CN116179059A - Transparent photo-curing coating and preparation method thereof - Google Patents
Transparent photo-curing coating and preparation method thereof Download PDFInfo
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- CN116179059A CN116179059A CN202310035214.1A CN202310035214A CN116179059A CN 116179059 A CN116179059 A CN 116179059A CN 202310035214 A CN202310035214 A CN 202310035214A CN 116179059 A CN116179059 A CN 116179059A
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention discloses a filler modified dispersion and a preparation method of a photo-curing organic-inorganic hybrid coating thereof, belonging to the technical field of preparation of photo-curing organic-inorganic hybrid coatings. The invention combines the filler modified dispersion technology and the photo-curing technology into a whole, and improves the dispersibility of the filler in the photo-curing coating by adjusting the grafting groups on the surface of the filler and the dispersion mode of the filler. And then the adhesive force, hardness, wear resistance and transparency of the photo-curing coating with the metal substrate are adjusted by adjusting the addition amount of the surface groups of the filler and the modified filler. Compared with a coating pencil without MMT, the photo-curing coating with the MMT has the advantages that the hardness of the photo-curing coating with the MMT is improved by 1-2 grades; the drawing adhesive force is improved by 0-60%; the abrasion mass loss of the rubber grinding wheel for 500 times under the load of 1000g is reduced by 0-30%; the ultraviolet transmittance of the 60 μm coating at 600nm can still be maintained at 80-88%.
Description
Technical Field
The invention relates to a filler modified dispersion and a preparation method of a photo-curing organic-inorganic hybrid coating thereof, belonging to the technical field of preparation of photo-curing organic-inorganic hybrid coatings.
Background
The photo-curing coating has the characteristic of 5E and has been widely applied to the fields of automobiles, optical devices, mobile phones, electric appliances, woodware and the like. The coating is mainly used for protecting the surface of the substrate and preventing the surface from being damaged and destroyed by external action, and the damage can lead the coating to generate optical haze, influence the appearance of a product, lead the substrate to lose adhesion and even completely destroy the coating. Therefore, hardness and abrasion resistance are one of the important application indexes of the coating. Inorganic nano particles are introduced into a photo-curing resin system, so that the method is a simple method for enhancing the hardness, wear resistance, thermal stability and other properties of the coating. The polar group is introduced into the inorganic filler, so that the adhesive force between the coating and the metal substrate can be improved. However, the fillers are added industrially by direct addition of dry powder, which has problems such as excessive addition of fillers, which causes agglomeration in the coating and thus a decrease in the coating properties and no longer transparency of the coating.
Therefore, there is a need to develop a new filler modification and dispersion process to produce a clear coating with enhanced hardness, adhesion and abrasion resistance.
Disclosure of Invention
In order to improve the hardness, adhesive force and wear resistance of the photo-curing coating and ensure the transparency of the coating, the invention provides a modified dispersion of filler and a preparation method of a hybrid coating thereof, by which the problem of difficult dispersion of dry powder in the photo-curing coating can be avoided, so that the dispersibility of the dry powder in the coating is improved, and the hardness and wear resistance of the coating are improved on the premise of ensuring the transparency of the coating.
A first object of the present invention is to prepare a modified MMT (montmorillonite)/reactive diluent dispersion to avoid the influence of drying on the dispersibility of MMT, the method comprising the steps of:
preparation of modified MMT: the method comprises the steps of respectively modifying MMT by using a cationic surfactant, (methyl) acrylic acid and a silane coupling agent, wherein the cationic surfactant is a long-chain cationic surfactant with a methacrylate group at one end, the silane coupling agent is a silane coupling agent with an amino group at one end, and finally, the obtained modified MMT is dispersed in a solvent (drying is avoided in the process), and the final modified MMT is modified MMT/solvent dispersion;
preparation of modified MMT/reactive diluent dispersion: the modified MMT/solvent dispersion is mixed uniformly (preferably by ultrasonic agitation) with a reactive diluent, which is a photocuring reactive diluent, and the solvent is removed by evaporation (preferably by rotary evaporation).
In one embodiment, the MMT includes, but is not limited to, one of natural MMT and inorganic modified MMT.
In one embodiment, the MMT may be: natural MMT, sodium-based MMT, calcium-based MMT, lithium-based MMT, K10, KSF, etc.
In one embodiment, the cationic surfactant is one of long-chain cationic surfactants with methacrylate groups at one end, and the silane coupling agent is one of silane coupling agents with amino groups at one end; solvents include, but are not limited to, one of a class of solvents that facilitate dispersion of the modified MMT and have a boiling point less than 80 ℃.
In one embodiment, the cationic surfactant may be: cetyl (ethyl methacrylate) dimethyl ammonium bromide.
In one embodiment, the silane coupling agent may be: 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, and the like.
In one embodiment, the dispersing solvent may be: ethanol, methanol, ethyl acetate, methylene chloride, acetone, methyl acetate, tetrahydrofuran, and the like.
In one embodiment, the photocuring reactive diluent comprises any one or a combination of more than two of acrylate compounds with the viscosity of less than 200cp, wherein the acrylate compounds have 1 or more than 1 acrylate group in a structure.
In one embodiment, the photocurable reactive diluent may be: 4-tert-butylcyclohexyl acrylate, ethyleneurea ethoxy methacrylate, m-phenoxybenzyl methacrylate, biscyclopentenyl acrylate, 2-phenoxyethyl acrylate, ethoxyethoxyethyl acrylate, cyclotrimethylolpropane methylal acrylate, 2-carboxyethyl acrylate, tetrahydrofurfuryl acrylate, lauric acid acrylate, stearic acid acrylate, nonylphenol acrylate, isodecyl acrylate, acrylic acid ester, biscyclopentenyl ethoxylated methacrylate, oxetane methacrylate, isodecyl methacrylate, 2-phenoxyethyl methacrylate, methoxypolyethylene glycol (350) methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, benzyl acrylate, biscyclopentyl methacrylate, 2-ethylhexyl methacrylate, tricyclodecanedimethanol diacrylate, polypropylene glycol (700) diacrylate, 1, 6-hexanediol diacrylate are homogeneously mixed (preferably by ultrasonic stirring), the solvent is removed by evaporation (preferably by rotary evaporation), and the reactive diluent is a photocuring reactive diluent.
In one embodiment, the MMT includes, but is not limited to, one of natural MMT and inorganic modified MMT.
In one embodiment, the MMT may be: natural MMT, sodium-based MMT, calcium-based MMT, lithium-based MMT, K10, KSF, etc.
In one embodiment, the cationic surfactant is one of long-chain cationic surfactants with methacrylate groups at one end, and the silane coupling agent is one of silane coupling agents with amino groups at one end; solvents include, but are not limited to, one of a class of solvents that facilitate dispersion of the modified MMT and have a boiling point less than 80 ℃.
In one embodiment, the cationic surfactant may be: cetyl (ethyl methacrylate) dimethyl ammonium bromide.
In one embodiment, the silane coupling agent may be: 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, and the like.
In one embodiment, the dispersing solvent may be: ethanol, methanol, ethyl acetate, methylene chloride, acetone, methyl acetate, tetrahydrofuran, and the like.
In one embodiment, the photocuring reactive diluent comprises any one or a combination of more than two of acrylate compounds with the viscosity of less than 200cp, wherein the acrylate compounds have 1 or more than 1 acrylate group in a structure.
In one embodiment, the photocurable reactive diluent may be: 4-tert-butylcyclohexyl acrylate, ethyleneurea ethoxy methacrylate, m-phenoxybenzyl methacrylate, biscyclopentenyl acrylate, 2-phenoxyethyl acrylate, ethoxyethoxyethyl acrylate, cyclotrimethylolpropane methylal acrylate, 2-carboxyethyl acrylate, tetrahydrofurfuryl acrylate, lauric acid acrylate, stearic acid acrylate, nonylphenol acrylate, isodecyl acrylate, acrylic acid, biscyclopentenyl ethoxylated methacrylate, oxetane methacrylate, isodecyl methacrylate, 2-phenoxyethyl methacrylate, methoxypolyethylene glycol (350) methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, benzyl acrylate, biscyclopentyl methacrylate, 2-ethylhexyl methacrylate, tricyclodecane dimethanol diacrylate, polypropylene glycol (700) diacrylate, 1, 6-hexanediol diacrylate, ethoxylated 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol (200) diacrylate, 1, 4-butanediol diacrylate, propylene glycol diacrylate, polyethylene glycol (400), polyethylene glycol diacrylate, polyethylene glycol (600), polyethylene glycol (3-propanediol (2-3-propanediol) diacrylate, 1, 3-propanediol (300-propanediol (2-propanediol) diacrylate), 3-methyl-1, 5-pentanediol diacrylate, ethylene glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, tripropylene glycol dimethacrylate, polyethylene glycol (200) dimethacrylate, 1, 4-butanediol dimethacrylate, polyethylene glycol (400) dimethacrylate, polyethylene glycol (600) dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, trimethylolpropane trimethacrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, 1, 6-hexanediol dimethacrylate, and the like.
In one embodiment, the modifying agents in the modified MMT/solvent dispersion material are cetyl (ethyl methacrylate) dimethyl ammonium bromide, MAA (methacrylic acid) and 3-aminopropyl triethoxysilane, respectively, MMT is K10, and the solvent is absolute ethanol.
In one embodiment, the reactive diluent in the modified MMT/reactive diluent is isobornyl acrylate.
In one embodiment, the amount of cationic surfactant, on an ion exchange capacity basis, may be: 1-2CEC; the amount of MAA may be: 1-10mmol/g cationic surfactant; the amount of the silane coupling agent may be: 2-10mmol/g MMT.
In one embodiment, the amount of cationic surfactant is 1CEC on an ion exchange capacity basis; the amount of MAA was 10mmol/g cationic surfactant; the amount of the silane coupling agent is 5mmol/g MMT.
In one embodiment, the solid content of the resulting modified MMT/solvent dispersion may be: 2-30wt%; the solids content of the modified MMT/reactive diluent may be: 20-40wt%.
Esters, ethoxylated 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol (200) diacrylate, 1, 4-butanediol diacrylate, propoxylated neopentyl glycol diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, polyethylene glycol (300) diacrylate, 2-methyl-1, 3-propanediol diacrylate, ethoxylated 2-methyl-1, 3-propanediol diacrylate, 3-methyl-1, 5-pentanediol diacrylate, ethylene glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, tripropylene glycol dimethacrylate, polyethylene glycol (200) dimethacrylate, 1, 4-butanediol dimethacrylate polyethylene glycol (400) dimethacrylate, polyethylene glycol (600) dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, propoxylated glycerol triacrylate, trimethylolpropane trimethacrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylol propane triacrylate, ethoxylated trimethylol propane triacrylate, propoxylated glycerol triacrylate, 1, 6-hexanediol dimethacrylate, and the like.
In one embodiment, the modifying agents in the modified MMT/solvent dispersion material are cetyl (ethyl methacrylate) dimethyl ammonium bromide, MAA (methacrylic acid) and 3-aminopropyl triethoxysilane, respectively, MMT is K10, and the solvent is absolute ethanol.
In one embodiment, the reactive diluent in the modified MMT/reactive diluent is isobornyl acrylate.
In one embodiment, the amount of cationic surfactant, on an ion exchange capacity basis, may be: 1-2CEC; the amount of MAA may be: 1-10mmol/g cationic surfactant; the amount of the silane coupling agent may be: 2-10mmol/g MMT.
In one embodiment, the amount of cationic surfactant is 1CEC on an ion exchange capacity basis; the amount of MAA was 10mmol/g cationic surfactant; the amount of the silane coupling agent is 5mmol/g MMT.
In one embodiment, the solid content of the resulting modified MMT/solvent dispersion may be: 2-30wt%; the solids content of the modified MMT/reactive diluent may be: 20-40wt%.
In one embodiment, the modified MMT/solvent dispersion has a solids content of 10wt%; the modified MMT/reactive diluent has a solids content of 30wt%.
In one embodiment, the modified MMT/solvent dispersion is stirred with the reactive diluent at 100-1000rpm for 30-60 minutes and sonicated for 30-60 minutes.
In one embodiment, the rotary vacuum evaporator has a temperature of 40-60℃and a rotational speed of 20-50rpm.
A second object of the present invention is to produce a clear coating having enhanced hardness, adhesion and abrasion resistance, said method comprising the steps of:
preparation of photo-curing coating: uniformly mixing the photo-curing resin, the reactive diluent, the modified MMT/reactive diluent dispersion liquid, the auxiliary agent and the photoinitiator according to the formula proportion;
preparation of a photo-cured coating: and coating the prepared coating on a substrate, and curing by a photo-curing device.
In one embodiment, the photo-curable resin includes, but is not limited to, any one or a combination of two or more of acrylic acid esters, acrylic acid derivatives, methacrylic acid esters, and methacrylic acid ester derivatives, and preferably, the photo-curable resin includes any one or a combination of two or more of epoxy (meth) acrylic acid esters, polyester (meth) acrylic acid esters, polyether (meth) acrylic acid esters, amino acrylic acid esters, polyurethane (meth) acrylic acid esters, and photosensitive acrylic acid ester resins.
In one embodiment, the photocurable resin is a (meth) acrylate. The (meth) acrylic acid esters represent the corresponding acrylic acid esters, i.e. derivatives of acrylic acid, and methacrylic acid esters, i.e. derivatives of methacrylic acid esters.
In one embodiment, the photocurable resin includes, but is not limited to, any one or a combination of two or more of epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, amino acrylate, polyurethane (meth) acrylate, photosensitive acrylate resin.
In one embodiment, the epoxy acrylates include, but are not limited to, bisphenol a type epoxy acrylates, hydrogenated bisphenol a type epoxy acrylates, bisphenol F type epoxy acrylates, hydrogenated bisphenol F type epoxy acrylates, phenolic epoxy acrylates, epoxidized oil acrylates, and modified epoxy acrylates modified with these resins that retain the photocuring function. The modified epoxy acrylates include, but are not limited to, alcohol modified epoxy acrylates, acid or anhydride modified epoxy acrylates, polyurethane modified epoxy acrylates, silicone modified epoxy acrylates, fluoromonomer modified epoxy acrylates, and the like.
In one embodiment, the epoxy acrylate is specifically bisphenol a epoxy acrylate, bisphenol F epoxy acrylate, fatty acid modified epoxy acrylate, and the like.
In one embodiment, the polyester (meth) acrylates include, but are not limited to, polyester acrylates containing different polyacids and different polyols and polyester (meth) acrylates obtained by modification of these resins. The modified polyester acrylate comprises polyurethane modified polyester acrylate, polyether modified polyester acrylate, organosilicon modified polyester acrylate, fluorine-containing monomer modified polyester acrylate and the like.
In one embodiment, the polyester acrylate is specifically a silicone modified polyester acrylate, a polyurethane modified polyester acrylate, a polyether modified polyester acrylate, or the like.
In one embodiment, the polyether acrylates include, but are not limited to, polyether acrylates of varying chain lengths made from ethylene glycol, propylene glycol, tetrahydrofuran, and polyether acrylates modified from these resins. The modified polyether acrylate comprises polyurethane modified polyether acrylate, organosilicon modified polyether acrylate, fluorine-containing monomer modified polyether acrylate and the like. Specifically, the silicone modified polyether acrylate, polyurethane modified polyether acrylate and the like can be used.
In one embodiment, the amino acrylates include, but are not limited to, urea formaldehyde acrylates, melamine formaldehyde acrylates, benzomelamine formaldehyde acrylates, and amino acrylates modified from these resins.
In one embodiment, the urethane acrylate includes, but is not limited to, aliphatic urethane acrylates, cycloaliphatic urethane acrylates, aromatic urethane acrylates, and urethane acrylates modified from these resins. The modified polyurethane acrylic ester comprises organosilicon modified polyurethane acrylic ester, polyether modified polyurethane acrylic ester, fluorine-containing monomer modified polyurethane acrylic ester and the like.
In one embodiment, the photosensitive acrylate resin includes, but is not limited to, glycidyl (meth) acrylate modified acrylate resins, maleic anhydride modified acrylate resins, and the like.
In one embodiment, the adjuvants include, but are not limited to, leveling agents, adhesion promoters, and the like suitable for use in the photocurable coating system.
In one embodiment, the leveling agent is polyether modified silicone or the like and the adhesion promoter is a methacrylate-esterified phosphate functional monomer.
In one embodiment, the photoinitiator includes, but is not limited to, a class of substances capable of initiating polymerization of the acrylate under ultraviolet or visible light irradiation.
In one embodiment, the photoinitiator includes, but is not limited to, 2-hydroxy-methylphenyl propane-1-one, 1-hydroxycyclohexylphenyl ketone, benzoin ethyl ether, benzoin propyl ether, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, benzoin dimethyl ether, camphorquinone, 1-phenyl-1, 2-propanedione, 2,4, 6-trimethylbenzoyl diphenyl phosphorus, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylphenylphosphine oxide, isopropylthioxanthone, bis (1- (2, 4-difluorophenyl) -3-pyrrolyl) titanocene, 2-benzyl-2-methylamino-1- (4-morpholinphenyl) -1-butanone, and the like.
In one embodiment, the photo-curable resin in the photo-curable material is epoxy acrylate, polyester acrylate, reactive diluent is isobornyl acrylate, and the photo-curable material is attached
The force promoter is methyl propylene esterified phosphate functional monomer, the leveling agent is polyether modified organosilicon, and the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
In one embodiment, the light-cured material formula comprises, by mass, 30-70 parts of light-cured resin, 30-70 parts of reactive diluent, 1-5 parts of auxiliary agent, 0.1-10 parts of photoinitiator, and 3-10wt% of modified MMT/reactive diluent dispersion liquid.
In one embodiment, the mixing of the photocurable resin, reactive diluent, modified MMT/reactive diluent dispersion, auxiliary agent, photoinitiator is conventional in the art, and may be, for example, a high speed disperser, with preferred operating conditions of the high speed disperser being: the rotation speed is 2000-3500rpm, and the dispersing time is 2-10min.
In one embodiment, the light waves emitted by the light curing device contain a wave band with a wavelength in the range of 256-500 nm.
In one embodiment, the light curing device emits ultraviolet or visible light having a wavelength in the range of 256-500 nm.
In one embodiment, the energy density of the irradiation of the light curing device is 10-200mJ/cm 2 。
In one embodiment, the coating properties of the hybrid coating include transparency, adhesion, hardness, and abrasion resistance.
In one embodiment, the prepared photo-cured coating incorporating the modified MMT can still maintain a UV transmission of 80% -88% at 600nm thickness of 60. Mu.m.
In one embodiment, the prepared photo-cured coating added with the modified MMT has 0-60% improvement in drawing adhesion compared with a coating without the modified MMT.
In one embodiment, the resulting photo-cured coating incorporating modified MMT has a pencil hardness 1-2 levels higher than the coating without modified MMT.
In one embodiment, the resulting photo-cured coating incorporating modified MMT has a 0-30% reduction in abrasion mass loss of the 500 times rubber grinding wheel under 1000g load compared to the coating without modified MMT.
A third object of the present invention is to provide the application of the transparent coating with enhanced hardness, adhesion and abrasion resistance of any of the above embodiments, such as in the fields of automobiles, woodware, plastic articles, and the like.
The beneficial effects are that: compared with the prior art, the modified MMT/solvent dispersion liquid and the photocuring active diluent are uniformly mixed, and then the solvent is removed to form the modified MMT/active diluent dispersion liquid, so that MMT agglomeration caused by drying treatment is avoided, the adhesion of the coating and a steel plate substrate can be enhanced by grafting polar groups on the surface of the MMT, and finally the transparent coating with enhanced hardness, adhesion and wear resistance is obtained. The invention has the following advantages:
1. the prepared photo-curing coating added with the modified MMT can still maintain the ultraviolet transmittance at 600nm with the thickness of 60 mu m at 80-88% compared with the coating without the modified MMT.
2. The drawing adhesive force of the prepared photo-curing coating added with the modified MMT is improved by 0-60% compared with that of a coating without the modified MMT.
3. The prepared photo-cured coating added with the modified MMT has the advantage that the pencil hardness is improved by 1-2 grades compared with a coating without the modified MMT.
4. Compared with a coating without modified MMT, the prepared photo-curing coating with modified MMT has the advantages that the abrasion mass loss of the rubber grinding wheel for 500 times under the load of 1000g is reduced by 0-30%.
Drawings
Fig. 1 SEM and TEM images of MMT in different modified states. SEM: ethanol dispersion sample preparation of dry powder: (a) raw MMT, (b) MMT-n+, (c) MMT-n+ -M, (d) and (e) MMT-n+ -M-N; and (3) redispersing and preparing an ethanol dispersion liquid: (f) MMT-N+ -M-N. TEM: and (3) redispersing and preparing an ethanol dispersion liquid: (g) MMT-N+ -M-N.
FIG. 2 digital photographs of MMT coatings (10 wt%) in different modified states, left for 6 months at room temperature.
FIG. 3 is a bar graph of the coating pullout adhesion variation for different modified states MMT with an add-on level of 10wt%.
FIG. 4 different additions of MMT-N + -histogram of coating pullout adhesion variation of M-N.
FIG. 5 is a bar graph of the change in wear mass loss of a coating with an add-on of 10wt% MMT for different modification states.
FIG. 6 different amounts of MMT-N added + -a histogram of coating wear mass loss change for M-N.
FIG. 7 different MMT-N + -uv transmittance profile of M-N additive amount coating.
Detailed Description
The preparation method of the invention comprises the following steps: modifying MMT, preparing modified MMT/solvent dispersion, uniformly mixing the modified MMT/solvent dispersion with a photocuring reactive diluent, and removing the solvent through a rotary vacuum evaporator to obtain modified MMT/reactive diluent dispersion; and uniformly mixing the modified MMT/reactive diluent dispersion liquid according to the formula proportion by using a high-speed dispersing machine, and curing by using a photocuring device. The method specifically comprises the following steps:
(1) Preparation of modified MMT: MMT was modified with a long chain cationic surfactant having a methacrylate group, (meth) acrylic acid and a silane coupling agent having an amino group, respectively. MMT with amino groups and carboxyl groups grafted on the surface is obtained.
(2) Preparation of modified MMT/solvent dispersion: and (3) washing the modified MMT cleanly (avoiding drying), directly dispersing the MMT in a solvent, and uniformly mixing to obtain a modified MMT/solvent dispersion liquid. The solvent should be chosen to be suitable for modifying SiO 2 The nano particles and the photo-curing reactive diluent are dispersed and have low boiling point and are easy to remove.
(3) Preparation of modified MMT/reactive diluent dispersion: and uniformly mixing the modified MMT/solvent dispersion liquid and the reactive diluent by stirring and ultrasonic, and removing the solvent in the mixed liquid by using a rotary vacuum evaporator to obtain the modified MMT/reactive diluent dispersion liquid. The reactive diluent is a photocuring reactive diluent, the viscosity is less than 200cp, and the viscosity is not easy to be too large so as to facilitate the dispersion of the modified MMT in the reactive diluent.
(3) Preparation of the coating: according to the formula proportion, a high-speed dispersing machine is used for uniformly mixing photosensitive resin (namely photo-curing resin), photosensitive monomer (namely photo-curing reactive diluent), photoinitiator, auxiliary agent and modified MMT/reactive diluent dispersion liquid, and curing treatment is carried out by a photo-curing device.
Example 1: influence of modification and dispersion methods on MMT morphology
The present example experiments the impact of different modification states and dispersion methods on MMT morphology.
The raw materials are as follows: montmorillonite K10, hexadecyl (ethyl methacrylate) dimethyl ammonium bromide (QAC), 3-aminopropyl triethoxysilane (APTES), methacrylic acid (MAA), ammonium Persulfate (APS), hydrochloric acid, silver nitrate standard titration solution, ultrapure water, absolute ethanol.
The specific flow is as follows:
1. cationic surfactant modified MMT (MMT-N) + ): firstly, 10g of MMT was dispersed in 500mL of ultra pure water, and put into a 1L three-necked flask, and stirred at 700rpm at 80℃for 1 hour; then, 4.62g of QAC (1 CEC) was taken in a mixture of 150mL of absolute ethanol and 800. Mu.L of hydrochloric acid, and stirred at 80℃and 600rpm until the solution was clear and transparent; finally, adding the solution mixed with QAC into a flask mixed with MMT suspension, reacting for 24 hours, centrifuging with ethanol, ultrasonically washing for 3-4 times until no bromide ion exists in the supernatant, determining by titration with silver nitrate solution, drying in an oven at 80 ℃ for 24 hours, and obtaining the modified MMT which is marked as MMT-N + 。
MAA grafted MMT-N + (MMT-N + -M): first, 10g of MMT-N was added + Dispersing in 500mL of ultrapure water, performing ultrasonic dispersion for 1h, and putting the mixture into a 1L three-neck flask; then, 8.6g MAA was added to the three-necked flask, and stirred at 50℃and 700rpm for 30min; most preferably, the first to fourthAfter that, 8.6g of APS aqueous solution (1 wt%) was added, the reaction was carried out for 24 hours, the mixture was washed with ethanol by centrifugation and ultrasonic washing for 3 to 4 times, and dried in an oven at 80℃for 24 hours, and the obtained modified MMT was designated as MMT-N + -M。
APTES modified MMT-N + -M(MMT-N + -M-N): first, 10g of MMT-N was added + M is dispersed in 500mL of ultrapure water, and ultrasonic dispersion is carried out for 1h to obtain MMT water suspension; then, the pH of the MMT suspension was adjusted to 4 using 1M aqueous hydrochloric acid, and the suspension was added to a 1L three-necked flask, and stirred at 80℃and 700rpm for 30 minutes; finally, 10g of APTES was dissolved in 150mL of ultra pure water and added dropwise into a flask for reaction for 24 hours, and the mixture was washed with ethanol by centrifugation and ultrasonic washing for 3 to 4 times, and dried in an oven at 80℃for 24 hours, and the obtained modified MMT was designated as MMT-N + -M-N. MMT-N was run according to the method described above + Modifying to obtain MMT-N + -N。
The MMT and the modified MMT were prepared into ethanol dispersion liquid with the same concentration, and SEM and TEM morphology photographing were performed, and the results are shown in fig. 1.
As can be seen from fig. 1, the more pronounced the lamellar structure of MMT is with increasing number of modifications (fig. 1 (d) and (e)). Furthermore, the MMT morphology SEM (fig. 1 (f)) obtained by modifying the MMT/ethanol dispersion form showed a more fluffy lamellar structure. This example shows that MMT can be provided with a pronounced lamellar structure by multi-step modification and the use of an ethanol dispersion (avoiding drying) to achieve better dispersion.
Example 2: effect of modification of MMT on paint settleability
This example experiments the effect of modification of MMT on its dispersibility in photocurable coatings.
1. The centrifugal precipitate of various modified MMTs before drying, obtained in example 1 above, was dispersed in absolute ethanol to prepare MMT/ethanol dispersion having a solid content of 10wt%.
2. Mixing the above modified MMT/ethanol dispersion with isobornyl acrylate (IBOA), stirring at 300rpm for 30min, and ultrasonic treating for 30min. Ethanol was removed using a rotary vacuum evaporator at 40rpm at 50℃to give a modified MMT/IBOA dispersion (30 wt% solids).
3. Epoxy acrylate 6215-100, polyester acrylate DR-E524, isobornyl acrylate IBOA (total IBOA in the formulation=modified MMT/IBOA dispersion+extra), leveling agent BYK333, adhesion promoter CD-9051, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), modified MMT added in an amount of 10wt% of the total amount of resin and reactive diluent, and the individual components were mixed uniformly using a high speed disperser 3000rpm for 4 min.
Table 1 basic photo-curable formulation 1
| Raw materials of the formula | Content/wt% |
| 6215-100 | 30 |
| DR- |
40 |
| |
30 |
| BYK333 | 1 |
| CD-9051 | 2 |
| 1173 | 2 |
The prepared MMT coating added with different modification times is placed for 6 months at room temperature, and a digital photo is shown in figure 2. As can be seen from FIG. 2, after the coating added with the unmodified MMT is left at room temperature for 6 months, the MMT has sunk, while the other several coatings added with the modified MMT still maintain the overall uniformity, and no precipitation occurs. The embodiment shows that the interaction force between the MMT and the resin can be increased by carrying out surface organic modification on the MMT, so that the compatibility between the MMT and the resin matrix is improved, and the sinking phenomenon is avoided.
Example 3: influence of modified MMT on adhesion of photo-cured coatings
This example tested MMT-N in different modification states and different addition amounts + The effect of M-N on the adhesion of the photo-cured coating to the metal substrate.
The specific flow is as follows: MMT coatings with different addition amounts were prepared according to the procedure of example 2 and the formulation prepared in example 2 was coated on a low carbon steel sheet, and the coating was cured using a photo-curing apparatus, and the thickness of the cured coating was 60. Mu.m. The coating was subjected to a pullout adhesion test.
MMT with different modification states and MMT-N with different addition amounts are tested + The change in the coating pullout adhesion of M-N is shown in fig. 3, 4.
The drawing adhesion of the coating without MMT added in FIG. 3 is 1.64MPa, and as the polar groups (amino and carboxyl) on MMT are increased, MMT-N is shown + M-N, the coating adhesion of which increases to 2.6MPa.
MMT-N with different quality scores added in FIG. 4 + M-N, the pull-out adhesion of the coating decreases and then increases with increasing mass fraction, reaching 2.6MPa when the mass fraction is 10wt%. This example shows that the adhesion of the coating to the metal substrate can be improved by modifying the MMT surface to be filled with polar amino and/or carboxyl groups, and selecting the appropriate amount of addition.
Example 4: influence of modified MMT on wear resistance of photo-cured coating
This example tested MMT-N in different modification states and different addition amounts + The effect of M-N on the adhesion of the photo-cured coating to the metal substrate.
The specific experimental procedure is as follows: the MMT-added formulation prepared in example 3 was applied to a BGD paint film abrader specific substrate, cured to a film, and tested for 1000g loading, and mass change before and after 500 times abrasion.
MMT with different modification states and MMT-N with different addition amounts are tested + The change in coating wear mass loss of M-N is shown in fig. 5, 6.
In FIG. 5, the mass loss of the coating without MMT is 34.7mg after abrasion, the organic chain segment on the MMT is increased along with the progress of modification, the interaction force between the MMT and the resin matrix is increased, the compatibility is improved, when abrasion occurs, the MMT can resist the external force and is not easily separated from the coating by the external force, and the abrasion resistance is improved, for example, MMT-N is added + The loss of coating mass of M-N was reduced to 25.7mg. MMT-N followed in FIG. 6 + An increase in the amount of M-N added, a decrease and then an increase in the wear mass loss of the coating. This example shows that by modifying to increase the interaction force between MMT and the resin matrix and selecting a suitable amount of addition, the wear mass loss of the coating can be effectively reduced and the wear resistance improved.
Example 5: influence of modified MMT on hardness of photo-cured coating
This example describes different MMT-N + Effect of the amount of M-N added on pencil hardness of the photo-cured coating.
The specific experimental procedure is as follows: for the different MMT-N obtained by curing in example 3 + The coatings were subjected to pencil hardness tests in the presence of M-N additions.
Different MMT-N's tested + The pencil hardness results of the coating at the level of M-N addition are shown in Table 2.
TABLE 2 different MMT-N + Pencil hardness variation of M-N additive coating
As can be seen from the table, the pencil hardness of the coating without MMT was B, and the pencil hardness was found to be a function of MMT-N + The pencil hardness of the coating is also gradually increased to F by gradually increasing the addition amount of M-N. This example shows that within a certain range, MMT-N is improved + The addition of M-N can effectively improve the hardness of the coating.
Example 6: effect of modified MMT on the transparency of light-cured coatings
This example describes different MMT-N + The effect of the amount of M-N added on the transparency of the photocurable coating.
The specific experimental procedure is as follows: the coating prepared in example 3 was applied to a polytetrafluoroethylene sheet, cured to a film, and the thickness of the cured coating was 60 μm, which was peeled off from the sheet, and its transmittance in the visible light wavelength range was measured using an ultraviolet-visible spectrophotometer.
Different MMT-N's tested + The UV transmittance of the M-N addition coating is shown in FIG. 7.
As can be seen from the graph, the UV transmittance of the coating without MMT at 600nm wavelength is 88.5%, and the UV transmittance is 88.5% along with MMT-N + The uv transmittance of the coating gradually decreases to 83.6% by increasing the amount of M-N added to 10% by weight, but the coating remains transparent as a whole. This example shows that when MMT is added in an amount of 10wt% or less, the ultraviolet transmittance of the coating layer remains 80% or more, and the transparency as a whole remains.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that although the invention has been described in terms of preferred embodiments, it is not intended to limit the invention, but rather that modifications and adaptations can be made by those skilled in the art without departing from the principles of the invention. The products of the examples are all commercially available.
Claims (9)
1. A photo-curable coating, wherein the photo-curable coating is prepared by the steps of:
modification of MMT: modifying MMT by using a cationic surfactant, (methyl) acrylic acid and a silane coupling agent respectively, wherein the cationic surfactant is a long-chain cationic surfactant with a methacrylate group at one end, the silane coupling agent is a silane coupling agent with an amino group at one end, and dispersing the obtained modified MMT in a solvent to obtain a modified MMT/solvent dispersion;
preparation of modified MMT/reactive diluent dispersion: uniformly mixing the modified MMT/solvent dispersion liquid with a reactive diluent, and removing the solvent by adopting an evaporation mode, wherein the reactive diluent is a photocuring reactive diluent;
preparation of photo-curing coating: uniformly mixing the photo-curing resin, the reactive diluent, the MMT/reactive diluent dispersion liquid, the auxiliary agent and the photoinitiator;
preparation of a photo-cured coating: and coating the prepared coating on a substrate, and curing by a photo-curing device.
2. The photocurable coating according to claim 1, wherein said MMT is natural MMT and various inorganic-modified MMTs, has an ion exchange capacity of 60-120mmol/100g, and has a particle size of several tens nanometers to several tens micrometers; the cationic surfactant is one of long-chain cationic surfactants with methacrylate groups at one end; the silane coupling agent is one of silane coupling agents with amino at one end; the solvent is one of solvents which are easy to disperse the modified MMT and have a boiling point of less than 80 ℃.
3. The photocurable coating according to claim 1, wherein said photocurable reactive diluent is a combination of any one or two or more of acrylate compounds having a structure containing 1 or more acrylate groups and a viscosity of less than 200 cp.
4. The photocurable coating according to claim 1, characterized in that the photocurable resin comprises any one or a combination of two or more of acrylate, acrylic acid derivatives, methacrylate derivatives, preferably the photocurable resin comprises any one or a combination of two or more of epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, amino acrylate, polyurethane (meth) acrylate, photosensitive acrylate resin;
the auxiliary agent comprises a leveling agent and an adhesion promoter which are suitable for a photo-curing coating system;
the photoinitiator comprises a substance capable of initiating polymerization of acrylic ester substances under ultraviolet or visible light irradiation.
5. The photocurable coating according to claim 1, characterized in that the amount of cationic surfactant is 1CEC-2CEC on an ion exchange capacity basis; the amount of MAA is 1-10mmol/g cationic surfactant; the amount of the silane coupling agent is 2-10mmol/g MMT; the solid content of the prepared modified MMT/solvent dispersion liquid is 5-30wt%; the solid content of the modified MMT/reactive diluent is 20-40wt%.
6. The light-cured coating according to claim 1, wherein the light-cured coating comprises, by mass, 30-70 parts of light-cured resin, 30-70 parts of light-cured reactive diluent, 1-5 parts of auxiliary agent and 0.1-10 parts of photoinitiator.
7. The photocurable coating according to claim 1, characterized in that said modified MMT/reactive diluent dispersion is used in an amount of 3-10wt% of the total mass of photocurable resin and reactive diluent.
8. A method of preparing a photocurable coating according to claim 1, characterized in that the method comprises the steps of:
modification of MMT: modifying MMT by using a cationic surfactant, (methyl) acrylic acid and a silane coupling agent respectively, wherein the cationic surfactant is a long-chain cationic surfactant with a methacrylate group at one end, the silane coupling agent is a silane coupling agent with an amino group at one end, and dispersing the obtained modified MMT in a solvent to obtain a modified MMT/solvent dispersion;
preparation of modified MMT/reactive diluent dispersion: uniformly mixing the modified MMT/solvent dispersion liquid with a reactive diluent, and removing the solvent by adopting an evaporation mode, wherein the reactive diluent is a photocuring reactive diluent;
preparation of photo-curing coating: uniformly mixing the photo-curing resin, the reactive diluent, the MMT/reactive diluent dispersion liquid, the auxiliary agent and the photoinitiator;
preparation of a photo-cured coating: and coating the prepared coating on a substrate, and curing by a photo-curing device.
9. Use of a photocurable coating according to claim 1, characterized in that the coating is applicable to the protection of substrate surfaces in the automotive, optical, cell phone, electrical and wood fields.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050261413A1 (en) * | 2001-09-28 | 2005-11-24 | Miriam Rafailovich | Flame retardant and uv absorptive polymethylmethacrylate nanocomposites |
| CN101423678A (en) * | 2008-10-29 | 2009-05-06 | 国家纳米科学中心 | Light curing nano composite coating |
| EP3327108A1 (en) * | 2016-11-25 | 2018-05-30 | Henkel AG & Co. KGaA | Easy ironing/anti-wrinkle/less crease benefit of detergents with the help of bentonite or its derivatives |
| CN111040355A (en) * | 2019-12-31 | 2020-04-21 | 六盘水师范学院 | Random stripping type polymethyl methacrylate/montmorillonite nano composite material and preparation method thereof |
| CN112625480A (en) * | 2020-12-02 | 2021-04-09 | 杭州福斯特应用材料股份有限公司 | Photocuring transparent coating |
-
2023
- 2023-01-10 CN CN202310035214.1A patent/CN116179059A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050261413A1 (en) * | 2001-09-28 | 2005-11-24 | Miriam Rafailovich | Flame retardant and uv absorptive polymethylmethacrylate nanocomposites |
| CN101423678A (en) * | 2008-10-29 | 2009-05-06 | 国家纳米科学中心 | Light curing nano composite coating |
| EP3327108A1 (en) * | 2016-11-25 | 2018-05-30 | Henkel AG & Co. KGaA | Easy ironing/anti-wrinkle/less crease benefit of detergents with the help of bentonite or its derivatives |
| CN111040355A (en) * | 2019-12-31 | 2020-04-21 | 六盘水师范学院 | Random stripping type polymethyl methacrylate/montmorillonite nano composite material and preparation method thereof |
| CN112625480A (en) * | 2020-12-02 | 2021-04-09 | 杭州福斯特应用材料股份有限公司 | Photocuring transparent coating |
Non-Patent Citations (2)
| Title |
|---|
| 王月欣, 李英, 张留成: "聚合物层状硅酸盐纳米复合材料的研究进展――层状硅酸盐粘土的有机改性", 化学世界, no. 09, pages 562 - 565 * |
| 陈海群;徐义荣;赵银芝;: "蒙脱土的表面修饰", 化工矿物与加工, no. 08, pages 35 - 38 * |
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