CN106398512B - Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating - Google Patents
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating Download PDFInfo
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- CN106398512B CN106398512B CN201610865448.9A CN201610865448A CN106398512B CN 106398512 B CN106398512 B CN 106398512B CN 201610865448 A CN201610865448 A CN 201610865448A CN 106398512 B CN106398512 B CN 106398512B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- 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
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- 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 present invention relates to super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coatings.The super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating includes the component of following parts by weight: containing ethylene linkage and 8-20 parts of the phosphoric acid hydrogen zirconium of sulfonic acid group, 5-30 parts of UV resin oligomers, containing 2-6 parts of 10-50 parts of 0.5-2 parts of 5-15 parts of reactive diluent, levelling agent, solvent, the photoinitiator of 1-6 functional group；The preparation method of the coating is: dispersing the phosphoric acid hydrogen zirconium ultrasonic wave containing ethylene linkage and sulfonic acid group in the solvent, then UV resin oligomers, the reactive diluent containing 1-6 functional group, levelling agent and photoinitiator is added, ultrasonic wave disperses again after mixing evenly to obtain the final product.Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention, hydrophilic antifogging performance is good, and water resistance and weather resistance are good, lasts a long time；Its coating hardness height prepared, wearability, scratch resistance, anti-fingerprint print, anti-pollution characteristic are higher.
Description
Technical field
The present invention relates to technical field of coatings, and in particular to a kind of super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating.
Background technique
Water the surface of transparent material such as glass, plastics, film contact angle all in 40o or more, have temperature in surfaces externally and internally
When poor, steam can condense to form mist on the surface of the material to the cold, influence the transparency of material.Coating has super hydrophilic on the surface of the material
The clear coat of performance can make the contact angle of water on the surface of the material in 5o hereinafter, the water mist of material surface or droplet is made to exist
Material surface drawout, forms moisture film, and moisture film does not influence the transparency of material, so achievees the purpose that antifog.Commercialization at present
Super hydrophilic anti-fog coating be mainly pure high molecular material system, it is to connect that this material, which plays the role of super hydrophilic hydrophilic radical,
On high polymer main chain, so that the water resistance of this coating is poor, the service life for ultimately causing super-hydrophilic coating is shorter, weatherability
It is poor.The hardness of coating prepared by this coating is relatively low simultaneously, and wearability, scratch resistance, anti-fingerprint print, anti-pollution characteristic are all
It is poor.
Summary of the invention
Based on this, the present invention provides a kind of super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating, and hydrophilic antifogging performance is good,
Water resistance and weather resistance are good, last a long time；And coating hardness height, wearability, scratch resistance, the anti-finger of the coating preparation
Escutcheon, anti-pollution characteristic are higher.
In order to achieve the object of the present invention, the invention adopts the following technical scheme:
A kind of super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating comprising the component of following parts by weight:
8-20 parts of phosphoric acid hydrogen zirconium, 5-30 parts of low coloration UV resin oligomers containing ethylene linkage and sulfonic acid group contain 1-6 function
5-15 parts of reactive diluent, 0.5-2 parts of the levelling agent, 10-50 parts of solvent, 2-6 parts of photoinitiator of group.
In wherein some embodiments, the super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating includes following parts by weight
Component:
10 parts of phosphoric acid hydrogen zirconium, low 10 parts of coloration UV resin oligomers containing ethylene linkage and sulfonic acid group, containing 1-6 functional group
15 parts of reactive diluent, 0.5 part of levelling agent, 50 parts of solvent, 3 parts of photoinitiator.
In wherein some embodiments, the phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group is the preparation method comprises the following steps: with sheet
Phosphoric acid hydrogen zirconium nano particle is raw material, reacts by organic amine intercalation stripping, generates the phosphoric acid hydrogen zirconium nano particle of single layer, then divide
Not with the phosphoric acid hydrogen zirconium nano particle of the silane coupling agent with ethylene linkage and the silane coupling agent with sulfydryl and single layer through surface grafting
Reaction, then with oxidant by sulfhydryl oxidase at sulfonic acid group, be prepared into containing with high-molecular organic material excellent compatibility
The phosphoric acid hydrogen zirconium nano particle of ethylene linkage and sulfonic acid group.
In wherein some embodiments, the phosphoric acid hydrogen zirconium nano particle of the sheet is alpha-phosphate hydrogen zirconium and γ-phosphoric acid hydrogen
One of zirconium or alpha-phosphate hydrogen zirconium and γ-phosphoric acid hydrogen zirconium mixture.
In wherein some embodiments, the silane coupling agent with ethylene linkage includes vinyltriethoxysilane, second
Alkenyl trimethoxy silane, vinyl three (methoxy ethoxy) silane, methacryloxypropyl, 3-
One in (methacryloxypropyl) propyl trimethoxy silicane and 3- methacryloxypropylmethyl dimethoxysilane
Kind or several mixtures.
In wherein some embodiments, the silane coupling agent with sulfydryl is double-[3- (triethoxysilicane) propyl]-four
The mixture of one or more of sulfide, mercaptopropyl trimethoxysilane and 3- mercaptopropyltriethoxysilane.
In wherein some embodiments, the oxidant is hydrogen peroxide, in permanganate, sodium peroxide, oleum
One or more of mixtures.
In wherein some embodiments, the low coloration UV resin oligomers include low coloration urethane acrylate, low
The mixture of one or more of coloration polyester acrylate, low coloration polyether acrylate, low coloration p thiodipropionic acid ester,
Coloration Fe-Co≤2 of the low coloration UV resin oligomers, the molecular weight of the low coloration UV resin oligomers are 1000-
3000, the functional group of the low coloration UV resin oligomers is 2-6.
In wherein some embodiments, the reactive diluent containing 1-6 functional group is (methyl) esters of acrylic acid 1-6
The free radical type monomer of a functional group, including simple function group (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate and
Hexanediyl ester bifunctional.
In wherein some embodiments, the super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating the preparation method comprises the following steps: will
The phosphoric acid hydrogen zirconium ultrasonic wave containing ethylene linkage and sulfonic acid group is scattered in the solvent, and the low coloration UV is then added
Resin oligomers, the reactive diluent containing 1-6 functional group, levelling agent and photoinitiator, after mixing evenly ultrasonic wave again
Disperse to obtain the final product.
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium the hybridization coating of the present invention ,-OH on stratiform phosphoric acid hydrogen zirconium surface have
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 at single layer, the ethylene linkage of radical reaction can be carried out in phosphoric acid hydrogen zirconium surface grafting, phosphoric acid can be improved
The compatibility of hydrogen zirconium and organic polymer monomer；In phosphoric acid hydrogen zirconium surface grafting sulfonic acid group, the parent of phosphoric acid hydrogen zirconium can be improved
Aqueous energy；By surface graft modification, it is grafted ethylene linkage and sulfonic acid group simultaneously on phosphoric acid hydrogen zirconium surface, phosphoric acid hydrogen zirconium can be improved
With the compatibility and hydrophilicity of organic polymer monomer；By the phosphoric acid hydrogen zirconium of this modification 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 testing, this super hydrophilic anti-fog coating anti-fog performance is good, and water resistance and weather resistance are good, and the coating of the coating preparation
Hardness height, wearability, scratch resistance, anti-fingerprint print, anti-pollution characteristic are higher, in vehicle backing rear-view mirror, windshield, wall mirror, trip
Swimming glasses, optical protection ball cover etc. have a good application prospect.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.But the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes
It is more thorough and comprehensive to the understanding of the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention comprising the component of following parts by weight:
8-20 parts of phosphoric acid hydrogen zirconium, 5-30 parts of low coloration UV resin oligomers containing ethylene linkage and sulfonic acid group contain 1-6 function
5-15 parts of reactive diluent, 0.5-2 parts of the levelling agent, 10-50 parts of solvent, 2-6 parts of photoinitiator of group.
In wherein some embodiments, the super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating includes following parts by weight
Component: 10 parts of phosphoric acid hydrogen zirconium, low 10 parts of coloration UV resin oligomers, the work containing 1-6 functional group containing ethylene linkage and sulfonic acid group
Property 15 parts of diluent, 0.5 part of levelling agent, 50 parts of solvent, 3 parts of photoinitiator.
Wherein, the phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group is the preparation method comprises the following steps: with the phosphoric acid hydrogen zirconium nanometer of sheet
Grain is raw material, reacts by organic amine intercalation stripping, generates the phosphoric acid hydrogen zirconium nano particle of single layer, then respectively with the silicon with ethylene linkage
The phosphoric acid hydrogen zirconium nano particle of alkane coupling agent and the silane coupling agent with sulfydryl and single layer is through Surface grafting reaction, then uses oxidant
By sulfhydryl oxidase at sulfonic acid group, be prepared into with high-molecular organic material excellent compatibility containing ethylene linkage and sulfonic acid group
Phosphoric acid hydrogen zirconium nano particle.Following reaction process occurs:
Specifically, such as: by the phosphoric acid hydrogen zirconium of sheet with propylamine solution ultrasound remove, then be added hydrochloric acid replace removal third
Amine is replaced with ethyl alcohol with water and washs extra hydrochloric acid, disperses the phosphoric acid hydrogen zirconium after removing in ethanol solution through ultrasound, is added
Vinyltriethoxysilane and mercaptopropyl trimethoxysilane, acetic acid, which is added, makes the pH value of system be maintained at 2.0~6.0, in
It is stirred to react at 50 DEG C 3 hours, adds hydroperoxidation 3 hours, surface is made and contains ethylene linkage and sulfonic phosphorus simultaneously
Sour hydrogen zirconium.It takes the phosphoric acid hydrogen zirconium with ethylene linkage and sulfonic acid group to be scattered in solvent, after ultrasonic wave disperses 20min, low color is added
UV resin oligomers, reactive diluent, levelling agent and ultraviolet initiator are spent, 10min, then ultrasound 20min are first stirred, is made
The super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating of uV curable.
Wherein, the phosphoric acid hydrogen zirconium nano particle of the sheet is one of alpha-phosphate hydrogen zirconium and γ-phosphoric acid hydrogen zirconium or α-
Phosphoric acid hydrogen zirconium and γ-phosphoric acid hydrogen zirconium mixture.
Wherein, the silane coupling agent with ethylene linkage includes vinyltriethoxysilane, vinyl trimethoxy silicon
Alkane, vinyl three (methoxy ethoxy) silane, methacryloxypropyl, 3- (methacryloxypropyl)
The mixing of one or more of propyl trimethoxy silicane and 3- methacryloxypropylmethyl dimethoxysilane
Object.
Wherein, the silane coupling agent with sulfydryl is double-[3- (triethoxysilicane) propyl]-tetrasulfide, mercapto propyl
The mixture of one or more of trimethoxy silane and 3- mercaptopropyltriethoxysilane.
Wherein, the oxidant is one or more of hydrogen peroxide, permanganate, sodium peroxide, oleum
Mixture.
Wherein, the low coloration UV resin oligomers include low coloration urethane acrylate, low coloration polyester acrylic
The mixture of one or more of ester, low coloration polyether acrylate, low coloration p thiodipropionic acid ester；The low coloration UV tree
Coloration Fe-Co≤2 of rouge oligomer, the molecular weight of the low coloration UV resin oligomers are 1000-3000, the low coloration UV
The functional group of resin oligomers is 2-6.
Wherein, the 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) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate and it is bifunctional oneself two
Alcohol diacrylate.
Wherein, the super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating the preparation method comprises the following steps: described ethylene linkage and sulphur will be contained
The phosphoric acid hydrogen zirconium ultrasonic wave of acid groups is scattered in the solvent, the UV resin oligomers is then added, containing 1-6 official
Reactive diluent, levelling agent and the photoinitiator that can be rolled into a ball, ultrasonic wave disperses again after mixing evenly to obtain the final product.
Several embodiment to further illustrate the technical scheme of the present inventions will be passed through below.
Embodiment one
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention comprising the component of following parts by weight: contain
10 grams of the phosphoric acid hydrogen zirconium of ethylene linkage and sulfonic acid group, low 10 grams of coloration UV resin oligomers, the reactive diluent containing 1-6 functional group
15 grams, 0.5 gram of levelling agent, 50 grams, 2-6 grams of photoinitiator of solvent, wherein low coloration UV resin oligomers are low coloration polyurethane
UV oligomer, coloration Fe-Co≤2；Reactive diluent is hydroxy ethyl methacrylate and hexanediyl ester with the quality of 2:1
Than mixing, levelling agent is siliceous levelling agent, and solvent is isopropanol, and photoinitiator is ultraviolet initiator 184.
Phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group is prepared with the following method: by 10 grams of alpha-phosphate hydrogen zirconiums, 100 milliliters
The propylamine solution ultrasound of 0.1 mol/L is removed, and the hydrochloric acid that 0.1 mol/L of 110 milliliters is added replaces removal propylamine, with water with
Ethyl alcohol alternately washs extra hydrochloric acid, disperses the phosphoric acid hydrogen zirconium after removing in 100mL ethanol solution through ultrasound, is added 1.5
Gram vinyltriethoxysilane and 2.5 grams of mercaptopropyl trimethoxysilane, acetic acid, which is added, is maintained at the pH value of system
3.0, it is stirred to react in 50 degrees Celsius 3 hours, the mass concentration for adding 5.0 milliliters is hydroperoxidation 3 hours of 25%,
The obtained surface phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group simultaneously.Take 10 grams of phosphoric acid hydrogen zirconiums with ethylene linkage and sulfonic acid group point
It dissipates in 50 grams of isopropanol solvents, after ultrasonic wave disperses 20min, 10 grams of low coloration polyurethane UV oligomer, 10 grams of hydroxyls is added
3 grams of ultraviolet initiators 184 are added in ethyl propylene acid esters, 5 grams hexylene glycol diacrylates and 0.5 gram of siliceous levelling agent, first
10min, then ultrasound 20min are stirred, the super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating of uV curable is made.
Above-mentioned super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating showering made from the present embodiment is solidified in glass surface through UV
The performance of obtained coating such as table one afterwards:
Table one
By table one it is apparent that the super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hydridization of preparation of the embodiment of the present invention applies
Material, contact angle is significantly less than existing anti-fog coating, and hydrophilic antifogging performance is good, water resistance, weather resistance and wear-resisting
Property, scratch resistance, anti-fingerprint print, anti-pollution characteristic it is higher, in addition coating hardness is also higher.
Embodiment two
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention comprising the component of following parts by weight:
15 grams of phosphoric acid hydrogen zirconium, low 5 grams of coloration UV resin oligomers containing ethylene linkage and sulfonic acid group, containing 1-6 functional group
10 grams of reactive diluent, 1.2 grams of levelling agent, 20 grams of solvent, 2 grams of photoinitiator, wherein low coloration UV resin oligomers are low color
Spend urethane acrylate, coloration Fe-Co≤2；Reactive diluent is (methyl) hydroxypropyl acrylate, and levelling agent is siliceous levelling
Agent, solvent are ethyl alcohol, and photoinitiator is ultraviolet initiator 184.
Phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group is prepared with the following method: by 15 grams of γ-phosphoric acid hydrogen zirconium, 120 milliliters
The propylamine solution ultrasound of 0.1 mol/L is removed, and the hydrochloric acid that 0.1 mol/L of 140 milliliters is added replaces removal propylamine, with water with
Ethyl alcohol alternately washs extra hydrochloric acid, disperses the phosphoric acid hydrogen zirconium after removing in 150mL ethanol solution through ultrasound, is added 2 grams
Vinyltrimethoxysilane and 3 grams double-[3- (triethoxysilicane) propyl]-tetrasulfide, acetic acid, which is added, makes system
PH value is maintained at 3.0, is stirred to react in 50 degrees Celsius 3 hours, adds the sodium peroxide that the mass concentration of 10 milliliters is 20%
The surface phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group simultaneously is made in reaction 3 hours.Take 15 grams with ethylene linkage and sulfonic acid group
Phosphoric acid hydrogen zirconium is scattered in 20 grams of alcohol solvents, and after ultrasonic wave disperses 20min, 5 grams of low coloration polyurethane acrylate, 10 are added
Gram (methyl) hydroxypropyl acrylate and 1.2 grams of siliceous levelling agents, 2 grams of ultraviolet initiators 184 are added, first stir 10min,
The super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating of uV curable is made in ultrasound 20min again.
Above-mentioned super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating showering made from the present embodiment is solidified in glass surface through UV
The performance of obtained coating such as table two afterwards:
Table two
By table two it is apparent that the super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hydridization of preparation of the embodiment of the present invention applies
Material, contact angle is significantly less than existing anti-fog coating, and hydrophilic antifogging performance is good, water resistance, weather resistance and wear-resisting
Property, scratch resistance, anti-fingerprint print, anti-pollution characteristic it is higher, in addition coating hardness is also higher.
Embodiment three
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention comprising the component of following parts by weight:
20 grams of phosphoric acid hydrogen zirconium, low 30 grams of coloration UV resin oligomers containing ethylene linkage and sulfonic acid group, containing 1-6 functional group
5 grams of reactive diluent, 2 grams of levelling agent, 40 grams of solvent, 5 grams of photoinitiator, wherein low coloration UV resin oligomers are low coloration
Polyether acrylate is mixed with low coloration p thiodipropionic acid ester with the mass ratio of 1:1, coloration Fe-Co≤2；Reactive diluent is double
The hexanediyl ester of functional group, levelling agent are siliceous levelling agent, and solvent is isopropanol, and photoinitiator is ultraviolet light-initiated
Agent 184.
Phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group is prepared with the following method: by 10 grams of alpha-phosphate hydrogen zirconiums and γ-phosphoric acid
Hydrogen zirconium is removed with the propylamine solution ultrasound of the mixture of the mass ratio of 1:1 100 milliliter, 0.1 mol/L, and 110 milliliters are added
The hydrochloric acid of 0.1 mol/L replaces removal propylamine, is replaced with water with ethyl alcohol and washs extra hydrochloric acid, through ultrasound by the phosphorus after removing
Sour hydrogen zirconium is scattered in 100mL ethanol solution, and 1.5 grams of 3- (methacryloxypropyl) propyl trimethoxy silicane and 2.5 is added
Gram 3- mercaptopropyltriethoxysilane, be added acetic acid so that the pH value of system is maintained at 3.0, it is small to be stirred to react 3 in 50 degrees Celsius
When, it adds 8.0 milliliter permanganates and reacts 3 hours, the surface phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group simultaneously is made.It takes
20 grams of phosphoric acid hydrogen zirconiums with ethylene linkage and sulfonic acid group are scattered in 40 grams of isopropanol solvents, after ultrasonic wave disperses 20min, are added
15 grams of low coloration polyether acrylates and 15 grams of low coloration p thiodipropionic acid esters, 5 grams hexylene glycol diacrylates and 2 grams are siliceous
5 grams of ultraviolet initiators 184 are added in levelling agent, first stir 10min, then ultrasound 20min, and the super parent of uV curable is made
The antifog phosphoric acid hydrogen zirconium hybridization coating of water.
Above-mentioned super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating showering made from the present embodiment is solidified in glass surface through UV
The performance of obtained coating such as table three afterwards:
Table three
By table three it is apparent that the super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hydridization of preparation of the embodiment of the present invention applies
Material, contact angle is significantly less than existing anti-fog coating, and hydrophilic antifogging performance is good, water resistance, weather resistance and wear-resisting
Property, scratch resistance, anti-fingerprint print, anti-pollution characteristic it is higher, in addition coating hardness is also higher.
Example IV
Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating of the present invention comprising the component of following parts by weight: contain
8 grams of the phosphoric acid hydrogen zirconium of ethylene linkage and sulfonic acid group, low 7 grams of coloration 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 photoinitiator, wherein low coloration UV resin oligomers be low coloration polyurethane UV it is low
Polymers, coloration Fe-Co≤2；Reactive diluent is that hydroxy ethyl methacrylate and hexanediyl ester are mixed with the mass ratio of 1:1
It closes, levelling agent is siliceous levelling agent, and solvent is isopropanol, and photoinitiator is ultraviolet initiator 184.
Phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group is prepared with the following method: by 10 grams of alpha-phosphate hydrogen zirconiums, 100 milliliters
The propylamine solution ultrasound of 0.1 mol/L is removed, and the hydrochloric acid that 0.1 mol/L of 110 milliliters is added replaces removal propylamine, with water with
Ethyl alcohol alternately washs extra hydrochloric acid, disperses the phosphoric acid hydrogen zirconium after removing in 100mL ethanol solution through ultrasound, is added 1.5
Gram vinyltriethoxysilane and 2.5 grams of mercaptopropyl trimethoxysilane, acetic acid, which is added, is maintained at the pH value of system
3.0, it is stirred to react in 50 degrees Celsius 3 hours, the mass concentration for adding 5.0 milliliters is hydroperoxidation 3 hours of 25%,
The obtained surface phosphoric acid hydrogen zirconium containing ethylene linkage and sulfonic acid group simultaneously.Take 8 grams of phosphoric acid hydrogen zirconiums with ethylene linkage and sulfonic acid group point
It dissipates in 50 grams of isopropanol solvents, after ultrasonic wave disperses 20min, 7 grams of low coloration polyurethane UV oligomer, 3 grams of hydroxyl second is added
Base acrylate, 3 grams hexylene glycol diacrylates and 0.6 gram of siliceous levelling agent, are added 6 grams of ultraviolet initiators 184, first stir
10min, then ultrasound 20min are mixed, the super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating of uV curable is made.
Above-mentioned super hydrophilic antifog phosphoric acid hydrogen zirconium hybridization coating showering made from the present embodiment is solidified in glass surface through UV
The performance of obtained coating such as table four afterwards:
Table four
By table four it is apparent that the super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hydridization of preparation of the embodiment of the present invention applies
Material, contact angle is significantly less than existing anti-fog coating, and hydrophilic antifogging performance is good, water resistance, weather resistance and wear-resisting
Property, scratch resistance, anti-fingerprint print, anti-pollution characteristic it is higher, in addition coating hardness is also higher.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot 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, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating, which is characterized in that the component including following parts by weight:
8-20 parts of phosphoric acid hydrogen zirconium, 5-30 parts of low coloration UV resin oligomers containing ethylene linkage and sulfonic acid group, containing 1-6 functional group
5-15 parts of reactive diluent, 0.5-2 parts of levelling agent, 10-50 parts of solvent, 2-6 parts of photoinitiator；The low coloration UV resin is oligomeric
Object includes low coloration urethane acrylate, low coloration polyester acrylate, low coloration polyether acrylate, low coloration phosphoric acid third
The mixture of one or more of olefin(e) acid ester.
2. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 1, which is characterized in that including weighing as follows
Measure the component of part:
10 parts of phosphoric acid hydrogen zirconium, low 10 parts of coloration UV resin oligomers, the activity containing 1-6 functional group containing ethylene linkage and sulfonic acid group
15 parts of diluent, 0.5 part of levelling agent, 50 parts of solvent, 3 parts of photoinitiator.
3. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 1 or 2, which is characterized in that described to contain
The phosphoric acid hydrogen zirconium of ethylene linkage and sulfonic acid group is the preparation method comprises the following steps: using the phosphoric acid hydrogen zirconium nano particle of sheet as raw material, by organic amine
Intercalation stripping reaction, generates the phosphoric acid hydrogen zirconium nano particle of single layer, then respectively with the silane coupling agent with ethylene linkage and with sulfydryl
The phosphoric acid hydrogen zirconium nano particle of silane coupling agent and single layer through Surface grafting reaction, then with oxidant by sulfhydryl oxidase at sulfonic group
Group is prepared into the 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, which is characterized in that the sheet
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, which is characterized in that the band alkene
The silane coupling agent of key includes vinyltriethoxysilane, vinyltrimethoxysilane, (the methoxyl group ethoxy of vinyl three
Base) silane, methacryloxypropyl, 3- (methacryloxypropyl) propyl trimethoxy silicane and 3-
The mixture of one or more of methacryloxypropylmethyl dimethoxysilane.
6. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 3, which is characterized in that the band sulfydryl
Silane coupling agent be double-[3- (triethoxysilicane) propyl]-tetrasulfide, mercaptopropyl trimethoxysilane and 3- mercapto propyl
The mixture of one or more of triethoxysilane.
7. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 3, which is characterized in that the oxidant
For the mixture of 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 or 2, which is characterized in that described low
Coloration Fe-Co≤2 of coloration UV resin oligomers, the molecular weight of the low coloration UV resin oligomers is 1000-3000, described
The functional group of low coloration UV resin oligomers is 2-6.
9. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 1 or 2, which is characterized in that described to 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, described (methyl)
The free radical type monomer of 1-6 functional group of esters of acrylic acid includes simple function group (methyl) hydroxy-ethyl acrylate, (methyl) propylene
Sour hydroxypropyl acrylate and hexanediyl ester bifunctional.
10. super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating according to claim 1 or 2, which is characterized in that described super
Hydrophilic antifogging nanometer phosphoric acid hydrogen zirconium hybridization coating the preparation method comprises the following steps: by the phosphoric acid hydrogen zirconium ultrasound containing ethylene linkage and sulfonic acid group
Wave is scattered in the solvent, and the low coloration UV resin oligomers, the activity dilution containing 1-6 functional group are then added
Agent, levelling agent and photoinitiator, ultrasonic wave disperses again after mixing evenly to obtain the final product.
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| 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 |
| 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 |
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