PVA aqueous solution and PAA aqueous solution that 5.51ml～7.82ml mass concentration is 53% fully
It is mixed to get mixed liquor under stirring condition, remains to obtain result same as in Example 1.
Embodiment 3
With reference to embodiment 1, difference is to mix, in temperature polyvinyl alcohol (PVA) powder with water
Be 85 DEG C heating in water bath and stirring under conditions of be configured to the PVA aqueous solution that mass concentration is 10%, so
After by PVA aqueous solution that 38.20ml～42.17ml mass concentration is 10% and 7.83ml～11.80ml mass
Concentration be 53% polyacrylic acid (PAA) aqueous solution carry out being mixed to get mixed under conditions of being sufficiently stirred for
Close liquid, replace with and PVA powder is mixed with water, in the heating in water bath that temperature is 85 DEG C and the condition of stirring
Under be configured to the PVA aqueous solution that mass concentration is 10%, then by 44.50ml～45.75ml mass concentration
Be 10% PVA aqueous solution and PAA aqueous solution that 4.25ml～5.50ml mass concentration is 53% fully
It is mixed to get mixed liquor under stirring condition, remains to obtain result same as in Example 1.
Embodiment 4
With reference to embodiment 1, difference is to mix, in temperature polyvinyl alcohol (PVA) powder with water
Be 85 DEG C heating in water bath and stirring under conditions of be configured to the PVA aqueous solution that mass concentration is 10%, so
After by PVA aqueous solution that 38.20ml～42.17ml mass concentration is 10% and 7.83ml～11.80ml mass
Concentration be 53% polyacrylic acid (PAA) aqueous solution carry out being mixed to get mixed under conditions of being sufficiently stirred for
Close liquid, replace with and PVA powder is mixed with water, in the heating in water bath that temperature is 85 DEG C and the condition of stirring
Under be configured to the PVA aqueous solution that mass concentration is 10%, then by 45.76ml～47.08ml mass concentration
Be 10% PVA aqueous solution and PAA aqueous solution that 2.92ml～4.24ml mass concentration is 53% fully
It is mixed to get mixed liquor under stirring condition, remains to obtain result same as in Example 1.
Embodiment 5
With reference to embodiment 1, difference is to mix, in temperature polyvinyl alcohol (PVA) powder with water
Be 85 DEG C heating in water bath and stirring under conditions of be configured to the PVA aqueous solution that mass concentration is 10%, so
After by PVA aqueous solution that 38.20ml～42.17ml mass concentration is 10% and 7.83ml～11.80ml mass
Concentration be 53% polyacrylic acid (PAA) aqueous solution carry out being mixed to get mixed under conditions of being sufficiently stirred for
Close liquid, replace with and PVA powder is mixed with water, in the heating in water bath that temperature is 85 DEG C and the condition of stirring
Under be configured to the PVA aqueous solution that mass concentration is 10%, then by 47.09ml～49.98ml mass concentration
Be 10% PVA aqueous solution and PAA aqueous solution that 0.02ml～2.91ml mass concentration is 53% fully
It is mixed to get mixed liquor under stirring condition, remains to obtain result same as in Example 1.
Embodiment 6
With reference to embodiment 1, it is resistant to elevated temperatures poly-that difference is to replace with simple glass substrate PET etc.
Compound sheet material, resistant to elevated temperatures thin polymer film, remain to obtain antifog anti-reflection coating.
Embodiment 7
With reference to embodiment 1, difference is that will regulate the pH of mixed liquor with hydrochloric acid or sodium hydroxide be
1～4, change into hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid, acetic acid, sodium hydroxide, potassium hydroxide, hydrogen sulfate
Potassium, sodium bisulfate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate etc. regulate
The pH of mixed liquor is 4.5 or 13, remains to obtain result same as in Example 1.
Embodiment 8
With reference to embodiment 5, difference is that by 47.09ml～49.98ml mass concentration be the PVA of 10%
Aqueous solution and the PAA aqueous solution that 0.02ml～2.91ml mass concentration is 53% replace with what equal proportion was amplified
PVA aqueous solution and PAA aqueous solution, such as, by the PVA aqueous solution that 49.98ml mass concentration is 10%
Replacing with 99.96ml mass concentration with the PAA aqueous solution that 0.02ml mass concentration is 53% is 10%
PVA aqueous solution and the PAA aqueous solution that 0.04ml mass concentration is 53%, remain to obtain and embodiment 5
Identical result.
Embodiment 9
With reference to embodiment 5, difference is that by 47.09ml～49.98ml mass concentration be the PVA of 10%
Aqueous solution and the PAA aqueous solution that 0.02ml～2.91ml mass concentration is 53% replace with equal in quality ratio
Polyvinyl alcohol water solution and polyacrylic acid aqueous solution, such as, be 10% by 47.09ml～49.98ml mass concentration
PVA aqueous solution and the PAA aqueous solution that 0.02ml～2.91ml mass concentration is 53% replace with
23.55ml～24.99ml mass concentration be 20% PVA aqueous solution and 0.04ml～5.82ml mass concentration be
The PAA aqueous solution of 26.5%, remains to obtain result same as in Example 5.
Embodiment 10
With reference to embodiment 5, difference is the time of high-temperature process is replaced with 1 minute or 720
Hour, remain to obtain result same as in Example 5.
Embodiment 11
With reference to embodiment 5, difference is that by 47.09ml～49.98ml mass concentration be the PVA of 10%
It is dense that aqueous solution and the PAA aqueous solution that 0.02ml～2.91ml mass concentration is 53% replace with 3.55ml mass
Degree is the PVA aqueous solution of 40% and PAA aqueous solution that 46.45ml mass concentration is 1%, remains to obtain
Result same as in Example 5.
Embodiment 12
With reference to embodiment 5, difference is that by 47.09ml～49.98ml mass concentration be the PVA of 10%
Aqueous solution and the PAA aqueous solution that 0.02ml～2.91ml mass concentration is 53% replace with 49.81ml mass
Concentration is the PVA aqueous solution of 1% and PAA aqueous solution that 0.19ml mass concentration is 85%, remains to obtain
Result same as in Example 5.
Embodiment 13
With reference to embodiment 5, difference is to replace with PVA the block of Polyethylene Glycol or Polyethylene Glycol
The main chains such as copolymer or side chain contain the polymer of hydroxyl, or replace with polypropylene amine or polyvinylamine
Contain the polymer of amino Deng main chain or side chain, PAA is replaced with the main chains such as polymethylacrylic acid or
Side chain contains the polymer of carboxyl, remains to obtain result same as in Example 5.
Embodiment 14
1) in a reservoir, PVA powder is mixed with water, in the heating in water bath that temperature is 85 DEG C and stirring
Under conditions of be configured to the PVA aqueous solution that mass concentration is 10%；
2) mixed by 2.07ml～3.55ml tetraethyl orthosilicate (TEOS) and ethanol (mass ratio is 1:3)
Close drop and be added to the step 1 that 50ml mass concentration is 10%) in the PVA aqueous solution that obtains, wherein, PVA
The amount of the amount of the material of middle hydroxyl and the material of tetraethyl orthosilicate is than for 6.6:1～11.4:1；Reaction temperature 0 DEG C
～be stirred 0.2～72 hour under the bath temperature of 100 DEG C, the pH adding nitre acid-conditioning solution is 1～7,
Proceed to stir 0.2～72 hour, after solution is transparent, adds 0.05ml 3-glycydoxy
Trimethoxy silane, wherein, the amount of the material of hydroxyl and 3-glycydoxy front three in PVA
The amount of the material of TMOS is than for 53973:1；Stir 0.2～72 hour, left at room temperature deaeration 0.2～72
Hour, after standing and defoaming PVA are cross-linked (degree of cross linking is to less than or equal to 60% more than or equal to 35%)
Liquid sucking filtration to remove precipitation；
3) by step 2) sucking filtration removes the liquid that obtains after precipitation, and use lifting, spraying, spin coating, scrape
Painting, roller coating or the manual method smeared are coated in unorganic glass (such as K7105 glass, the work of 5 millimeters thick
Art glass, microscope slide etc.), polymer plate or thin film be (such as Merlon (PC), polymethylacrylic acid
Methyl ester (PMMA), automobile sun film, resin lens, polyethylene terephthalate (PET)) etc.
In solid substrate, naturally dry or dry in the baking oven of 20 DEG C～150 DEG C, obtaining that there is network structure
The water-fast long-acting antifog frost-resistant clear coat of Controllable cross-linking degree.
4) 0.1 gram～0.7 gram of polyacrylic acid are dissolved in the ammonia of 4.5 milliliters, ultrasonic disperse；Then by
Being added dropwise to be mounted with in the container of 90 milliliters of dehydrated alcohol, stirring obtains mixed liquor；By 1 milliliter～4
The tetraethoxysilane of milliliter is added drop-wise in this mixed liquor with the speed of 45 microlitres per minute；After completion of dropwise addition,
Gained solution is at room temperature stirred, and obtains the sol solutions containing hollow silica ball nanoparticle；
5) by obtain containing hollow silica ball nanoparticle sol solutions use lifting, spraying, spin coating,
Blade coating, roller coating or the manual method smeared are coated on antifogging coating, i.e. obtain anti-reflection antifogging coating.
Embodiment 15
With reference to embodiment 14, difference be 2.07ml～3.55ml tetraethyl orthosilicate (TEOS) and
The mixed liquor of ethanol (mass ratio is 1:3) is added drop-wise to the step 1 that 50ml mass concentration is 10%) obtain
PVA aqueous solution in, wherein, the amount of the material of the amount of the material of hydroxyl and tetraethyl orthosilicate in PVA
Ratio is 6.6:1～11.4:1；It is stirred 0.2～72 hour under the bath temperature of reaction temperature 0 DEG C～100 DEG C,
The pH adding nitre acid-conditioning solution is 1～7, proceeds to stir 0.2～72 hour, adds after solution is transparent
Enter 0.05ml 3-glycydoxy trimethoxy silane, wherein, the material of hydroxyl in PVA
Measure amount with the material of 3-glycydoxy trimethoxy silane ratio for 53973:1；Stirring
0.2～72 hour, left at room temperature deaeration 0.2～72 hours, (crosslinking after standing and defoaming PVA are cross-linked
Degree for more than or equal to 35% to less than or equal to 60%) liquid sucking filtration to remove precipitation；Replacing with will
The mixed liquor of 0.30ml～2.06ml tetraethyl orthosilicate (TEOS) and ethanol (mass ratio is 1:7) is added drop-wise to
50ml mass concentration is the step 1 of 10%) in the PVA aqueous solution that obtains, reaction temperature 0 DEG C～100 DEG C
Bath temperature under be stirred 0.2～72 hour, add nitre acid-conditioning solution pH be 1～7, continue into
Row stirring 0.2～72 hour, adds 0.05ml 3-glycydoxy trimethoxy after solution is transparent
Base silane, stirs 0.2～72 hour, and left at room temperature deaeration 0.2～72 hours, by standing and defoaming PVA
After crosslinking, the liquid sucking filtration of (degree of cross linking is to less than 35% more than or equal to 5%) is to remove precipitation；Remain to obtain
Result that must be identical with embodiment 14.
Embodiment 16
With reference to embodiment 14, difference is tetraethyl orthosilicate replaces with 3-aminopropyl triethoxy
Silane, chlorosilane, tetramethoxy-silicane, positive silicic acid propyl ester or positive isopropyl silicate etc., all can obtain and
The result that embodiment 14 is identical.
Embodiment 17
With reference to embodiment 14, difference is to replace with nitric acid hydrochloric acid, sulphuric acid or phosphoric acid, equal energy
Obtain the result identical with embodiment 14.
Embodiment 18
With reference to embodiment 14, difference be 2.07ml～3.55ml tetraethyl orthosilicate (TEOS) and
The mixed liquor of ethanol (mass ratio is 1:3) is added drop-wise in the PVA aqueous solution that 50ml mass concentration is 10%,
Replace with 0.21ml～0.35ml tetraethyl orthosilicate (TEOS) and the mixing of ethanol (mass ratio is 1:3)
Drop is added in the PVA aqueous solution that 50ml mass concentration is 1%, all can obtain identical with embodiment 14
Result.
Embodiment 19
With reference to embodiment 14, difference be 2.07ml～3.55ml tetraethyl orthosilicate (TEOS) and
The mixed liquor of ethanol (mass ratio is 1:3) is added drop-wise in the PVA aqueous solution that 50ml mass concentration is 10%,
Replace with 8.27ml～14.18ml tetraethyl orthosilicate (TEOS) and ethanol (mass ratio is 10:1) is mixed
Close drop to be added in the PVA aqueous solution that 50ml mass concentration is 40%, all can obtain and embodiment 14 phase
Same result.
Embodiment 20
With reference to embodiment 14, difference is to replace 3-glycydoxy trimethoxy silane
It is changed to selected from aminopropyl triethoxysilane, γ-aminopropyl trimethoxysilane, γ-methacryl
Epoxide propyl trimethoxy silicane, VTES, vinyltrimethoxy silane, second
In thiazolinyl three ('beta '-methoxy ethyoxyl) silane, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane
One or more, all can obtain the result identical with embodiment 14.
Embodiment 21
With reference to embodiment 14, difference is in tetraethyl orthosilicate (TEOS) and the mixed liquor of ethanol
Tetraethyl orthosilicate (TEOS) and the mass ratio of ethanol be 1:3, replacing with mass ratio is 1:10 to 1:0
Not containing mass ratio in scope is the arbitrary proportion of 1:3, all can obtain the result identical with embodiment 14.
Embodiment 22
With reference to embodiment 14, difference is the amount of the material of hydroxyl in PVA and tetraethyl orthosilicate
The amount of material than for 6.6:1～11.4:1, replaces with both amount than for not content ratio in 5:1～100:1 scope
For the arbitrary proportion of 6.6:1～11.4:1, all the result identical with embodiment 14 can be obtained.
Embodiment 23
With reference to embodiment 14, difference is the amount of the material of hydroxyl in PVA and 3-glycidyl ether
The amount of the material of epoxide propyl trimethoxy silicane than for 53973:1, replaces with both amount than for 5:1～1:0
In scope, content, than the arbitrary proportion for 53973:1, all can not obtain the result identical with embodiment 14.
Embodiment 24
With reference to embodiment 14, difference is nitric acid replaces with hydrochloric acid, sulphuric acid or phosphorus acid-conditioning solution
PH to 1～7, all can obtain the result identical with embodiment 14.
Embodiment 25
With reference to embodiment 14, difference is PVA, tetraethyl orthosilicate, ethanol, nitric acid, 3-contracting
The amount of the materials such as water glycerin ether epoxide propyl trimethoxy silicane is enlarged, and also can obtain the same degree of cross linking
PVA liquid.Such as, by 2.07ml～3.55ml tetraethyl orthosilicate (TEOS) and ethanol (mass ratio
For 1:3) mixed liquor be added drop-wise in the PVA aqueous solution that 50ml mass concentration is 10%, in reaction temperature
Being stirred under the bath temperature of 0 DEG C～100 DEG C 0.2～72 hour, the pH adding nitre acid-conditioning solution is
1～7, proceed to stir 0.2～72 hour, after solution is transparent, adds 0.05ml 3-glycidyl ether oxygen
Base propyl trimethoxy silicane, stirs 0.2～72 hour, and left at room temperature deaeration 0.2～72 hours, by quiet
Put the liquid sucking filtration after deaeration PVA crosslinking to remove precipitation；Replace with positive for 4.14ml～7.10ml silicon
The mixed liquor of acetoacetic ester (TEOS) and ethanol (mass ratio is 1:3) is added drop-wise to 100ml mass concentration and is
In the PVA aqueous solution of 10%, under the bath temperature of reaction temperature 0 DEG C～100 DEG C, it is stirred 0.2～72
Hour, the pH adding nitre acid-conditioning solution is 1～7, proceeds to stir 0.2～72 hour, treats that solution is saturating
Add 0.1ml 3-glycydoxy trimethoxy silane after bright, stir 0.2～72 hour, room
The lower standing and defoaming 0.2 of temperature～72 hours, the liquid sucking filtration after standing and defoaming PVA being cross-linked is to remove precipitation；
All can obtain the result identical with embodiment 14.
Embodiment 26
With reference to embodiment 14, difference is that polyvinyl alcohol is replaced with other main chain or side chain contains hydroxyl
The polymer of base, such as one or more in Polyethylene Glycol, polyethyleneglycol block copolymer, equal energy
Obtain the result identical with embodiment 14.
Embodiment 27
With reference to embodiment 1-26, difference is, will outside anti-fog layer coating silicon dioxide hollow ball
Replace with other materials with anti-reflection performance, such as mesoporous silicon dioxide nano particle, remain to obtain with
The result that embodiment 1-26 is similar.
Embodiment 28
With reference to embodiment 1-26, difference is, will outside anti-fog layer coating silicon dioxide hollow ball
Layer replaces with other materials that can make penetration by water, can obtain the antifog multi-functional coatings of other functions, example
As coated the zirconium oxide nano-particle of high rigidity outside anti-fog layer, high intensity hardness and antifog can be obtained
Coating.
Embodiment 29
With reference to embodiment 1-26, difference is, will outside anti-fog layer coating silicon dioxide hollow ball
Layer replaces with optical Limiting coating, such as C60Coatings etc., can obtain not only optical Limiting but also antifog coating, its
Anti-fog effect is similar to embodiment 1-26.
Embodiment 30
With reference to embodiment 1-26, difference is, will outside anti-fog layer coating silicon dioxide hollow ball
Layer replaces with automatic cleaning coating, and such as coating of titanium dioxide etc. can obtain not only automatically cleaning but also antifog painting
Layer, its anti-fog effect is similar to embodiment 1-26.
Embodiment 31
With reference to embodiment 1-26, difference is, will outside anti-fog layer coating silicon dioxide hollow ball
Layer replaces with hydrophobic coating, and such as silicon fluoride coating etc., can obtain the most hydrophobic but also antifog coating, its
Anti-fog effect is similar to embodiment 1-26.
Embodiment 32
With reference to embodiment 1-26, difference is, will outside anti-fog layer coating silicon dioxide hollow ball
Layer replaces with Anti Glare Coatings, such as TiN-Si02Coatings etc., can obtain not only anti-dazzle but also antifog coating,
Its anti-fog effect is similar to embodiment 1-26.
Obviously, the above embodiment of the present invention is only for clearly demonstrating example of the present invention, and
It is not the restriction to embodiments of the present invention, for those of ordinary skill in the field,
Can also make other changes in different forms on the basis of described above, here cannot be to all
Embodiment give exhaustive, every belong to the obvious change that technical scheme extended out
Change or change the row still in protection scope of the present invention.
Claims (8)
1. a multi-functional antifogging coating, it is characterised in that: described multi-functional antifogging coating includes being coated on
Suprabasil at least one of which antifogging coating and at least one of which functional coat being coated on antifogging coating；
Described antifogging coating has hygroscopicity；Described functional coat can make water pass through.
The multi-functional antifogging coating of one the most according to claim 1, it is characterised in that: described antifog
Coating is selected from having hygroscopic polymer coating, having hygroscopic polymer and inorganic material crosslinking painting
Layer, there is hygroscopic polymer and crosslinked polymer coating or there is hygroscopic polymer and inorganic material
Material mixed coating.
The multi-functional antifogging coating of one the most according to claim 1, it is characterised in that: described function
Property coating selected from there is the coating of reflection preventing ability, there is the coating of self-cleaning performance, there is anti-glare properties
Can coating, there is the coating of optical limiting properties and there is the coating of hydrophobic performance in one or more.
The multi-functional antifogging coating of one the most according to claim 3, it is characterised in that have described in:
The coating of reflection preventing ability is hollow silica ball coating.
The multi-functional antifogging coating of one the most according to claim 4, it is characterised in that: described many merits
Energy antifogging coating is by being coated on suprabasil one layer of antifogging coating and the two-layer two being coated on antifogging coating
Silicon oxide hollow ball coating forms.
The multi-functional antifogging coating of one the most according to claim 1, it is characterised in that: described substrate
Selected from unorganic glass, polymer plate, thin polymer film, organo-mineral complexing sheet material, cable or fly
Machine shell.
7. the preparation method of a kind of multi-functional antifogging coating as described in claim 1-6 is arbitrary, its feature
It is, comprises the steps:
Substrate coats at least one of which there is hygroscopic antifogging coating；
Antifogging coating coats the functional coat that at least one of which can make water pass through, i.e. obtains multi-functional
Antifogging coating.
The preparation method of a kind of multi-functional antifogging coating the most according to claim 7, it is characterised in that
The mode of coating is lifting, spraying, spin coating, blade coating, roller coating or smears by hand.
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