CN106398512A - Superhydrophilic anti-fogging nano zirconiumhydrogen phosphate hybrid coating - Google Patents
Superhydrophilic anti-fogging nano zirconiumhydrogen phosphate hybrid coating Download PDFInfo
- Publication number
- CN106398512A CN106398512A CN201610865448.9A CN201610865448A CN106398512A CN 106398512 A CN106398512 A CN 106398512A CN 201610865448 A CN201610865448 A CN 201610865448A CN 106398512 A CN106398512 A CN 106398512A
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- hydrogen zirconium
- acid hydrogen
- group
- nanometer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a superhydrophilic anti-fogging nano zirconiumhydrogen phosphate hybrid coating. The superhydrophilic anti-fogging nano zirconiumhydrogen phosphate hybrid coating comprises, by weight, 8 to 20 parts of zirconiumhydrogen phosphate containing olefinic bonds and sulfonic acid groups, 5 to 30 parts of a UV resin oligomer, 5 to 15 parts of a reactive diluent containing 1 to 6 functional groups, 0.5 to 2 parts of a levelling agent, 10 to 50 parts of a solvent, and 2 to 6 parts of a photoinitiator. A preparation method of the superhydrophilic anti-fogging nano zirconiumhydrogen phosphate hybrid coating comprises following steps: the zirconiumhydrogen phosphate containing olefinic bonds and sulfonic acid groups is subjected to ultrasonic dispersion in the solvent; the UV resin oligomer, the reactive diluent containing 1 to 6 functional groups, the leveling agent, and the photoinitiator are added; and ultrasonic dispersion is carried out for a second time after uniform stirring. The superhydrophilic anti-fogging nano zirconiumhydrogen phosphate hybrid coating possesses excellent superhydrophilic anti-fogging performance, water resistance, and weathering resistance, and long service life; and hardness, wear resistance, scratch resistance, finger print pollution resistance, and stain resistance of coating layers prepared from the superhydrophilic anti-fogging nano zirconiumhydrogen phosphate hybrid coating are excellent.
Description
Technical field
The present invention relates to technical field of coatings is and in particular to a kind of super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating.
Background technology
The contact angle on transparent material such as glass, plastics, the surface of thin film for the water, all more than 40 °, has temperature in surfaces externally and internally
During difference, steam can condense in material surface to the cold and form mist, the transparency of impact material.Have super hydrophilic in material surface coating
The clear coat of performance, can make water material surface contact angle below 5 ° so that the water smoke of material surface or the globule exist
Material surface drawout, forms moisture film, and moisture film does not affect the transparency of material, so reaches antifog purpose.Commercialization at present
Super hydrophilic anti-fog coating be mainly pure macromolecular material system, the hydrophilic group that this material plays super hydrophilic effect is to be connected on
So that the resistance to water of this coating is poor on high polymer main chain, the service life ultimately causing super-hydrophilic coating is shorter, weatherability
Poor.The hardness of the coating prepared by this coating is relatively low simultaneously, and wearability, scratch resistance, anti-fingerprint print, anti-pollution characteristic are all
Poor.
Content of the invention
Based on this, the present invention provides a kind of super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating, and its hydrophilic antifogging performance is good,
Water resistance and weather resistance are good, last a long time；And the coating hardness height of this coating preparation, wearability, scratch resistance, anti-finger
Escutcheon, anti-pollution characteristic are all higher.
In order to realize the purpose of the present invention, the present invention employs the following technical solutions：
A kind of super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating, it includes the component of following weight portion：
Phosphoric acid hydrogen zirconium 8-20 part containing ethylene linkage and sulfonic acid group, low colourity UV resin oligomers 5-30 part, contain 1-6 sense
Reactive diluent 5-15 part of group, levelling agent 0.5-2 part, solvent 10-50 part, light trigger 2-6 part.
Wherein in some embodiments, described super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating includes following weight portion
Component：
10 parts of the phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group, 10 parts of low colourity UV resin oligomers, containing 1-6 functional group
15 parts of reactive diluent, 0.5 part of levelling agent, 50 parts of solvent, 3 parts of light trigger.
Wherein in some embodiments, the described phosphoric acid hydrogen zirconium preparation method containing ethylene linkage and sulfonic acid group is：With lamellar
Phosphoric acid hydrogen zirconium nano-particle is raw material, through organic amine intercalation stripping reaction, generates the phosphoric acid hydrogen zirconium nano-particle of monolayer, then divides
Not with the phosphoric acid hydrogen zirconium nano-particle of the silane coupler with ethylene linkage and the silane coupler with sulfydryl and monolayer through surface grafting
Sulfhydryl oxidase then is become sulfonic acid group with oxidant by reaction, is prepared into and has and the containing of high-molecular organic material excellent compatibility
Ethylene linkage and the described phosphoric acid hydrogen zirconium nano-particle of sulfonic acid group.
Wherein in some embodiments, the phosphoric acid hydrogen zirconium nano-particle of described lamellar is alpha-phosphate hydrogen zirconium and γ-phosphoric acid hydrogen
One of zirconium or the mixture of alpha-phosphate hydrogen zirconium and γ-phosphoric acid hydrogen zirconium.
Wherein in some embodiments, the described silane coupler with ethylene linkage includes VTES, second
Thiazolinyl trimethoxy silane, vinyl three (methoxy ethoxy) silane, methacryloxypropyl, 3-
In (methacryloxypropyl) propyl trimethoxy silicane and 3- methacryloyloxypropyl methyl dimethoxysilane one
Plant or several mixture.
Wherein in some embodiments, the described silane coupler with sulfydryl is double-[3- (triethoxysilicane) propyl group]-four
The mixture of one or more of sulfide, mercaptopropyl trimethoxysilane and 3- mercaptopropyltriethoxysilane.
Wherein in some embodiments, described oxidant is hydrogen peroxide, permanganate, sodium peroxide, in oleum
The mixture of one or more.
Wherein in some embodiments, described low colourity UV resin oligomers include low colourity polyurethane acrylate, low
The mixture of one or more of colourity polyester acrylate, low colourity polyether acrylate, low colourity p thiodipropionic acid ester,
Colourity Fe-Co≤2 of described low colourity UV resin oligomers, the molecular weight of described low colourity UV resin oligomers is 1000-
3000, the functional group of described low colourity UV resin oligomers is 2-6.
Wherein in some embodiments, the described reactive diluent containing 1-6 functional group is (methyl) esters of acrylic acid 1-6
The free radical type monomer of individual functional group, including simple function group (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate and
The hexanediyl ester of difunctional.
Wherein in some embodiments, the preparation method of described super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating is：Will
The described phosphoric acid hydrogen zirconium ultrasound wave containing ethylene linkage and sulfonic acid group is scattered in described solvent, is subsequently adding described UV resin low
Polymers, the reactive diluent containing 1-6 functional group, levelling agent and light trigger, after stirring, ultrasound wave dispersion is again
?.
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention ,-the OH on stratiform phosphoric acid hydrogen zirconium surface has
Acidity, can occur neutralization reaction with containing the amido in organic amine molecule, can be shelled by the phosphoric acid hydrogen zirconium of this reaction stratiform
From the nanoplatelet becoming monolayer, the ethylene linkage of radical reaction can be carried out in phosphoric acid hydrogen zirconium surface grafting, phosphoric acid can be improved
Hydrogen zirconium and the compatibility of organic polymer monomer；In phosphoric acid hydrogen zirconium surface grafting sulfonic acid group, the parent of phosphoric acid hydrogen zirconium can be improved
Aqueouss energy；By surface graft modification, it is grafted ethylene linkage and sulfonic acid group on phosphoric acid hydrogen zirconium surface simultaneously, phosphoric acid hydrogen zirconium can be improved
The compatibility with organic polymer monomer and hydrophilicity；By this modified phosphoric acid hydrogen zirconium and organic polymer monomer copolymerizable
Reaction, can prepare a kind of nanometer phosphoric acid hydrogen zirconium/super hydrophilic coating of organic polymer hybridization compounding with super hydrophilicity,
Through test, this super hydrophilic anti-fog coating anti-fog performance is good, and water resistance and weather resistance are good, and the coating of this coating preparation
Hardness height, wearability, scratch resistance, anti-fingerprint print, anti-pollution characteristic are all higher, in vehicle backing rear-view mirror, windshield, wall mirror, trip
The aspects such as swimming glasses, optical protection ball cover have good application prospect.
Specific embodiment
For the ease of understanding the present invention, the present invention will be described more fully below.But, the present invention can be to be permitted
How different forms is realizing however it is not limited to embodiment described herein.On the contrary, providing the purpose of these embodiments to be to make
Understanding to the disclosure is more thoroughly comprehensive.
Unless otherwise defined, all of technology used herein and scientific terminology and the technical field belonging to the present invention
The implication that technical staff is generally understood that is identical.The term being used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body is it is not intended that in limiting the present invention.
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention, it includes the component of following weight portion：
Phosphoric acid hydrogen zirconium 8-20 part containing ethylene linkage and sulfonic acid group, low colourity UV resin oligomers 5-30 part, contain 1-6 sense
Reactive diluent 5-15 part of group, levelling agent 0.5-2 part, solvent 10-50 part, light trigger 2-6 part.
Wherein in some embodiments, described super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating includes following weight portion
Component：10 parts of the phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group, 10 parts of low colourity UV resin oligomers, the work containing 1-6 functional group
15 parts of diluent of property, 0.5 part of levelling agent, 50 parts of solvent, 3 parts of light trigger.
Wherein, the described phosphoric acid hydrogen zirconium preparation method containing ethylene linkage and sulfonic acid group is：Phosphoric acid hydrogen zirconium nanometer with lamellar
Grain is raw material, through organic amine intercalation stripping reaction, generates the phosphoric acid hydrogen zirconium nano-particle of monolayer, then uses the silicon with ethylene linkage respectively
The phosphoric acid hydrogen zirconium nano-particle of alkane coupling agent and the silane coupler with sulfydryl and monolayer is through Surface grafting reaction, then uses oxidant
Sulfhydryl oxidase is become sulfonic acid group, is prepared into and has with high-molecular organic material excellent compatibility containing ethylene linkage and sulfonic acid group
Phosphoric acid hydrogen zirconium nano-particle.There is following course of reaction：
Specifically, for example：By the phosphoric acid hydrogen zirconium ultrasonic stripping of propylamine solution of lamellar, it is subsequently adding hydrochloric acid and replaces removal third
Amine, is replaced with ethanol with water and washs unnecessary hydrochloric acid, through ultrasonic, phosphoric acid hydrogen zirconium after peeling off is scattered in ethanol solution, adds
VTES and mercaptopropyl trimethoxysilane, add acetic acid to make the pH value of system be maintained at 2.0～6.0, in
Stirring reaction 3 hours at 50 DEG C, add hydroperoxidation 3 hours, and ethylene linkage and sulfonic phosphorus are contained in prepared surface simultaneously
Sour hydrogen zirconium.Take the phosphoric acid hydrogen zirconium with ethylene linkage and sulfonic acid group to be scattered in solvent, after ultrasound wave dispersion 20min, add UV tree
Fat oligomer, reactive diluent, levelling agent and ultraviolet initiator, first stir 10min, more ultrasonic 20min, and being obtained can ultraviolet
The super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating of photocuring.
Wherein, the phosphoric acid hydrogen zirconium nano-particle of described lamellar be alpha-phosphate hydrogen zirconium with one of γ-phosphoric acid hydrogen zirconium or α-
Phosphoric acid hydrogen zirconium and the mixture of γ-phosphoric acid hydrogen zirconium.
Wherein, the described silane coupler with ethylene linkage includes VTES, vinyl trimethoxy silicon
Alkane, vinyl three (methoxy ethoxy) silane, methacryloxypropyl, 3- (methacryloxypropyl)
The mixing of one or more of propyl trimethoxy silicane and 3- methacryloyloxypropyl methyl dimethoxysilane
Thing.
Wherein, the described silane coupler with sulfydryl is double-[3- (triethoxysilicane) propyl group]-tetrasulfide, mercapto propyl group
The mixture of one or more of trimethoxy silane and 3- mercaptopropyltriethoxysilane.
Wherein, described oxidant is one or more of hydrogen peroxide, permanganate, sodium peroxide, oleum
Mixture.
Wherein, described low colourity UV resin oligomers include low colourity polyurethane acrylate, low colourity polyester acrylic acid
The mixture of one or more of ester, low colourity polyether acrylate, low colourity p thiodipropionic acid ester；Described low colourity UV tree
Colourity Fe-Co≤2 of fat oligomer, the molecular weight of described low colourity UV resin oligomers is 1000-3000, described low colourity UV
The functional group of resin oligomers is 2-6.
Wherein, the described reactive diluent containing 1-6 functional group is the freedom of 1-6 functional group of (methyl) esters of acrylic acid
Fundamental mode monomer, including simple function group (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate and difunctional oneself two
Alcohol diacrylate.
Wherein, the preparation method of described super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating is：By described containing ethylene linkage and sulphur
The phosphoric acid hydrogen zirconium ultrasound wave of acid groups is scattered in described solvent, is subsequently adding described UV resin oligomers, contains 1-6 official
Reactive diluent, levelling agent and the light trigger that can roll into a ball, after stirring, ultrasound wave dispersion obtains final product again.
Hereinafter technical scheme will be further illustrated by several embodiments.
Embodiment one
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention, it includes the component of following weight portion：Contain
10 grams of the phosphoric acid hydrogen zirconium of ethylene linkage and sulfonic acid group, 10 grams of low colourity UV resin oligomers, the reactive diluent containing 1-6 functional group
15 grams, 0.5 gram of levelling agent, 50 grams of solvent, 2-6 gram of light trigger, wherein, low colourity UV resin oligomers be low colourity polyurethane
UV oligomer, colourity Fe-Co≤2；Reactive diluent is hydroxy ethyl methacrylate and hexanediyl ester with 2:1 quality
Ratio mixing, levelling agent is siliceous levelling agent, and solvent is isopropanol, and light trigger is ultraviolet initiator 184.
Phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group is adopted and is prepared with the following method：By 10 grams of alpha-phosphate hydrogen zirconium 100 milliliters
The ultrasonic stripping of propylamine solution of 0.1 mol/L, add 110 milliliters 0.1 mol/L hydrochloric acid replace remove propylamine, with water with
Ethanol alternately washs unnecessary hydrochloric acid, through ultrasonic, phosphoric acid hydrogen zirconium after peeling off is scattered in 100mL ethanol solution, adds 1.5
Gram VTES and 2.5 grams of mercaptopropyl trimethoxysilane, add acetic acid so that the pH value of system is maintained at
3.0, in 50 degrees Celsius of stirring reactions 3 hours, the mass concentration adding 5.0 milliliters was 25% hydroperoxidation 3 hours,
The prepared surface phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group simultaneously.10 grams of phosphoric acid hydrogen zirconiums with ethylene linkage and sulfonic acid group are taken to divide
Dissipate in 50 grams of isopropanol solvents, after ultrasound wave dispersion 20min, add 10 grams low colourity polyurethane UV oligomer, 10 grams of hydroxyls
Ethyl propylene acid esters, 5 grams hexylene glycol diacrylates and 0.5 gram of siliceous levelling agent, add 3 grams of ultraviolet initiators 184, first
Stirring 10min, more ultrasonic 20min, the super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating of prepared uV curable.
By the prepared above-mentioned super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating showering of the present embodiment in glass surface, through UV solidification
The performance of obtained coating such as table one afterwards：
Table one
By table one it is apparent that super hydrophilic antifog nanometer phosphoric acid hydrogen zirconaization of embodiment of the present invention preparation applies
Material, its contact angle is significantly less than existing antifogging coating, and hydrophilic antifogging performance is good, water resistance, weather resistance and wear-resisting
Property, scratch resistance, anti-fingerprint print, anti-pollution characteristic all higher, in addition coating hardness is also higher.
Embodiment two
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention, it includes the component of following weight portion：
15 grams of the phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group, 5 grams of low colourity UV resin oligomers, containing 1-6 functional group
10 grams of reactive diluent, 1.2 grams of levelling agent, 20 grams of solvent, 2 grams of light trigger, wherein, low colourity UV resin oligomers are low color
Degree polyurethane acrylate, colourity Fe-Co≤2；Reactive diluent is (methyl) Hydroxypropyl acrylate, and levelling agent is siliceous levelling
Agent, solvent is ethanol, and light trigger is ultraviolet initiator 184.
Phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group is adopted and is prepared with the following method：By 15 grams of γ-phosphoric acid hydrogen zirconium 120 milliliters
The ultrasonic stripping of propylamine solution of 0.1 mol/L, add 140 milliliters 0.1 mol/L hydrochloric acid replace remove propylamine, with water with
Ethanol alternately washs unnecessary hydrochloric acid, through ultrasonic, phosphoric acid hydrogen zirconium after peeling off is scattered in 150mL ethanol solution, adds 2 grams
Vinyltrimethoxy silane and 3 grams double-[3- (triethoxysilicane) propyl group]-tetrasulfide, add acetic acid to make system
PH value is maintained at 3.0, and in 50 degrees Celsius of stirring reactions 3 hours, the mass concentration adding 10 milliliters was 20% sodium peroxide
Reaction 3 hours, the prepared surface phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group simultaneously.15 grams are taken to carry ethylene linkage and sulfonic acid group
Phosphoric acid hydrogen zirconium is scattered in 20 grams of alcohol solvents, after ultrasound wave dispersion 20min, add 5 grams low colourity polyurethane acrylate, 10
Gram (methyl) Hydroxypropyl acrylate and 1.2 grams of siliceous levelling agents, add 2 grams of ultraviolet initiators 184, first stir 10min,
Ultrasonic 20min again, the super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating of prepared uV curable.
By the prepared above-mentioned super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating showering of the present embodiment in glass surface, through UV solidification
The performance of obtained coating such as table two afterwards：
Table two
By table two it is apparent that super hydrophilic antifog nanometer phosphoric acid hydrogen zirconaization of embodiment of the present invention preparation applies
Material, its contact angle is significantly less than existing antifogging coating, and hydrophilic antifogging performance is good, water resistance, weather resistance and wear-resisting
Property, scratch resistance, anti-fingerprint print, anti-pollution characteristic all higher, in addition coating hardness is also higher.
Embodiment three
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention, it includes the component of following weight portion：
20 grams of the phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group, 30 grams of low colourity UV resin oligomers, containing 1-6 functional group
5 grams of reactive diluent, 2 grams of levelling agent, 40 grams of solvent, 5 grams of light trigger, wherein, low colourity UV resin oligomers are low colourity
Polyether acrylate and low colourity p thiodipropionic acid ester are with 1:1 mass ratio mixing, colourity Fe-Co≤2；Reactive diluent is double
The hexanediyl ester of functional group, levelling agent is siliceous levelling agent, and solvent is isopropanol, and light trigger is that ultraviolet is light-initiated
Agent 184.
Phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group is adopted and is prepared with the following method：By 10 grams of alpha-phosphate hydrogen zirconiums and γ-phosphoric acid
Hydrogen zirconium is with 1:The ultrasonic stripping of propylamine solution of 100 milliliter 0.1 mol/L of the mixture of 1 mass ratio, adds 110 milliliters
The hydrochloric acid of 0.1 mol/L replaces removal propylamine, is replaced with ethanol with water and washs unnecessary hydrochloric acid, through ultrasonic by the phosphorus after peeling off
Sour hydrogen zirconium is scattered in 100mL ethanol solution, adds 1.5 grams of 3- (methacryloxypropyl) propyl trimethoxy silicane and 2.5
Gram 3- mercaptopropyltriethoxysilane, add acetic acid make the pH value of system be maintained at 3.0, little in 50 degrees Celsius of stirring reactions 3
When, add 8.0 milliliter permanganates and react 3 hours, the prepared surface phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group simultaneously.Take
20 grams are carried ethylene linkage and are scattered in 40 grams of isopropanol solvents with the phosphoric acid hydrogen zirconium of sulfonic acid group, after ultrasound wave dispersion 20min, add
15 grams low colourity polyether acrylates are siliceous with 15 grams low colourity p thiodipropionic acid esters, 5 grams hexylene glycol diacrylates and 2 grams
Levelling agent, adds 5 grams of ultraviolet initiators 184, first stirs 10min, more ultrasonic 20min, the super parent of prepared uV curable
Water antifog phosphoric acid hydrogen zirconium hybridization coating.
By the prepared above-mentioned super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating showering of the present embodiment in glass surface, through UV solidification
The performance of obtained coating such as table three afterwards：
Table three
By table three it is apparent that super hydrophilic antifog nanometer phosphoric acid hydrogen zirconaization of embodiment of the present invention preparation applies
Material, its contact angle is significantly less than existing antifogging coating, and hydrophilic antifogging performance is good, water resistance, weather resistance and wear-resisting
Property, scratch resistance, anti-fingerprint print, anti-pollution characteristic all higher, in addition coating hardness is also higher.
Example IV
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention, it includes the component of following weight portion：Contain
8 grams of the phosphoric acid hydrogen zirconium of ethylene linkage and sulfonic acid group, 7 grams of low colourity UV resin oligomers, the reactive diluent 6 containing 1-6 functional group
Gram, 0.6 gram of levelling agent, 10 grams of solvent, 6 grams of light trigger, wherein, low colourity UV resin oligomers be low colourity polyurethane UV low
Polymers, colourity Fe-Co≤2；Reactive diluent is hydroxy ethyl methacrylate and hexanediyl ester with 1:1 mass ratio mixes
Close, levelling agent is siliceous levelling agent, solvent is isopropanol, light trigger is ultraviolet initiator 184.
Phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group is adopted and is prepared with the following method：By 10 grams of alpha-phosphate hydrogen zirconium 100 milliliters
The ultrasonic stripping of propylamine solution of 0.1 mol/L, add 110 milliliters 0.1 mol/L hydrochloric acid replace remove propylamine, with water with
Ethanol alternately washs unnecessary hydrochloric acid, through ultrasonic, phosphoric acid hydrogen zirconium after peeling off is scattered in 100mL ethanol solution, adds 1.5
Gram VTES and 2.5 grams of mercaptopropyl trimethoxysilane, add acetic acid so that the pH value of system is maintained at
3.0, in 50 degrees Celsius of stirring reactions 3 hours, the mass concentration adding 5.0 milliliters was 25% hydroperoxidation 3 hours,
The prepared surface phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group simultaneously.8 grams of phosphoric acid hydrogen zirconiums with ethylene linkage and sulfonic acid group are taken to divide
Dissipate in 50 grams of isopropanol solvents, after ultrasound wave dispersion 20min, add 7 grams low colourity polyurethane UV oligomer, 3 grams of hydroxyl second
Base acrylate, 3 grams hexylene glycol diacrylates and 0.6 gram of siliceous levelling agent, add 6 grams of ultraviolet initiators 184, first stir
Mix 10min, more ultrasonic 20min, the super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating of prepared uV curable.
By the prepared above-mentioned super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating showering of the present embodiment in glass surface, through UV solidification
The performance of obtained coating such as table four afterwards：
Table four
By table four it is apparent that super hydrophilic antifog nanometer phosphoric acid hydrogen zirconaization of embodiment of the present invention preparation applies
Material, its contact angle is significantly less than existing antifogging coating, and hydrophilic antifogging performance is good, water resistance, weather resistance and wear-resisting
Property, scratch resistance, anti-fingerprint print, anti-pollution characteristic all higher, in addition coating hardness is also higher.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, some deformation can also be made and improve, these broadly fall into the guarantor of the present invention
Shield scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating is it is characterised in that include the component of following weight portion：
Phosphoric acid hydrogen zirconium 8-20 part containing ethylene linkage and sulfonic acid group, low colourity UV resin oligomers 5-30 part, containing 1-6 functional group
Reactive diluent 5-15 part, levelling agent 0.5-2 part, solvent 10-50 part, light trigger 2-6 part.
2. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 1 is it is characterised in that include weighing as follows
The component of amount part：
10 parts of the phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group, 10 parts of low colourity UV resin oligomers, the activity containing 1-6 functional group
15 parts of diluent, 0.5 part of levelling agent, 50 parts of solvent, 3 parts of light trigger.
3. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 1 and 2 is it is characterised in that described contain
Ethylene linkage with the phosphoric acid hydrogen zirconium preparation method of sulfonic acid group is：With the phosphoric acid hydrogen zirconium nano-particle of lamellar as raw material, through organic amine
Intercalation stripping reaction, generate monolayer phosphoric acid hydrogen zirconium nano-particle, more respectively with the silane coupler with ethylene linkage with sulfydryl
Sulfhydryl oxidase is become sulfonic group with the phosphoric acid hydrogen zirconium nano-particle of monolayer through Surface grafting reaction, then with oxidant by silane coupler
Group, is prepared into and has the described phosphoric acid hydrogen zirconium nanometer containing ethylene linkage and sulfonic acid group with high-molecular organic material excellent compatibility
Grain.
4. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 3 is it is characterised in that described lamellar
Phosphoric acid hydrogen zirconium nano-particle is one of alpha-phosphate hydrogen zirconium and γ-phosphoric acid hydrogen zirconium or alpha-phosphate hydrogen zirconium and γ-phosphoric acid hydrogen zirconium
Mixture.
5. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 3 is it is characterised in that described band alkene
The silane coupler of key includes VTES, vinyltrimethoxy silane, vinyl three (methoxyl group ethoxy
Base) silane, methacryloxypropyl, 3- (methacryloxypropyl) propyl trimethoxy silicane and 3-
The mixture of one or more of methacryloyloxypropyl methyl dimethoxysilane.
6. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 3 is it is characterised in that described band sulfydryl
Silane coupler be double-[3- (triethoxysilicane) propyl group]-tetrasulfide, mercaptopropyl trimethoxysilane and 3- mercapto propyl group
The mixture of one or more of triethoxysilane.
7. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 3 is it is characterised in that described oxidant
Mixture for one or more of hydrogen peroxide, permanganate, sodium peroxide, oleum.
8. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 1 and 2 is it is characterised in that described low
Colourity UV resin oligomers include low colourity polyurethane acrylate, low colourity polyester acrylate, low colourity polyoxyalkylene acrylate
The mixture of one or more of ester, low colourity p thiodipropionic acid ester；Colourity Fe-Co of described low colourity UV resin oligomers
≤ 2, the molecular weight of described low colourity UV resin oligomers is 1000-3000, the functional group of described low colourity UV resin oligomers
For 2-6.
9. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 1 and 2 is it is characterised in that described contain
The reactive diluent of 1-6 functional group is the free radical type monomer of 1-6 functional group of (methyl) esters of acrylic acid, including simple function
The hexanediyl ester of group's (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate and difunctional.
10. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 1 and 2 is it is characterised in that described surpass
The preparation method of hydrophilic antifogging nanometer phosphoric acid hydrogen zirconium hybridization coating is：Will be described ultrasonic with the phosphoric acid hydrogen zirconium of sulfonic acid group containing ethylene linkage
Ripple is scattered in described solvent, is subsequently adding described UV resin oligomers, the reactive diluent containing 1-6 functional group, stream
Flat agent and light trigger, after stirring, ultrasound wave dispersion obtains final product again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610865448.9A CN106398512B (en) | 2016-09-29 | 2016-09-29 | Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610865448.9A CN106398512B (en) | 2016-09-29 | 2016-09-29 | Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106398512A true CN106398512A (en) | 2017-02-15 |
| CN106398512B CN106398512B (en) | 2019-01-04 |
Family
ID=59228172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610865448.9A Active CN106398512B (en) | 2016-09-29 | 2016-09-29 | Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106398512B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110657400A (en) * | 2019-11-19 | 2020-01-07 | 湖南德霸照明制造有限公司 | Antifog automobile headlamp |
| CN112574383A (en) * | 2020-12-14 | 2021-03-30 | 上海华峰超纤科技股份有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN116535889A (en) * | 2023-05-26 | 2023-08-04 | 天津大学浙江研究院 | Anticorrosive filler, water-based epoxy anticorrosive paint and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5760126A (en) * | 1996-12-20 | 1998-06-02 | Minnesota Mining And Manufacturing Company | Aqueous fluorochemical compositions and abrasion-resistant coatings therefrom |
| JP2000256577A (en) * | 1999-03-10 | 2000-09-19 | Sk Kaken Co Ltd | Aqueous glossy coating material composition |
| CN105176293A (en) * | 2015-08-31 | 2015-12-23 | 福州富兰机电技术开发有限公司 | Super-hydrophilic coating and preparation method thereof, and super-hydrophilic coating layer and preparation method thereof |
| CN105176371A (en) * | 2015-08-31 | 2015-12-23 | 福州富兰机电技术开发有限公司 | Ultraviolet curing coating and preparation method thereof, and super-hydrophilic transparent antifogging coating layer and preparation method thereof |
| EP3049483A1 (en) * | 2013-09-25 | 2016-08-03 | Schlenk Metallic Pigments GmbH | Metal effect pigments modified with a silane layer containing at least two different bifunctional silanes |
-
2016
- 2016-09-29 CN CN201610865448.9A patent/CN106398512B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5760126A (en) * | 1996-12-20 | 1998-06-02 | Minnesota Mining And Manufacturing Company | Aqueous fluorochemical compositions and abrasion-resistant coatings therefrom |
| JP2000256577A (en) * | 1999-03-10 | 2000-09-19 | Sk Kaken Co Ltd | Aqueous glossy coating material composition |
| EP3049483A1 (en) * | 2013-09-25 | 2016-08-03 | Schlenk Metallic Pigments GmbH | Metal effect pigments modified with a silane layer containing at least two different bifunctional silanes |
| CN105176293A (en) * | 2015-08-31 | 2015-12-23 | 福州富兰机电技术开发有限公司 | Super-hydrophilic coating and preparation method thereof, and super-hydrophilic coating layer and preparation method thereof |
| CN105176371A (en) * | 2015-08-31 | 2015-12-23 | 福州富兰机电技术开发有限公司 | Ultraviolet curing coating and preparation method thereof, and super-hydrophilic transparent antifogging coating layer and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110657400A (en) * | 2019-11-19 | 2020-01-07 | 湖南德霸照明制造有限公司 | Antifog automobile headlamp |
| CN112574383A (en) * | 2020-12-14 | 2021-03-30 | 上海华峰超纤科技股份有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN112574383B (en) * | 2020-12-14 | 2022-01-21 | 上海华峰超纤科技股份有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN116535889A (en) * | 2023-05-26 | 2023-08-04 | 天津大学浙江研究院 | Anticorrosive filler, water-based epoxy anticorrosive paint and preparation method thereof |
| CN116535889B (en) * | 2023-05-26 | 2024-02-02 | 天津大学浙江研究院 | Anticorrosive filler, water-based epoxy anticorrosive paint and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106398512B (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105176371B (en) | Ultraviolet-curing paint and preparation method and ultra-hydrophilic transparent antifogging coating and preparation method | |
| JP4959892B2 (en) | Coating composition providing an abrasion resistant and colorable coating | |
| JP4517590B2 (en) | Antifouling agent and antifouling article using the same | |
| JP4126521B2 (en) | Method for producing fluoroorganopolysiloxane resin for film forming composition | |
| JP4711080B2 (en) | Method for producing fluoroorganopolysiloxane resin for film forming composition | |
| JP4614813B2 (en) | Low refractive index film-forming composition and cured film-coated substrate | |
| KR20100112146A (en) | Hydrophilic members | |
| KR20020011863A (en) | Coating Compositions and Articles with Cured Coats Thereof | |
| CN106398512B (en) | Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating | |
| CN106519741B (en) | The compound super hydrophilic wear-resistant paint of silicon zirconium | |
| CN106380994B (en) | Amphipathic nature block polymer containing polyhedral oligomeric silsesquioxane and antifog/anti-fog coatings and preparation method | |
| JP2008308684A (en) | Aqueous paint composition | |
| EP2256153A1 (en) | Hydrophilic film | |
| CN114058199B (en) | UV-cured super-hydrophilic anti-fog coating and preparation method and application thereof | |
| JP4126522B2 (en) | Method for producing condensate and hydrolyzate for film-forming composition | |
| KR20100127791A (en) | Hydrophilic member, fin member, aluminum fin member, heat exchanger and air conditioner | |
| JPH1081839A (en) | Ultraviolet-curing coating composition | |
| KR20170098237A (en) | Aqueous emulsion paint with improved stain removal and anticlogging properties | |
| JP2007138105A (en) | Hydrophilic composition and hydrophilic member | |
| JP2010235783A (en) | Surface-modified silica particle and active energy ray-curable resin composition using the same | |
| CN105778693A (en) | Self-cleaning coating material polymer and preparation method and application thereof | |
| WO2019064973A1 (en) | Anti-fogging layer laminate | |
| CN106675129A (en) | High-hardness antifogging UV (ultraviolet) automobile varnish and preparation method thereof | |
| US7416781B2 (en) | Coatings, methods for producing the same, and the use thereof | |
| JP3728752B2 (en) | Curable composition and cured product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211130 Address after: 523000 No. 82, Dongkeng Avenue North, Dongkeng Town, Dongguan City, Guangdong Province Patentee after: Guangdong Binhao Technology Co.,Ltd. Address before: 523000 Room 201, building C, No. 82, Dongkeng Avenue North, Dongkeng Town, Dongguan City, Guangdong Province Patentee before: DONGGUAN RUILING COMPOSITE MATERIAL TECHNOLOGY CO.,LTD. |