CN106750235B - The preparation method of quaternary hydrophily UV-cured resin - Google Patents
The preparation method of quaternary hydrophily UV-cured resin Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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Abstract
The present invention provides a kind of preparation methods of quaternary hydrophily UV-cured resin, it includes the following steps: binary polyetheramine and acrylyl oxy-ethyl-trimethyl salmiac carrying out Michael addition reaction at room temperature, obtains double ends secondary amino compound intermediate；Double end secondary amino compound intermediates and polyfunctional acrylic ester are subjected to Michael addition reaction at 40~45 DEG C, obtain the quaternary hydrophily UV-cured resin.The present invention has the advantages that the preparation of 1, quaternary hydrophily UV-cured resin is simple, at a lower temperature, can be made in the short time by two step Michael addition reactions；2, the quaternary hydrophily UV-cured resin is fixed on the quaternary ammonium salt structure on the cross-linked network formed after photocuring because having with chemical bond, is applied in anti-fog coating, it is ensured that film has excellent initial and lasting anti-fog performance.
Description
Technical field
The present invention relates to a kind of preparation methods of quaternary hydrophily UV-cured resin, belong to high molecular material conjunction
At technical field.
Background technique
Vapor in air will condense into small drop and mist formation when temperature is lower than dew point.It is this undesirable
Influence frequently occurs in window, bathroom mirror, glasses, swimming and Lunettes, windshield, optical instrument camera lens, solar energy
Battery light-transmitting plate, car light, indicator light, agricultural film etc. these live on the transparent material that is closely related with us.Transparent material surface
Water droplet atomization as a result, not only light transmittance decline influence vision, harm is generated sometimes, such as when droplet is condensed in such as infrared light
When learning on the lens surfaces of sophisticated analytical instruments such as microscope, the accuracy of analysis can be reduced.And when droplet condenses in the sun
When on energy battery light-transmitting plate, causes the reduction of solar absorption efficiency, give full play to and should have to be unfavorable for solar cell device
Effect.
In order to solve these problems, super-hydrophobic or super hydrophilic processing can be generally carried out to material surface.It is super-hydrophobic common complete
Fluorine type resin, one side price is higher, and on the other hand the resinoid is generally softer, wears no resistance, while its hydrophobic property is also led
Its surface is caused to be easy absorption greasy dirt and dust, the effect not reached requirement instead.And organic hydrophilic coating price itself is more just
Preferably, its wearability can also be improved by some modifications.Not only compared to hydrophobic coating processing method using organic hydrophilic coating
It is easy for construction and cheap.
It is concentrated mainly on super hydrophilic research both at home and abroad now, as coating surface introducing can form the group such as carboxylic of hydrogen bond
Base, amino, sulfydryl, hydroxyl；Some ionic groups: carboxylate radical, sulfonate radical, ammonium root, phosphate radical etc.；Or introduce hydrophilic second
Oxygroup unit, when introducing these a certain number of groups or ion, the surface of coating can achieve super hydrophilic state, water
Sprawled after vapour condensation in substrate surface height, form one layer of uniform moisture film, eliminate tiny drops of water to the diffusing reflection of light and
Achieve the purpose that antifog.Super hydrophilic approach is prepared at present mainly passes through physical blending, Chemical modification, chemical bonding
Method.
Chinese patent CN 104053731A discloses a kind of thermosetting property anti-fog coating, which includes polyurethane
Dispersion, modified aziridine hardener, hydrophilic silicon oxides nanoparticle, surfactant.This is a kind of thermosetting aqueous
Coating, need 110 DEG C or more heat 20 minutes more than can just be cured, formation cross-linked network.Although anti-fog performance is preferable,
But energy consumption is high and to play the ingredient of hydrophilic antifogging performance here be mainly surfactant in fact, and it is not involved at all consolidates
Change reaction, be only crosslinked network physical and fix, in the case where high humility, is easy to be lost and influence to continue anti-fog properties
Energy.In addition, hydrophilic silicon oxides nanoparticle also needs to carry out nanometer using the silane coupling agent with hydrophilic radical
Silica dispersion is surface-treated to obtain, and technics comparing is complicated.And hydrophilic silane coupling agent price is somewhat expensive, and plants
Class is rare.Therefore manufacturing cost can improve.
Chinese patent CN102911582A discloses a kind of ultraviolet light curing anti fogging coating.The main body hydrophilic resin of the coating
Rouge is by polymerizable nonionic surfactant allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether, acrylate and acrylic acid
The polyacrylate that side chain contains carboxyl is obtained through free radical polymerization, then it is sweet to carry out open loop Glycidyl methacrylate for side chain carboxyl group
The epoxy group of grease and obtain side chain photocuring hydrophilic polyacrylic ester containing double bonds.But allyloxy monomer is poly-
It is more much lower than the polymerization activity of acrylic ester monomer to close activity, therefore a large amount of unreacted allyloxy nonyl benzene oxygen can be remained
Base propyl alcohol polyoxyethylene ether.Although light can also occur in coating for remaining allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether
Polymerization reaction, but its polymerization activity is lower, therefore still has part and remain in coating, is not engaged in curing reaction and is formed
Cross-linked network is only crosslinked network physical and fixes, and in the case where high humility, is easy to be lost and influence to continue anti-fog properties
Energy.
Summary of the invention
For the defects in the prior art, the object of the present invention is to provide a kind of solidifications of quaternary hydrophily ultraviolet light to set
Rouge is applied in ultraviolet light curing anti fogging coating formula, and after ultraviolet light solidifies, not only initial hydrophilicity is good for film, and
And water-tolerant, there is lasting anti-fog performance, hardness of film is high, resistance to wiping is good, is highly suitable to be applied for having anti-fog properties
The demanding field of energy, such as car light, windshield, bathroom mirror, optical lens material.
The present invention is achieved by the following technical solutions:
The present invention provides a kind of preparation method of quaternary hydrophily UV-cured resin comprising following steps:
Binary polyetheramine and acrylyl oxy-ethyl-trimethyl salmiac are subjected to Michael addition reaction at room temperature, obtained
Double end secondary amino compound intermediates；
Double end secondary amino compound intermediates and polyfunctional acrylic ester are subjected to mikey at 40~45 DEG C
That addition reaction, obtains the quaternary hydrophily UV-cured resin.
Preferably, the molar ratio of the binary polyetheramine and acrylyl oxy-ethyl-trimethyl salmiac is 1:2.
Preferably, the binary polyetheramine is selected from D-230, D-400, D-2000, ED-600, ED-900 and ED-
At least one of 2003.
Preferably, the polyfunctional acrylic ester is the acrylate monomer that degree of functionality is not less than 4.According to
Acrylate monomer of the degree of functionality less than 4, then the degree of functionality of the light-cured resin prepared is low, and water resistance can reduce, and continues antifog
Performance is poor, and in addition wearability also can be reduced accordingly.Preferably, the acrylate monomer is to contain ethoxy unit
More official's monomers.
Preferably, in more official's monomers containing ethoxy unit, the quantity of ethoxy unit is not less than 20
It is a.When the ethoxy unit is less than 20, it is too poor to will lead to polyfunctionality hydrophily UV-cured resin hydrophily, antifog
Performance is poor.
It can be by synthesizing using the hydrophilicrty of the quaternary hydrophily UV-cured resin of the method for the present invention preparation
Raw material controls, such as the molecular weight of binary polyetheramine is big, i.e. ethyoxyl or isopropoxy number is more, hydrophily is bigger；More officials
Ethoxy unit number is more in energy degree acrylate, and hydrophily is bigger.For polyfunctional acrylic ester, in same ethyoxyl list
In the case where first number, degree of functionality is bigger, and hydrophily is smaller.Therefore, made using the quaternary hydrophily UV-cured resin
Based on resin in photocuring anti-fog coating system, due to introducing a large amount of hydrophilic parts, film to have excellent parent
Aqueous energy, can make the condensation vapor in air be formed on its surface moisture film rather than water droplet, have initial anti-fog properties well
Energy.On the other hand, due to polyfunctionality structure, can with the other UV-cured resins or monomer in coating system, through purple
Cross-linked network structure is formed after outer photocuring, hydrophilic parts are not fixed on cross-linked network not instead of physically, to change
It learns key to be fixed on cross-linked network, water or vapor will not be caused to fall painting film bubble, so film protracted hydrophilicity is good, embodied
With lasting anti-fog performance.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, the preparation of quaternary hydrophily UV-cured resin is simple, at a lower temperature, passes through two steps in the short time
Michael addition reaction can be made；
2, the quaternary hydrophily UV-cured resin is formed after photocuring because having to be fixed on chemical bond
Quaternary ammonium salt structure on cross-linked network, is applied in anti-fog coating, it is ensured that film has excellent initial and continues antifog
Performance；
3, the hydrophilicrty of the quaternary hydrophily UV-cured resin can be controlled arbitrarily as desired, be met
When the Superhydrophilic in some fields needs, the binary polyetheramine and ethoxy radix more than ethyoxyl or isopropoxy number can choose
The slightly lower polyfunctional acrylic ester of more degrees of functionality will meet with excellent water resistance, i.e. guarantee is initial anti-fog properties, also has both
Have excellent when continuing the good domain requirement of anti-fog performance, can be reached by using the high polyfunctional acrylic ester of degree of functionality
It arrives；
4, ultraviolet light curing anti fogging coating formula is used for using quaternary hydrophily UV-cured resin of the invention
In, after ultraviolet light solidifies, film initial hydrophilicity is good, while having good water resistance, is reflected on anti-fog performance and is exactly
Not only initial anti-fog performance is good, and has lasting anti-fog performance.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Ammonium salt type hydrophily UV-cured resin of the invention the preparation method is as follows:
Since commercially available raw material limit, more official's acrylate are only with following four:
3 officials: ethyoxyl trimethylolpropane trimethacrylate (EO35mol), ethyoxyl quantity therein are 35；
4 officials: ethoxylated pentaerythritol tetraacrylate (EO15mol), ethyoxyl quantity therein are 15；
4 officials: ethoxylated pentaerythritol tetraacrylate (EO35mol), ethyoxyl quantity therein are 35；
4 officials: ethoxylated pentaerythritol tetraacrylate (EO120mol), ethyoxyl quantity therein are 120；
6 officials: ethyoxyl double pentaerythritol methacrylate (EO96mol), ethyoxyl quantity therein are 96.
Embodiment 1
The present embodiment is related to a kind of preparation method of quaternary hydrophily UV-cured resin, specifically includes following step
It is rapid:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (70 grams), resistance
Poly- agent p-hydroxyanisole (0.14 gram), polyetheramine D400 (2.30 grams, 5mmol) and 80% acrylyl oxy-ethyl-trimethyl chlorination
Aqueous ammonium (24.2 grams, 10mmol) reacts at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption peak of double bond, the
Single step reaction terminates.Then ethyoxyl double pentaerythritol methacrylate (EO96mol) (48.02 grams, 10mmol) are added, heating
It is reacted 3 hours to 45 DEG C, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, obtains light yellow
Transparency liquid.Then it is precipitated with n-hexane, then is dried in vacuo the quaternary for obtaining that degree of functionality is 10 for 12 hours through 50 DEG C
Hydrophily UV-cured resin.
Embodiment 2
The present embodiment is related to a kind of preparation method of quaternary hydrophily UV-cured resin, specifically includes following step
It is rapid:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (78 grams), resistance
Poly- agent p-hydroxyanisole (0.16 gram), polyetheramine D400 (2.30 grams, 5mmol) and 80% acrylyl oxy-ethyl-trimethyl chlorination
Aqueous ammonium (24.2 grams, 10mmol) reacts at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption peak of double bond, the
Single step reaction terminates.Then ethoxylated pentaerythritol tetraacrylate (EO120mol) (56.32 grams, 10mmol) are added, heating
It is reacted 3 hours to 45 DEG C, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, obtains light yellow
Transparency liquid.Then it is precipitated with n-hexane, then is dried in vacuo the quaternary parent for obtaining that degree of functionality is 6 for 12 hours through 50 DEG C
Waterborne ultraviolet curing resin.
Embodiment 3
The present embodiment is related to a kind of preparation method of quaternary hydrophily UV-cured resin, specifically includes following step
It is rapid:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (70 grams), resistance
Poly- agent p-hydroxyanisole (0.14 gram), polyetheramine ED-600 (2.64 grams, 5mmol) and 80% acrylyl oxy-ethyl-trimethyl chlorine
Change aqueous ammonium (24.2 grams, 10mmol), reacts at room temperature 1.5 hours, FT-IR can't detect 810cm-1Locate the absorption peak of double bond,
First step reaction terminates.Then ethyoxyl double pentaerythritol methacrylate (EO96mol) (48.02 grams, 10mmol) are added, rise
Temperature to 45 DEG C react 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, obtains pale yellow
Color transparency liquid, is then precipitated with n-hexane, then the quaternary ammonium salt for obtaining that degree of functionality is 10 for 12 hours is dried in vacuo through 50 DEG C
Type hydrophily UV-cured resin.
Embodiment 4
The present embodiment is related to a kind of preparation method of quaternary hydrophily UV-cured resin, specifically includes following step
It is rapid:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (76 grams), resistance
Poly- agent p-hydroxyanisole (0.17 gram), polyetheramine ED-900 (10.0 grams, 10mmol) and 80% acrylyl oxy-ethyl-trimethyl
Aqueous ammonium chloride solution (48.4 grams, 20mmol) reacts at room temperature 1.5 hours, and FT-IR can't detect the absorption of double bond at 810cm-1
Peak, first step reaction terminate.Then ethoxylated pentaerythritol tetraacrylate (EO35mol) (37.8 grams, 20mmol) are added, rise
Temperature to 45 DEG C react 3 hours, FT-IR can't detect 3400~3300cm-1Locate the absorption peak of secondary amine, reaction was completed, obtains pale yellow
Color transparency liquid, is then precipitated with n-hexane, then the quaternary for obtaining that degree of functionality is 6 for 12 hours is dried in vacuo through 50 DEG C
Hydrophily UV-cured resin.
Embodiment 5
The present embodiment is related to a kind of preparation method of quaternary hydrophily UV-cured resin, specifically includes following step
It is rapid:
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (75 grams), resistance
Poly- agent p-hydroxyanisole (0.17 gram), polyetheramine ED-900 (5.0 grams, 5mmol) and 80% acrylyl oxy-ethyl-trimethyl chlorine
Change aqueous ammonium (24.2 grams, 10mmol), reacts at room temperature 1.5 hours, FT-IR can't detect 810cm-1Locate the absorption peak of double bond,
First step reaction terminates.Then ethoxylated pentaerythritol tetraacrylate (EO120mol) (56.32 grams, 10mmol) are added, rise
Temperature to 45 DEG C react 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, obtains light yellow
Then transparency liquid is precipitated with n-hexane, then the quaternary parent for obtaining that degree of functionality is 6 for 12 hours is dried in vacuo through 50 DEG C
Waterborne ultraviolet curing resin.
Comparative example 1
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (72 grams), resistance
Poly- agent p-hydroxyanisole (0.14 gram), hexamethylene diamine (0.58 gram, 5mmol) and 80% acrylyl oxy-ethyl-trimethyl salmiac water
Solution (24.2 grams, 10mmol) reacts at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption peak of double bond, the first step
Reaction terminates.Then ethyoxyl double pentaerythritol methacrylate (EO96mol) (48.02 grams, 10mmol) are added, are warming up to 45
DEG C reaction 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, obtains light yellow clear liquid
Then body is precipitated with n-hexane, then the quaternary hydrophily for obtaining that degree of functionality is 10 for 12 hours is dried in vacuo through 50 DEG C
UV-cured resin.
Comparative example 2
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (62 grams), resistance
Poly- agent p-hydroxyanisole (0.12 gram), polyetheramine D400 (4.6 grams, 5mmol) and dimethylaminoethyl acrylate (14.22 grams,
10mmol), it reacts at room temperature 1.5 hours, FT-IR can't detect 810cm-1Locate the absorption peak of double bond, first step reaction terminates.Then
It is added ethoxylated pentaerythritol tetraacrylate (EO120mol) (56.32 grams, 10mmol), is warming up to 45 DEG C and reacts 3 hours,
FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, light yellow clear liquid is obtained, then with just
Hexane is precipitated, then the hydrophily UV-cured resin for obtaining that degree of functionality is 6 for 12 hours is dried in vacuo through 50 DEG C.
Comparative example3
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (60 grams), resistance
Poly- agent p-hydroxyanisole (0.14 gram), polyetheramine ED-900 (10.0 grams, 10mmol) and 80% acrylyl oxy-ethyl-trimethyl
Aqueous ammonium chloride solution (48.4 grams, 20mmol) reacts at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption of double bond
Peak, first step reaction terminate.Then ethoxylated pentaerythritol tetraacrylate (EO15mol) (20.24 grams, 20mmol) are added,
It is warming up to 45 DEG C to react 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed, obtains pale yellow
Color transparency liquid, is then precipitated with n-hexane, then the hydrophily purple for obtaining that degree of functionality is 6 for 12 hours is dried in vacuo through 50 DEG C
Outer light-cured resin.
Comparative example 4
Equipped with mechanical stirring, thermometer, nitrogen gatherer 250 milliliters of four-hole bottles in, be added ethyl alcohol (75 grams), resistance
Poly- agent p-hydroxyanisole (0.17 gram), polyetheramine ED-900 (10.0 grams, 10mmol) and 80% acrylyl oxy-ethyl-trimethyl
Aqueous ammonium chloride solution (48.4 grams, 20mmol) reacts at room temperature 1.5 hours, and FT-IR can't detect 810cm-1Locate the absorption of double bond
Peak, first step reaction terminate.Then be added ethyoxyl trimethylolpropane trimethacrylate (EO35mol) (36.72 grams,
20mmol), it is warming up to 45 DEG C to react 3 hours, FT-IR can't detect 3400-3300cm-1Locate the absorption peak of secondary amine, reaction was completed,
Light yellow clear liquid is obtained, is then precipitated with n-hexane, then is dried in vacuo through 50 DEG C and obtains within 12 hours degree of functionality as 4
Hydrophily UV-cured resin.
Performance test
To quaternary hydrophily UV-cured resin prepared by institute's Examples 1 to 5 and comparative example 1~4, it is made into respectively
After the ultraviolet light curing anti fogging coating of the Application Example 1~5 and Comparison study example 1~4 that are listed in Table 1 below, using PET as base
Coating prepared by Application Example and Comparison study example is coated on its surface with No. 10 line stick, is put into 60 DEG C of baking oven 1min by material,
Solidify later by ultraviolet light, energy 500mJ/cm2。
It respectively corresponds the coating made from Examples 1 to 5 and Comparison study example 1~4 and carries out performance detection, measure coating
Adhesive force, pencil hardness, wearability, initial stage water contact angle and sustained water contact angle and anti-fog performance.Concrete outcome is listed in table 1
In.
Specific performance detection project and corresponding method are as follows:
One, adhesive force
Using baige method, specimen page adhesive force is tested with 3M Pressure sensitive adhesive tape.
Appraisal procedure:
5B- scribing edge is smooth, falls off the edge and intersection of scribing line are uncoated；
4B- has the coating shedding of small pieces in the intersection of scribing line, and the gross area that falls off is less than 5%；
3B- has the coating shedding of small pieces at the edge and intersection of scribing line, and fall off the gross area 5~15% it
Between；
2B- has sheet of coating shedding at the edge and intersection of scribing line, and fall off the gross area 15~35% it
Between；
1B- has sheet of coating shedding at the edge and intersection of scribing line, and fall off the gross area 35~65% it
Between；
0B- has sheet of coating shedding at the edge and intersection of scribing line, and the gross area that falls off is greater than 65%.
Two, pencil hardness
Referring to standard GB/T/T6739 " hardness of paint film pencil measuring method ".
Three, wear-resisting property
Using 0000# steel wool, 300g power, one is denoted as once back and forth, and the number scratched occurs in recording surface.
Appraisal procedure: after the friction of certain number, whether observation coating has scratch, is resistant to when recording without scratch
Most Rubbing numbers.
Four, initial stage hydrophilic angle
4 μ L deionized waters are dripped in the specimen surface being cured, are measured within the scope of 20~25 DEG C with contact angle tester.
Five, continue hydrophilic angle
The sample being cured is put into deionized water and is impregnated for 24 hours, is measured after drying with contact angle measurement.
Six: anti-fog properties: the test board that surface temperature is 25 degree being horizontally placed above 80 DEG C of the water surface at 10cm, sample is observed
The time that plate hazes.
X hazes in 1 second,
Δ: haze after 10 seconds,
Haze after zero: 30 second,
◎: it does not haze.
Table 1
As can be seen from Table 1, Application Example 1~5 has preferable anti-fog performance.Initial water contact is below 10
Degree, the water contact angle after impregnating for 24 hours are below 35 degree, and anti-fog performance is excellent, while wearability might as well.
Comparison study example 1 is compared with Application Example 1, since quaternary hydrophily purple light solidified resin used synthesizes
When, polyetheramine D400, the hydrophily ratio of the final quaternary hydrophily UV-cured resin of gained are replaced using hexamethylene diamine
It is poor, therefore be used in anti-fog coating formula, although coating abrasion performance improves a lot, cause the hydrophily of coating poor,
Because without having anti-fog performance.
Comparison study example 2 is compared with Application Example 2, when due to hydrophily UV-cured resin used synthesis, first
When step reaction, using presoma-dimethylaminoethyl acrylate of acrylyl oxy-ethyl-trimethyl salmiac come when replacing it, institute
Hydrophily UV-cured resin be it is non-ionic, be free of quaternary ammonium salt, hydrophily is poor, thus be used in antifog painting
In material formula, the hydrophily of coating is poor, does not have anti-fog performance.
Comparison study example 3 is compared with Application Example 4, since quaternary hydrophily UV-cured resin used synthesizes
When, using ethoxylated pentaerythritol tetraacrylate (EO15mol), the final quaternary hydrophily UV-cured resin of gained
Hydrophily it is poor, therefore be used in anti-fog coating formula in, although coating abrasion performance slightly improves, lead to the parent of coating
Aqueous difference, because without having anti-fog performance.
Comparison study example 4 is compared with Application Example 4, since quaternary ammonium salt hydrophily UV-cured resin used synthesizes
When, using ethyoxyl trimethylolpropane trimethacrylate (EO35mol), obtain tetra functional quaternary hydrophily ultraviolet light
Solidified resin.Because final resin degree of functionality is lower, hydrophily is very good, and final coating is caused to make hydrophilic portion subnetting due to water-swellable
Network is detached from from substrate surface, and hydrophobic part in coating is caused to be in the great majority, and substantially reduces hydrophily.Coating is wear-resisting simultaneously
It is significantly reduced with hardness.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (3)
1. a kind of preparation method of quaternary hydrophily UV-cured resin, which comprises the steps of:
Binary polyetheramine and acrylyl oxy-ethyl-trimethyl salmiac are subjected to Michael addition reaction at room temperature, obtain double ends
Hold secondary amino compound intermediate；
Double end secondary amino compound intermediates and polyfunctional acrylic ester are carried out Michael to add at 40~45 DEG C
At reaction, the quaternary hydrophily UV-cured resin is obtained；
The polyfunctional acrylic ester is the acrylate monomer that degree of functionality is not less than 4；
The acrylate monomer is more official's monomers containing ethoxy unit；
In more official's monomers containing ethoxy unit, the quantity of ethoxy unit is not less than 20.
2. the preparation method of quaternary hydrophily UV-cured resin as described in claim 1, which is characterized in that described
The molar ratio of binary polyetheramine and acrylyl oxy-ethyl-trimethyl salmiac is 1:2.
3. the preparation method of quaternary hydrophily UV-cured resin as claimed in claim 1 or 2, which is characterized in that
The binary polyetheramine is selected from least one of D-230, D-400, D-2000, ED-600, ED-900 and ED-2003.
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| CN1265408A (en) * | 2000-03-30 | 2000-09-06 | 吉林大学 | Hydrophilic antifogging and antifrosting anti-friction coating and its application |
| CN1472268A (en) * | 2003-06-20 | 2004-02-04 | 上海小糸车灯有限公司 | Lyophilic high-molecular antifogging coating and preparing method thereof |
| JP2009226729A (en) * | 2008-03-21 | 2009-10-08 | Fujifilm Corp | Anti-fogging film |
| CN106118173A (en) * | 2016-07-28 | 2016-11-16 | 上海维凯光电新材料有限公司 | Hydrophilic antifogging coating composition of photo-thermal dual curable and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1265408A (en) * | 2000-03-30 | 2000-09-06 | 吉林大学 | Hydrophilic antifogging and antifrosting anti-friction coating and its application |
| CN1472268A (en) * | 2003-06-20 | 2004-02-04 | 上海小糸车灯有限公司 | Lyophilic high-molecular antifogging coating and preparing method thereof |
| JP2009226729A (en) * | 2008-03-21 | 2009-10-08 | Fujifilm Corp | Anti-fogging film |
| CN106118173A (en) * | 2016-07-28 | 2016-11-16 | 上海维凯光电新材料有限公司 | Hydrophilic antifogging coating composition of photo-thermal dual curable and preparation method thereof |
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