CN112175489B - Hybrid epoxy acrylate UV coating with high surface hardness - Google Patents
Hybrid epoxy acrylate UV coating with high surface hardness Download PDFInfo
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- CN112175489B CN112175489B CN202010921543.2A CN202010921543A CN112175489B CN 112175489 B CN112175489 B CN 112175489B CN 202010921543 A CN202010921543 A CN 202010921543A CN 112175489 B CN112175489 B CN 112175489B
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated 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
- 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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- 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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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 invention discloses a high-surface-hardness hybrid epoxy acrylate UV coating, which comprises the following components: epoxy acrylate oligomer, modified silicon dioxide, reactive diluent, photoinitiator, auxiliary agent or hybrid epoxy acrylate oligomer, reactive diluent, photoinitiator and auxiliary agent; the hybrid epoxy acrylate oligomer is an in-situ hydrolysis polymerization product prepared by adopting an in-situ sol-gel method to prepare a silicon dioxide precursor in an epoxy acrylate oligomer system. The invention improves the compatibility of the silicon dioxide particles and the light-cured resin system by preparing transparent silicon dioxide nano particles and modifying the transparent silicon dioxide nano particles to match with the ultraviolet light-cured resin system; the hybrid epoxy acrylate UV coating has low viscosity and low inorganic component addition amount, and the prepared coating has excellent hardness and wear resistance and has great value in the fields of furniture such as floors, 3C products and other wear-resistant fields.
Description
Technical Field
The invention belongs to the field of photocuring resin and paint, relates to a high-surface-hardness hybrid epoxy acrylate UV paint, and particularly relates to a high-surface-hardness hybrid epoxy acrylate UV paint prepared from modified silicon dioxide nanoparticles and photocuring epoxy acrylate resin.
Background
The ultraviolet curing coating has the characteristic of 5E, and is an environment-friendly high-efficiency coating. In recent years, ultraviolet curable coatings have been widely used in the fields of packaging, furniture, electronics, automotive coatings, and the like. The traditional light-cured resin is mainly obtained by the grafting reaction of light-curable acrylate groups, polyurethane and epoxy resin. The light-cured resin is mainly composed of organic components, so that the hardness and the wear resistance of the light-cured resin after being prepared into a coating are low, and the application of the light-cured resin in some fields is hindered. In the field of wood floors, conventional epoxy acrylate has poor hardness and wear resistance, so that the gloss and texture of the floor surface are quickly lost, and the service life of the wood floor is shortened.
Currently, there are two main strategies for increasing the hardness and abrasion resistance of photocurable resins. Firstly, a high-functionality monomer is introduced into a light-cured resin system, so that the crosslinking density of the light-cured resin is increased, and the hardness and the wear resistance of a coating are increased. However, the addition of high-functionality components leads to an increase in the viscosity of the system, which is not favorable for storage and construction; in addition, the introduction of a high-functional group causes problems such as brittleness and reduced adhesion of the coating film. Secondly, inorganic components are introduced into a light-cured resin system, and the nano-hybrid photochemical coating is prepared in an organic-inorganic compounding manner. In general, the hardness and wear resistance of a coating can be improved by directly adding an inorganic filler into a light-cured resin system, but the dispersibility and sedimentation of the inorganic filler in the light-cured resin system are difficult to solve, so that the following three problems exist: firstly, the inorganic filler generally has a larger particle size and a higher density than the light-cured resin, so that the inorganic particles are rapidly settled in a resin system, and the method for increasing the hardness and the wear resistance of the light-cured coating by directly adding the filler is not suitable; secondly, theoretically, the sedimentation rate of the nano inorganic filler in the light-cured resin system can be ignored, but the nano particles have extremely high surface energy, so that the nano inorganic filler is difficult to disperse in the resin system, and the nano inorganic filler forms aggregates, so that the system is unstable; third, a large amount of inorganic components are generally required to be added into a photocurable resin system to obtain a photocurable coating with better hardness and abrasion resistance, which generally causes the problems of increased system viscosity and phase separation of inorganic fillers in the system, coating defects and reduced coating adhesion. How to obtain the photocureable coating with high surface hardness and high wear resistance by a nano hybridization method is always a research hotspot and a technical difficulty in the field.
Disclosure of Invention
The invention aims to solve the problems of dispersibility and sedimentation of inorganic filler in a photocuring resin system, and provides an ultraviolet-curable nano hybrid epoxy acrylate system which has lower viscosity and lower inorganic component addition, a coating film is prepared by using blade coating, roller coating, spraying and other modes, and a coating with extremely high surface hardness and wear resistance can be obtained after full photocuring.
The purpose of the invention is realized by the following technical scheme:
a high-surface-hardness hybrid epoxy acrylate UV coating comprises 35-75 wt%, 5-20 wt% and 10-45 wt% of epoxy acrylate oligomer, 5-20 wt% and 10-45 wt% of reactive diluent, wherein the sum of the epoxy acrylate oligomer, the modified silica and the reactive diluent is 100%, and the photoinitiator and the auxiliary agent are respectively 2-4 wt% and 1-2 wt% of the total amount of the epoxy acrylate oligomer, the modified silica and the reactive diluent;
or the composition comprises 55-90 wt% of hybrid epoxy acrylate oligomer and 10-45 wt% of reactive diluent, wherein the sum of the hybrid epoxy acrylate oligomer and the reactive diluent is 100%, and the photoinitiator and the auxiliary agent are 2-4 wt% and 1-2 wt% of the total amount of the hybrid epoxy acrylate oligomer and the reactive diluent.
The molecular weight of the epoxy acrylate oligomer is 200-3000.
The epoxy acrylate oligomer is prepared by reacting succinic anhydride with trimethylolpropane di (methyl) acrylate or (methyl) hydroxyethyl acrylate or pentaerythritol triacrylate under the action of a catalyst and a polymerization inhibitor to prepare a carboxyl-containing acrylate intermediate, and then reacting the acrylate intermediate with neopentyl glycol diglycidyl ether or trimethylolpropane triglycidyl ether or pentaerythritol glycidyl ether or 1, 2-cyclohexanediol diglycidyl ether under the action of a catalyst and a polymerization inhibitor to prepare the epoxy acrylate. The trimethylolpropane di (methyl) acrylate is selected from any one of trimethylolpropane diacrylate or trimethylolpropane dimethacrylate, and the hydroxyethyl (methyl) acrylate is selected from any one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate or hydroxypropyl acrylate.
Specifically, reference may be made to CN104003872A, CN104003873A, CN104003874A, CN104003875A, CN104003876A, CN104003877A, CN104003878A, CN104003879A, CN104003880A and CN104003881A for the preparation of epoxy acrylate oligomers. The epoxy acrylate oligomer can also be prepared by other methods.
The modified silicon dioxide is prepared by a silicon dioxide precursor by adopting a nano dispersion method; the hybrid epoxy acrylate oligomer is an in-situ hydrolysis polymerization product prepared by adopting an in-situ sol-gel method to prepare a silicon dioxide precursor in an epoxy acrylate oligomer system. The invention introduces nano modified silicon dioxide particles into an ultraviolet curing resin system by a nano dispersion method or an in-situ sol-gel method to obtain an organic/inorganic hybrid epoxy acrylate resin system capable of being cured by ultraviolet light. Compared with a method of directly adding and blending, the method for preparing and modifying the silicon dioxide nano particles by adopting the in-situ sol-gel method has better uniformity and better dispersity, and the prepared coating has more excellent hardness and wear resistance. Therefore, the in-situ hydrolysis polymerization to generate the modified silica by the in-situ sol-gel method is the preferred method.
The silicon dioxide precursor is tetraethyl orthosilicate.
The modified silicon dioxide is prepared by a nano-dispersion method: tetraethyl orthosilicate and lower alcohol are mixed and dissolved, silicon dioxide sol is obtained through hydrolysis and condensation reaction under the action of alkali or acid catalysts, a modifying reagent is added into the silicon dioxide sol to modify silicon dioxide, the modified silicon dioxide particles in an alcohol-water system can not be dispersed in light-cured resin, after the reaction is finished, water and lower alcohol in the modified silicon dioxide sol system are removed through reduced pressure distillation or centrifugation until the water content is less than or equal to 3%, and the modified silicon dioxide dispersion liquid is obtained through dispersing in an organic solvent mixed and dissolved with water. According to the invention, the modified silicon dioxide prepared by a nano-dispersion method is mixed with the epoxy acrylate oligomer in a dispersion liquid form, the modified silicon dioxide dispersion liquid and the epoxy acrylate oligomer have good compatibility and stability, the problem that dry inorganic nanoparticles are difficult to disperse is solved, and the phenomenon that aggregates or incomplete dispersion can be caused when the dry inorganic nanoparticles are directly added into an ultraviolet curing resin system to affect the final performance of a coating film is avoided.
The weight percentage of the tetraethyl orthosilicate in the lower alcohol solution is 10-55 wt%.
The lower alcohol is selected from C1-C6 monohydric alcohol, and can be selected from methanol, ethanol, isopropanol and the like.
The modifying reagent is at least one of gamma-methacryloxypropyltrimethoxysilane (MPTMS) and 3-mercaptopropyltriethoxysilane, allyl double bonds are introduced through the gamma-methacryloxypropyltrimethoxysilane, sulfydryl is introduced through the 3-mercaptopropyltriethoxysilane, and the organic functional groups are introduced to effectively improve the compatibility of the silicon dioxide nanoparticles and a resin system. The dosage of the modifying reagent is 1-10 wt% of tetraethyl orthosilicate.
In the modified silicon dioxide dispersion liquid, the amount of the organic solvent miscible with water is 5-20 wt% of the weight of the modified silicon dioxide. The organic solvent miscible with water is tetrahydrofuran, acetone, 1-butanone and the like. The content of the organic solvent miscible with water in the hybrid epoxy acrylate UV coating is extremely low, the overall performance of the coating film is not influenced, and the organic solvent miscible with water can be removed by means of reduced pressure distillation and the like after the modified silicon dioxide dispersion liquid is uniformly mixed with the epoxy acrylate oligomer, the reactive diluent and the auxiliary agent.
The system needs to be kept uniform in the process of preparing the modified silicon dioxide by adopting a nano dispersion method, and the system can be ensured to be uniform by stirring, wherein the stirring speed is 50-1000 rpm, and preferably 100-500 rpm.
In the process of preparing the modified silicon dioxide by the nano-dispersion method, the reaction temperature is between room temperature (20 ℃) and 70 ℃, and preferably between 30 and 60 ℃.
More specifically, the modified silica is prepared by a nano-dispersion method, which comprises the following steps: tetraethyl orthosilicate and lower alcohol are stirred and mixed, alkali or acid catalyst is dropped into the mixture through a constant pressure funnel while stirring, and the mixture is hydrolyzed and condensed at room temperature to 70 ℃ and preferably 30 to 60 ℃ to obtain clear and transparent blue-emitting silica sol (the blue-emitting light is a result of scattering of small particles, which indicates that small-particle silica is generated); adding a modifying reagent into the silica sol, and carrying out heat preservation reaction to obtain modified silica with the particle size (measured by a laser light scattering method) of less than 100nm, preferably less than 50 nm; and (3) removing water and lower alcohol in the modified silica sol system by reduced pressure distillation or centrifugation until the water content is less than or equal to 3%, and dispersing in an organic solvent miscible with water to obtain the modified silica dispersion.
The dispersion of the silicon dioxide usually needs instruments such as a high-speed homogenizer, high-power ultrasound and the like, and the silicon dioxide can be dispersed to an ideal state by consuming more energy; in the dispersion process, a phenomenon of difficult dispersion often occurs. The inventor proposes an in-situ sol-gel method, and obtains modified silicon dioxide nano particles by in-situ self-preparation and in-situ modification in an ultraviolet light curing resin system through reasonably designing a dispersion system, so as to obtain the ultraviolet light curing nano hybrid epoxy acrylate resin.
The hybrid epoxy acrylate oligomer is prepared by adopting an in-situ sol-gel method: mixing epoxy acrylate oligomer, organic solvent and tetraethyl orthosilicate, carrying out hydrolysis and condensation reaction under the action of an alkali or acid catalyst, after reacting for at least 2 hours, adding siloxane with double bonds to modify the generated silica when the gel phenomenon caused by the condensation of the silica nanoparticles is observed, wherein the double bonds are on the surfaces of the silica nanoparticles, so that the compatibility of inorganic components and organic components is improved, and the bonding force between the organic components and the inorganic components after the coating is cured can also be improved through modification; and after the reaction is finished, carrying out reduced pressure distillation to remove the organic solvent and the water in the dispersion system, thus obtaining the uniform and transparent organic/inorganic hybrid epoxy acrylate oligomer.
The mass ratio of the epoxy acrylate oligomer to the organic solvent to the tetraethyl orthosilicate is (30-80): (10-60): (5-30); the using amount of the siloxane with the double bonds is 1-10 wt% of the weight of tetraethyl orthosilicate, and is preferably 1-5 wt%.
The organic solvent is at least one of alcohol, ketone and tetrahydrofuran; the alcohol is isopropanol, and the ketone is acetone or butanone. The epoxy acrylate oligomer is capable of being dissolved in a solvent of at least one of an alcohol, a ketone, or tetrahydrofuran, and the system is free of phase separation.
The siloxane with double bonds is gamma-methacryloxypropyltrimethoxysilane (MPTMS).
In the process of preparing the hybrid epoxy acrylate oligomer by adopting an in-situ sol-gel method, the reaction temperature is 30-80 ℃.
Preparing a hybrid epoxy acrylate oligomer by using an in-situ sol-gel method, which comprises the following steps: mixing epoxy acrylate oligomer, organic solvent and tetraethyl orthosilicate, and stirring to obtain uniform mixed solution; slowly dripping alkali or acid catalyst into the mixed solution; heating to 30-80 ℃, carrying out hydrolysis and condensation reaction, and adding siloxane with double bonds to modify the generated silicon dioxide after the reaction is carried out for at least 2 hours and the gel phenomenon is observed; and after the reaction is finished, carrying out reduced pressure distillation to remove more organic solvent and trace moisture in the dispersion system to obtain uniform and transparent organic/inorganic hybrid epoxy acrylate oligomer. Generally, the catalyst is added dropwise with stirring at a stirring speed of 300 to 1000 rpm.
The particle size of the modified silica in the hybrid epoxy acrylate oligomer is 100nm or less, preferably 50nm or less.
The amount of the alkali or acid catalyst (calculated as solute) is 1-20 wt% of tetraethyl orthosilicate, and preferably 1.0-5.0 wt%. The dripping speed of the catalyst is controlled to be 0.5-2 drops/second, and the catalyst is dripped within 10-80 min.
The alkali catalyst is at least one selected from ammonia water with the concentration of 10-25 wt%, urea solution with the concentration of 3-20 wt% and lysine solution with the concentration of 5-25 wt%; the acid catalyst is diluted hydrochloric acid with the concentration of 1N (namely 1 mol/L).
The photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide and the like.
The reactive diluent is selected from difunctional neopentyl glycol diacrylate (NPGDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA) and the like, polyfunctional acrylates such as trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), ditrimethylolpropane tetraacrylate (Di-TMPTA), dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate (DPHA) and the like.
The auxiliary agent comprises common auxiliary agents for forming a film by the coating, such as a leveling agent, a defoaming agent and the like. The leveling agent comprises, but is not limited to BYK-3455, BYK-3550 and the like; the defoaming agent comprises, but is not limited to BYK052N, BYK-053N, BYK-061, BYK-065, BYK-1719, BYK-A535, BYK-088 and the like.
The resin in the hybrid epoxy acrylate UV coating plays a role in binding agent and providing adhesion, and the inorganic component, namely the silicon dioxide nano particles play a role in improving hardness and wear resistance. According to the invention, the inorganic component matched with the photocuring epoxy acrylate resin system on a nanometer scale is provided, so that the whole system is stable in composition, and the comprehensive performance of the finally prepared coating film is improved.
It is another object of the present invention to provide the use of the hybrid epoxy acrylate UV coating for preparing wear resistant coatings in the field of furniture, 3C products (computers, communications, consumer electronics) or other wear resistant fields, preferably for preparing coatings on wood, metal or plastic substrates.
The metal is a galvanized plate, a tinplate, an aluminum plate, a magnesium aluminum alloy and a stainless steel base material.
Preparing a coating film: uniformly mixing all the components through mechanical stirring and defoaming, and coating a wet film on the surface of a base material by using blade coating, roll coating, spraying and other modes; and pre-baking the film in a baking oven at 50-60 ℃ for 5-20 minutes, and curing the film by using an ultraviolet curing machine with a crawler belt to obtain a transparent organic/inorganic hybrid film.
The ultraviolet curing time is 1-60 seconds;
the thickness of the coating film is 1 to 100 μm.
Compared with the prior art, the invention has the following advantages:
1. the invention improves the compatibility of the silicon dioxide particles and the light-cured resin system by preparing transparent silicon dioxide nano particles and modifying the transparent silicon dioxide nano particles to match with the ultraviolet light-cured resin system;
2. the hybrid epoxy acrylate UV coating has low viscosity and low inorganic component addition amount, and the prepared coating has excellent hardness and wear resistance, the hardness and wear resistance of the coating are greatly improved, and the coating has great value in the fields of furniture such as floors, 3C products and other wear-resistant fields.
Detailed Description
The following examples illustrate the invention in further detail.
Example 1
In the embodiment, modified silica nanoparticles are prepared by a nano-dispersion method and are dispersed into an epoxy acrylate system in the form of a dispersion liquid to obtain a hybrid epoxy acrylate UV coating, wherein the hybrid epoxy acrylate UV coating comprises the following components in percentage by weight:
wherein the sum of the epoxy acrylate oligomer, the modified silica particles and the reactive diluent is 100 percent, and the dosage of the photoinitiator and the auxiliary agent is based on the total amount of the epoxy acrylate oligomer, the modified silica particles and the reactive diluent.
The epoxy acrylate oligomer is aliphatic epoxy tetrapropylene ester, the structure is shown as the following formula, and the molecular formula is C43H64O20And the molecular weight is 900.
The epoxy acrylate oligomer of this example was prepared by the following method:
in the first step, in an 8L reaction kettle1000 g succinic anhydride (CAS NO.108-30-5, molecular formula: C) is added4H4O3Molecular weight 100.07), 10 g benzyltriethylammonium chloride, 5 g tetramethylammonium chloride, 1.5 g p-hydroxyanisole, 3457 g trimethylolpropane diacrylate (molecular formula: c12H18O5Molecular weight 242, diester content 70%), starting stirring, heating to 70 ℃, preserving heat for 1 hour, heating to 80 ℃, preserving heat for 1 hour, heating to 100 ℃, preserving heat for 3 hours, reacting until the acid value is constant, and then cooling to below 50 ℃ to obtain 4473.5 g of 2-functionality acrylate intermediate containing 1 carboxyl. The second step reaction is directly carried out without separation and purification.
In a second step, 1075 g of neopentyl glycol diglycidyl ether (CAS:17557-23-2, molecular formula: C) were subsequently charged into an 8L reactor11H20O4Molecular weight: 216.27), 8g of triphenylphosphine and 1 g of hydroquinone, heating to 70 ℃, preserving heat for 1 hour, heating to 80 ℃, preserving heat for 1 hour, heating to 90 ℃, preserving heat for 1 hour, heating to 100 ℃, preserving heat for 1 hour, heating to 110 ℃, preserving heat for 5 hours, reacting until the acid value is constant, cooling to below 50 ℃, discharging to obtain a crude product, and filtering through a 200-mesh filter screen (gauze) to obtain 5235 g of clear transparent viscous liquid 4-functionality aliphatic epoxy acrylate.
The active diluent is TPGDA.
The photoinitiator is 1173.
The auxiliary agent comprises a flatting agent BYK-3455 and a defoaming agent BYK-1719 which are respectively 0.8 wt% and 0.7 wt%.
The modified silicon dioxide is added in the form of modified silicon dioxide dispersion liquid, and the preparation method of the modified silicon dioxide comprises the following steps: dispersing 18g of tetraethyl orthosilicate in 30g of ethanol, and magnetically stirring to form a uniform solution; the solution is placed in a three-neck flask, heated to 60 ℃, and is dropwise added with 12mL of 1N dilute hydrochloric acid through a constant pressure funnel while stirring, and the solution is completely added within 1 hour. After the dropwise addition, reacting for 5 hours, dropwise adding an ethanol solution of gamma-methacryloxypropyltrimethoxysilane (prepared by dissolving 0.6g of gamma-methacryloxypropyltrimethoxysilane in 12mL of ethanol) into the reaction system, completing the dropwise addition within 1 hour, and keeping the temperature of 60 ℃ for reacting for 3 hours. After the reaction is finished, removing the organic solvent and water in a reduced pressure distillation or centrifugal mode to obtain the modified silica dispersoid with milky blue light (the water content is less than or equal to 3 percent, the particle size of the modified silica particles is about 30nm through dynamic light scattering representation), and mixing the modified silica particles and tetrahydrofuran according to the weight ratio of 100:5 to obtain uniform modified silica dispersion liquid.
And (3) mixing the modified silicon dioxide dispersion liquid (based on the mass of the modified silicon dioxide) with the epoxy acrylate oligomer, TPGDA, the flatting agent BYK-3455 and the defoaming agent BYK-1719, and adding a photoinitiator 1173 before ultraviolet light initiation to obtain the hybrid epoxy acrylate UV coating.
Example 2
On the basis of the hybrid epoxy acrylate UV coating of example 1, the content of modified silica was increased to 20% by weight. The formula is as follows:
the epoxy acrylate oligomer, the modified silica, the reactive diluent, the photoinitiator and the auxiliary agent are the same as those in example 1.
Example 3
Dispersing modified silica nanoparticles into epoxy acrylate resin and reactive diluent systems involves separation and redispersion of the nanoparticles, increases operating costs and the risk of particle aggregation during dispersion, and re-dispersion of the system after destabilization presents a significant challenge.
In the embodiment, an in-situ sol-gel method is adopted to obtain a uniformly dispersed hybrid epoxy acrylate oligomer, the hybrid epoxy acrylate oligomer is mixed with an active diluent and an auxiliary agent, and a photoinitiator is added before ultraviolet light initiation to obtain the hybrid epoxy acrylate UV coating. The hybrid epoxy acrylate UV coating comprises the following components in percentage by weight:
the reactive diluent, photoinitiator and auxiliary agent were the same as in example 1.
The preparation method of the hybrid epoxy acrylate oligomer comprises the following steps:
30g of tetraethyl orthosilicate was dispersed in 54g of an isopropanol/tetrahydrofuran mixed solution (the volume ratio of isopropanol to tetrahydrofuran was 1:1), and then mixed with 60g of an epoxy acrylate resin oligomer (same as in example 1), and the epoxy acrylate resin oligomer was dissolved in the isopropanol/tetrahydrofuran mixed solution to obtain a homogeneous mixed system. And (3) placing the mixed system in a reflux device provided with a condenser tube, dropwise adding 12mL of 1N dilute hydrochloric acid through a constant-pressure funnel while stirring, and finishing dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃, the reaction is carried out for 5 hours, at the moment, the gel phenomenon is observed, then an ethanol solution of gamma-methacryloxypropyltrimethoxysilane (prepared by dissolving 0.6g of gamma-methacryloxypropyltrimethoxysilane in 12mL of ethanol) is dripped into the reaction system, the dripping is finished within 1 hour, and the heat preservation reaction at 60 ℃ is continued for 3 hours. After the reaction is finished, removing water and organic solvent in the system through reduced pressure distillation to obtain the organic-inorganic nano hybrid epoxy acrylate oligomer, wherein the hybrid epoxy acrylate oligomer contains modified silica nanoparticles with the particle size of about 30 nm.
Comparative example 1
On the basis of example 1, the epoxy acrylate UV coating formulation was adjusted without the addition of modified silica.
The epoxy acrylate UV coating consists of an epoxy acrylate oligomer, a reactive diluent, a photoinitiator and an auxiliary agent: the weight ratio of the epoxy acrylate oligomer to the reactive diluent is 55:45, and the dosage of the photoinitiator and the auxiliary agent is respectively 2 wt% and 1.5 wt% of the total amount of the epoxy acrylate oligomer and the reactive diluent.
The epoxy acrylate oligomer, reactive diluent, photoinitiator, and coagent were the same as in example 1.
The hybrid epoxy acrylate UV coatings of examples 1-3 and the epoxy acrylate UV coating of comparative example 1 were applied to a standard tinplate substrate (wet film thickness 30 μm) by means of a BYK frame coater. Prebaking in a 60 ℃ oven for 15 minutes, and curing for 10 seconds on a crawler-type ultraviolet curing machine to obtain a cured transparent coating. The coating films were tested for adhesion, hardness and abrasion resistance and the results are shown in table 1.
TABLE 1 coating film Properties
Note: the adhesive force is tested by a grid cutting method (GB9286-98), the hardness is measured by a pencil hardness method (GB/T6739-.
As can be seen from table 1, compared with the epoxy acrylate UV coating without the inorganic component, the hardness and wear resistance of the coating prepared by the hybrid epoxy acrylate UV coating are greatly improved, and especially, compared with the method of directly adding and blending, the method of preparing and modifying the silica nanoparticles by the in-situ sol-gel method has more excellent hardness and wear resistance of the coating prepared by the hybrid epoxy acrylate UV coating.
As mentioned above, the present invention can be well implemented, and the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; it is intended that all equivalent variations and modifications of the present invention be covered by the scope of the claims.
Claims (10)
1. The high-surface-hardness hybrid epoxy acrylate UV coating is characterized by comprising 35-75 wt%, 5-20 wt% and 10-45 wt% of epoxy acrylate oligomer, 5-20 wt% and reactive diluent respectively, wherein the sum of the epoxy acrylate oligomer, the modified silicon dioxide and the reactive diluent is 100%; the photoinitiator and the auxiliary agent are respectively 2-4 wt% and 1-2 wt% of the total amount of the epoxy acrylate oligomer, the modified silicon dioxide and the reactive diluent; the modified silicon dioxide is prepared by a nano-dispersion method: mixing tetraethyl orthosilicate and lower alcohol, hydrolyzing and condensing under the action of an alkali or acid catalyst to obtain silica sol, adding a modifying reagent into the silica sol to modify the silica, removing water and lower alcohol in a modified silica sol system by reduced pressure distillation or centrifugation after the reaction is finished until the water content is less than or equal to 3%, and dispersing in an organic solvent mixed with water to obtain a modified silica dispersion liquid; the modifying reagent is at least one of gamma-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane; in the modified silicon dioxide dispersion liquid, the amount of the organic solvent miscible with water is 5-20 wt% of the modified silicon dioxide;
or comprises a hybrid epoxy acrylate oligomer, a reactive diluent, a photoinitiator and an auxiliary agent, wherein the weight percentages of the hybrid epoxy acrylate oligomer and the reactive diluent are respectively 55-90 wt% and 10-45 wt%, and the sum of the hybrid epoxy acrylate oligomer and the reactive diluent is 100%; the photoinitiator and the auxiliary agent respectively account for 2-4 wt% and 1-2 wt% of the total amount of the hybrid epoxy acrylate oligomer and the reactive diluent; the hybrid epoxy acrylate oligomer is prepared by adopting an in-situ sol-gel method: mixing epoxy acrylate oligomer, organic solvent and tetraethyl orthosilicate, carrying out hydrolysis and condensation reaction under the action of an alkali or acid catalyst, adding siloxane with double bonds to modify generated silicon dioxide after the reaction is carried out for at least 2 hours until the gel phenomenon is observed, and after the reaction is finished, carrying out reduced pressure distillation to remove the organic solvent and water in a dispersion system to obtain organic/inorganic hybrid epoxy acrylate oligomer; the mass ratio of the epoxy acrylate oligomer to the organic solvent to the tetraethyl orthosilicate is 30-80: 10-60: 5-30; the using amount of the siloxane with the double bonds is 1-10 wt% of tetraethyl orthosilicate.
2. The hybrid epoxy acrylate UV coating according to claim 1, wherein the molecular weight of the epoxy acrylate oligomer is 200-3000.
3. The hybrid epoxy acrylate UV coating according to claim 1, characterized in that the weight fraction of tetraethyl orthosilicate in the lower alcohol solution thereof is 10-55 wt%; the lower alcohol is selected from C1-C6 monohydric alcohol;
the dosage of the modifying reagent is 1-10 wt% of tetraethyl orthosilicate.
4. The hybrid epoxy acrylate UV coating according to claim 1, characterized in that the water-miscible organic solvent is tetrahydrofuran, acetone, 1-butanone.
5. The hybrid epoxy acrylate UV coating according to claim 1, characterized in that the amount of the double-bonded siloxane is 1-5 wt% of tetraethyl orthosilicate;
the organic solvent is at least one of alcohol, ketone and tetrahydrofuran; the alcohol is isopropanol, and the ketone is butanone;
the siloxane with double bonds is gamma-methacryloxypropyltrimethoxysilane.
6. The hybrid epoxy acrylate UV coating as claimed in claim 1, wherein the amount of the alkali or acid catalyst is 1-20 wt% of tetraethyl orthosilicate;
the alkali catalyst is at least one selected from ammonia water with the concentration of 10-25 wt%, urea solution with the concentration of 3-20 wt% and lysine solution with the concentration of 5-25 wt%; the acid catalyst is diluted hydrochloric acid with the concentration of 1N.
7. The hybrid epoxy acrylate UV coating according to claim 1, characterized in that the amount of the alkali or acid catalyst is 1.0-5.0 wt% of tetraethyl orthosilicate.
8. The hybrid epoxy acrylate UV coating according to claim 1, characterized in that the photoinitiator is selected from the group consisting of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide;
the active diluent is selected from neopentyl glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate and dipentaerythritol penta/hexaacrylate;
the auxiliary agent is a leveling agent and a defoaming agent; the leveling agent is selected from BYK-3455 and BYK-3550; the defoaming agent is selected from BYK052N, BYK-053N, BYK-061, BYK-065, BYK-1719, BYK-A535 and BYK-088.
9. Use of the hybrid epoxy acrylate UV coating according to claim 1 for the preparation of abrasion resistant coatings in the field of furniture, 3C products or other abrasion resistant fields.
10. Use of the hybrid epoxy acrylate UV coating of claim 1 to prepare a coating film on a wood, metal or plastic substrate.
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