CN106010053B - Automatically cleaning photocuring anti-fog coating and preparation method thereof - Google Patents
Automatically cleaning photocuring anti-fog coating and preparation method thereof Download PDFInfo
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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Abstract
The present invention provides a kind of automatically cleaning photocuring anti-fog coatings, it is made of the raw material of following mass parts: 3-8 mass parts modified graphene nanoparticle, 20-80 mass parts hydrophilic photosensitive resin, 5-20 mass parts photoinitiator, 15-40 mass parts diluent, 1-3 mass parts curing accelerator.The present invention also provides the preparation methods of the automatically cleaning photocuring anti-fog coating.Compared with the relevant technologies, the beneficial effects of the invention are that, hydrophilic modifying is carried out on the surface of graphene, imparting graphene is good hydrophilic and dispersed, and it is good with hydrophilic photosensitive resin compatibility, greatly improve the intensity and wear-resisting property of coating；Cationic organic monomer modified hydrophilic resin, can be effectively suppressed the growth of coating surface bacterium, have good self-cleaning property；Cross-linked network is formed after solidification, the mechanical performances such as adhesive force, hardness, rub resistance, water resistance are promoted, can be persistently antifog；Low-temperature bake is applicable to various substrates.
Description
[technical field]
The present invention relates to technical field of coatings more particularly to a kind of automatically cleaning photocuring anti-fog coating and preparation method thereof.
[background technique]
Existing anti-fog coating makes coating have hydrophily, contact of the droplet in coating surface by introducing hydrophilic functional group
It is low, uniform water film is sprawled into, prevents light from scattering, it is antifog to achieve the purpose that.It is public in the patent of Publication No. CN104725640A
It has opened a kind of hydrophilic modifying silica solution and its has prepared the application in hydrophilic antifogging wear-resistant paint, by modified silane coupled of PEG
Agent and teos hydrolysis prepare hydrophilic modifying silica solution, this silica solution is added in anti-fog coating, the antifog painting of preparation
The problems such as material tool has good wearability and adhesive force, but silica solution and polyethylene glycol poor compatibility, causes coating light transmittance low；
A kind of super hydrophilic anti-fog coating is disclosed in the patent of Publication No. CN105038430A, by modified acrylic acid emulsion, nanometer
Silica, titanium dioxide and surfactant composition, are added nano silica and are obviously improved coating to substrate adhesive force and painting
Layer intensity improves persistently anti-fog effect, but surfactant long chain hydrophobic group is easily assembled, and mutually separates, inhales with hydrophilic component generation
Damp rear surface forms color film, influences optical characteristics, and the introducing of titanium dioxide will affect the transparency of coating；Publication No.
A kind of anti-fog properties lasting anti-fog coating is disclosed in CN102850924A, by modified hydrophilic resin, closure isocyanic acid
Ester curing agent and modified surface active's agent are deployed, and closure isocyanate curing agent must unseal thermosetting at 120 DEG C or more
Change, the heatproof of transparent substrate is required it is high, using being restricted.The deficiencies in the prior art are that existing system is difficult to take into account attached
Put forth effort, surface hardness, wearability, water resistance and lasting comprehensive performances such as anti-fog properties, improves another portion to sacrifice certain performances
Divide performance.
Therefore, it is really necessary to provide new automatically cleaning photocuring anti-fog coating of one kind and preparation method thereof to solve above-mentioned technology
Problem.
[summary of the invention]
It is good that the technical problem to be solved by the invention is to provide a kind of self-cleaning performances, and sustainable antifog automatically cleaning light is solid
Change anti-fog coating and preparation method thereof.
A kind of automatically cleaning photocuring anti-fog coating, is made of the raw material of following mass parts:
3-8 mass parts modified graphene nanoparticle,
20-80 mass parts hydrophilic photosensitive resin,
5-20 mass parts photoinitiator,
15-40 mass parts diluent,
1-3 mass parts curing accelerator.
Preferably, the photoinitiator be benzophenone, benzoin ethyl ether, 2- hydroxy-2-methyl -1- phenyl -1- acetone,
One or more of 1- hydroxycyclohexyl phenyl ketone, 2,4,6- trimethylbenzoyl diphenyl phosphine oxide.
Preferably, the diluent is ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, a contracting two
One or more of ethylene glycol monomethyl ether, diglycol ether.
Preferably, the curing accelerator is the salt of acid or acid, such as sulfuric acid, hydrochloric acid, chlorosulfonic acid, terephthalic acid (TPA), hydrogen bromine
One or more of the acids such as acid, perchloric acid or the ammonium salt of acid.
The present invention also provides the preparation methods of above-mentioned automatically cleaning photocuring anti-fog coating, comprising the following steps:
Step 1: preparing modified graphene nanoparticle
1) by 40-80 mass parts allyl glycidyl ether, 5-12 mass parts graphene, 20-50 mass parts diluent, 1-
3 mass parts Pyrogentisinic Acid's polymerization inhibitors are added in reaction vessel, and ultrasonic disperse 30min stirs 18 hours at 80-130 DEG C, obtains alkene
Propyl graft modification graphene；
2) by 15-30 mass parts allyl graft modification graphene, 50-90 parts of hydrophilic monomers, 35-60 mass parts diluent
It is added in reaction vessel, is stirred for 24 hours at being 50-80 DEG C in temperature, obtain modified graphene nanoparticle；
Step 2: preparing hydrophilic photosensitive resin
1) by 20-60 mass parts acrylic ester monomer, 10-40 mass parts dimethylaminoethyl methacrylate and 10-
20-60 mass parts are slowly added dropwise into diluent in the vinyl monomer of 50 mass parts nitrogen atoms, under the conditions of 90 DEG C, by 0.5-
5 mass parts initiators are added in aforementioned mixed solution, time for adding 6-8h, keep the temperature 2-3h after the completion and obtain hydrophilic photosensitive tree
Rouge；
It should be noted that step 1 and step 2 are limited without sequencing, modified graphene nanometer is specially first prepared
Particle or hydrophilic photosensitive resin are all possible.
Step 3: the preparation of automatically cleaning photocuring anti-fog coating
3-8 mass parts modified graphene nanoparticle obtained in step 1 is taken,
Take 20-80 mass parts hydrophilic photosensitive resin and 5-20 mass parts photoinitiator obtained, 15- in step 2
40 mass parts diluents, 1-3 mass parts curing accelerator are uniformly mixed and form automatically cleaning photocuring anti-fog coating.
Preferably, the hydrophilic monomer in step 1 includes acrylic acid, acrylate, hydroxyethyl methacrylate, methyl-prop
One or more of e pioic acid methyl ester, hydroxy-ethyl acrylate.
Preferably, the diluent in step 1 be ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether,
One or more of diglycol methyl ether, diglycol ether.
Preferably, the acrylic ester monomer in step 2 includes 2- acrylamide -2- methyl-propanesulfonic acid, metering system
The one or more of sour hydroxyl ethyl ester, hydroxy-ethyl acrylate, hy-droxybutyl, methacrylate.
Preferably, the vinyl monomer of the nitrogen atom in step 2 includes (methyl) acrylamide, N- methacryl
Amine, N,N-DMAA, N- ethyl acrylamide, N, N- acrylamide, N- propylacrylamide, N, N- bis-
Dimethylaminoethyl (methyl) acrylamide, N, one or more of N- dimethyl aminopropyl (methyl) acrylamide.
Preferably, the diluent in step 2 be ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether,
One or more of diglycol methyl ether, diglycol ether；The initiator is benzoyl peroxide, peroxide
Change lauroyl, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-t-butyl peroxide, cumyl peroxide, benzoyl peroxide
T-butyl formate, peroxidating trimethylacetic acid tertiary butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, azo-bis-isobutyl cyanide, azo two
One of different cyanogen in heptan, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate.
Compared with the relevant technologies, the beneficial effects of the invention are that, hydrophilic modifying is carried out on the surface of graphene, assigns graphene
It is good hydrophilic and dispersed, it is good with hydrophilic photosensitive resin compatibility, greatly improve the intensity and wear-resisting property of coating；Sun from
Sub- organic monomer modified hydrophilic resin, can be effectively suppressed the growth of coating surface bacterium, have good self-cleaning property；After solidification
Cross-linked network is formed, the mechanical performances such as adhesive force, hardness, rub resistance, water resistance are promoted, can be persistently antifog；Low-temperature bake, can
Suitable for various substrates.
[specific embodiment]
The invention will be further described With reference to embodiment.
Embodiment 1
I, the preparation of modified graphene nanoparticle:
(1) by 50 mass parts allyl glycidyl ethers, 6 mass parts graphenes, 43 mass parts ethylene glycol ethyl ethers, 1 mass
Part Pyrogentisinic Acid's polymerization inhibitor is added in reaction vessel, and ultrasonic disperse 30min is stirred 18 hours at 100 DEG C, obtains allyl grafting
Modified graphene；
(2) by 18 mass parts allyl graft modification graphenes, 42 mass parts acrylate, 40 mass parts ethylene glycol ethyl ethers
It is added in reaction vessel, is stirred for 24 hours at being 55 DEG C in temperature, obtain modified graphene nanoparticle.
II, the preparation of hydrophilic photosensitive resin:
By 25 mass parts 2- acrylamide -2- methyl-propanesulfonic acids, 25 mass parts dimethylaminoethyl methacrylates and 15
32 mass parts are slowly added dropwise into ethylene glycol ethyl ether in mass parts N, N- dimethylaminoethyl (methyl) acrylamide, in 90 DEG C of conditions
Under, 3 mass parts azo-bis-isobutyl cyanides are added in aforementioned mixed solution, time for adding 6h, keep the temperature 2.5h after the completion and obtain parent
Water photosensitive resin；
III, container is added in the hydrophilic photosensitive resin of 50 mass parts step IIs preparation and 25 mass parts ethylene glycol monomethyl ethers
In, modified graphene nanoparticle, the 18 mass parts benzophenone, 2 matter of the preparation of 5 mass parts step Is are sequentially added under stiring
Measure part terephthalic acid (TPA), it is every a kind of raw material is added after mixing evenly, to add another raw material.Mixing time is no less than
30min obtains automatically cleaning photocuring anti-fog coating.The automatically cleaning photocuring anti-fog coating that preparation is completed is coated in transparent substrate
Surface, the film-forming under ultraviolet light.Film performance test result is shown in Table 1
Embodiment 2
I, the preparation of modified graphene nanoparticle:
(1) by 45 mass parts allyl glycidyl ethers, 8 mass parts graphenes, 45 mass parts diglycol methyl ethers,
2 mass parts Pyrogentisinic Acid's polymerization inhibitors are added in reaction vessel, and ultrasonic disperse 30min stirs 18 hours at 90 DEG C, obtains allyl
Graft modification graphene；
(2) by 20 mass parts allyl graft modification graphenes, 60 mass parts hydroxyethyl methacrylates, 20 mass parts one
Diglycol ethylene methyl ether is added in reaction vessel, stirs for 24 hours at being 60 DEG C in temperature, obtains modified graphene nanoparticle.
II, the preparation of hydrophilic photosensitive resin:
By 30 mass parts methacrylates, 15 mass parts dimethylaminoethyl methacrylates and 21 mass parts N,
N- dimethylacrylamide is slowly added dropwise in 30 mass parts diglycol ether, under the conditions of 90 DEG C, by 4 mass parts peroxides
Change two dicyclohexyl carbonates to be added in aforementioned mixed solution, time for adding 7h, keeps the temperature 2h after the completion and obtain hydrophilic photosensitive tree
Rouge；
III, container is added in the hydrophilic photosensitive resin of 60 mass parts step IIs preparation and 20 mass parts propylene-glycol ethyl ethers
In, modified graphene nanoparticle, the 13 mass parts 1- hydroxy-cyclohexyls of the preparation of 4 mass parts step Is are sequentially added under stiring
Phenyl ketone, 3 mass parts chlorosulfonic acids, it is every a kind of raw material is added after mixing evenly, to add another raw material.Mixing time
No less than 30min obtains automatically cleaning photocuring anti-fog coating.The automatically cleaning photocuring anti-fog coating that preparation is completed is coated in saturating
Bright substrate surface, the film-forming under ultraviolet light.Film performance test result is shown in Table 1
Embodiment 3
I, the preparation of modified graphene nanoparticle:
(1) by 55 mass parts allyl glycidyl ethers, 10 mass parts graphenes, 33 mass parts diglycol second
Ether, 2 mass parts Pyrogentisinic Acid's polymerization inhibitors are added in reaction vessel, and ultrasonic disperse 30min stirs 18 hours at 110 DEG C, obtains alkene
Propyl graft modification graphene；
(2) by 16 mass parts allyl graft modification graphenes, 50 mass parts hydroxy-ethyl acrylates, 34 mass parts one contracting two
Ethylene glycol ethyl ether is added in reaction vessel, stirs for 24 hours at being 70 DEG C in temperature, obtains modified graphene nanoparticle.
II, the preparation of hydrophilic photosensitive resin:
By 31 mass parts hydroxy-ethyl acrylates, 15 mass parts dimethylaminoethyl methacrylates and 15 mass parts N, N- bis-
Ethyl acrylamide is slowly added dropwise in 35 mass parts propylene glycol monomethyl ethers, under the conditions of 90 DEG C, by 4 mass parts dibenzoyl peroxides
It is added in aforementioned mixed solution, time for adding 7.5h, keeps the temperature 2.5h after the completion and obtain hydrophilic photosensitive resin；
III, container is added in the hydrophilic photosensitive resin of 52 mass parts step IIs preparation and 25 mass parts propylene glycol monomethyl ethers
In, modified graphene nanoparticle, the 15 mass parts 2- hydroxyl -2- first of the preparation of 6 mass parts step Is are sequentially added under stiring
Base -1- phenyl -1- acetone, 2 mass parts sulfuric acid, it is every a kind of raw material is added after mixing evenly, to add another raw material.It stirs
Mixing the time is no less than 30min, obtains automatically cleaning photocuring anti-fog coating.The automatically cleaning photocuring anti-fog coating that preparation is completed applies
Transparent substrate surface is overlayed on, the film-forming under ultraviolet light.Film performance test result is shown in Table 1
Embodiment 4
I, the preparation of modified graphene nanoparticle:
(1) by 52 mass parts allyl glycidyl ethers, 9 mass parts graphenes, 37 mass parts propylene-glycol ethyl ethers, 2 mass
Part Pyrogentisinic Acid's polymerization inhibitor is added in reaction vessel, and ultrasonic disperse 30min is stirred 18 hours at 115 DEG C, obtains allyl grafting
Modified graphene；
(2) 20 mass parts allyl graft modification graphenes, 44 mass parts acrylic acid, 36 mass parts propylene-glycol ethyl ethers are added
Enter in reaction vessel, is stirred for 24 hours at being 75 DEG C in temperature, obtain modified graphene nanoparticle.
II, the preparation of hydrophilic photosensitive resin:
By 29 mass parts methacrylates, 20 mass parts dimethylaminoethyl methacrylates and 16 mass parts N-
Ethyl acrylamide is slowly added dropwise in 30 mass parts propylene glycol monomethyl ethers, under the conditions of 90 DEG C, by 5 mass parts dicetyl peroxydicarbonates two
Isopropyl ester is added in aforementioned mixed solution, time for adding 8h, keeps the temperature 3h after the completion and obtains hydrophilic photosensitive resin；
III, container is added in the hydrophilic photosensitive resin of 48 mass parts step IIs preparation and 28 mass parts ethylene glycol ethyl ethers
In, modified graphene nanoparticle, 16 mass parts, 2,4, the 6- trimethyl of the preparation of 7 mass parts step Is are sequentially added under stiring
Benzoyl diphenyl phosphine oxide, 1 mass parts hydrochloric acid, it is every a kind of raw material is added after mixing evenly, to add another raw material.
Mixing time is no less than 30min, obtains automatically cleaning photocuring anti-fog coating.The automatically cleaning photocuring anti-fog coating that preparation is completed
Coated in transparent substrate surface, the film-forming under ultraviolet light.Film performance test result is shown in Table 1.
1 automatically cleaning photocuring anti-fog coating film performance test result of table
Compared with the relevant technologies, the beneficial effects of the invention are that, hydrophilic modifying is carried out on the surface of graphene, assigns graphene
It is good hydrophilic and dispersed, it is good with hydrophilic photosensitive resin compatibility, greatly improve the intensity and wear-resisting property of coating；Sun from
Sub- organic monomer modified hydrophilic resin, can be effectively suppressed the growth of coating surface bacterium, have good self-cleaning property；After solidification
Cross-linked network is formed, the mechanical performances such as adhesive force, hardness, rub resistance, water resistance are promoted, can be persistently antifog；Low-temperature bake, can
Suitable for various substrates.
Above-described is only embodiments of the present invention, it should be noted here that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, improvement can also be made, but these belong to protection model of the invention
It encloses.
Claims (1)
1. a kind of automatically cleaning photocuring anti-fog coating, which is characterized in that be made of the raw material of following mass parts:
3-8 mass parts modified graphene nanoparticle,
20-80 mass parts hydrophilic photosensitive resin,
5-20 mass parts photoinitiator,
15-40 mass parts diluent,
1-3 mass parts curing accelerator；
The photoinitiator is benzophenone, benzoin ethyl ether, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy cyclohexylphenyl
One or more of base phenyl ketone, 2,4,6- trimethylbenzoyl diphenyl phosphine oxide；
The diluent be ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, diglycol methyl ether,
One or more of diglycol ether；
The curing accelerator is in the ammonium salt of sulfuric acid, hydrochloric acid, chlorosulfonic acid, terephthalic acid (TPA), hydrobromic acid, perchloric acid acids or acid
One or more；
Wherein: the preparation step of the modified graphene nanoparticle is as follows:
1) by 40-80 mass parts allyl glycidyl ether, 5-12 mass parts graphene, 20-50 mass parts diluent, 1-3 matter
It measures part Pyrogentisinic Acid polymerization inhibitor to be added in reaction vessel, ultrasonic disperse 30min stirs 18 hours at 80-130 DEG C, obtains allyl
Base graft modification graphene；
2) 15-30 mass parts allyl graft modification graphene, 50-90 parts of hydrophilic monomers, 35-60 mass parts diluent are added
In reaction vessel, is stirred for 24 hours at being 50-80 DEG C in temperature, obtain modified graphene nanoparticle；
The preparation method of the automatically cleaning photocuring anti-fog coating, comprising the following steps:
Step 1: preparing modified graphene nanoparticle
Step 2: preparing hydrophilic photosensitive resin
1) by 20-60 mass parts acrylic ester monomer, 10-40 mass parts dimethylaminoethyl methacrylate and 10-50 matter
20-60 mass parts are slowly added dropwise into diluent in the vinyl monomer of amount part nitrogen atom, under the conditions of 90 DEG C, by 0.5-5 matter
It measures part initiator to be added in aforementioned mixed solution, time for adding 6-8h, keeps the temperature 2-3h after the completion and obtain hydrophilic photosensitive resin；
Step 3: the preparation of automatically cleaning photocuring anti-fog coating
3-8 mass parts modified graphene nanoparticle obtained in step 1 is taken,
Take 20-80 mass parts hydrophilic photosensitive resin and 5-20 mass parts photoinitiator obtained, 15-40 matter in step 2
Part diluent is measured, 1-3 mass parts curing accelerator is uniformly mixed and forms automatically cleaning photocuring anti-fog coating；
Hydrophilic monomer in step 1 includes acrylic acid, acrylate, hydroxyethyl methacrylate, methyl methacrylate, third
One or more of olefin(e) acid hydroxyl ethyl ester；
Diluent in step 1 is ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, a contracting diethyl two
One or more of alcohol methyl ether, diglycol ether；
Acrylic ester monomer in step 2 includes 2- acrylamide -2- methyl-propanesulfonic acid, hydroxyethyl methacrylate, third
The one or more of olefin(e) acid hydroxyl ethyl ester, hy-droxybutyl, methacrylate；
Diluent in step 2 is ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, a contracting diethyl two
One or more of alcohol methyl ether, diglycol ether；The initiator be benzoyl peroxide, lauroyl peroxide,
The tertiary fourth of isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-t-butyl peroxide, cumyl peroxide, perbenzoic acid
Ester, peroxidating trimethylacetic acid tertiary butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, azo-bis-isobutyl cyanide, the different cyanogen in heptan of azo two,
One of di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate.
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| CN106827726B (en) * | 2017-01-24 | 2019-04-16 | 杭州科翼科技有限公司 | A kind of glass for protecting eyesight |
| CN107059415A (en) * | 2017-04-12 | 2017-08-18 | 三元控股集团有限公司 | A kind of preparation method of the multifunctional conductive fabric based on photocuring technology |
| CN108504146B (en) * | 2018-04-04 | 2019-08-20 | 江南大学 | A kind of UV photocuring antifoggant and preparation method thereof |
| CN109338735B (en) * | 2018-11-29 | 2020-12-08 | 牛墨石墨烯应用科技有限公司 | Graphene fiber heat-insulation mesh cloth and preparation method thereof |
| CN114045059B (en) * | 2021-12-10 | 2023-04-28 | 广州大学 | Liquid and bacteria adhesion preventing electrophoretic paint and application method thereof |
| CN115558408B (en) * | 2022-10-16 | 2023-10-24 | 杭州梵因科技有限公司 | Preparation method of high-performance anti-fog cream |
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