CN112175427A - Wear-resistant hybrid polyester acrylate UV (ultraviolet) coating - Google Patents
Wear-resistant hybrid polyester acrylate UV (ultraviolet) coating Download PDFInfo
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- CN112175427A CN112175427A CN202010939465.9A CN202010939465A CN112175427A CN 112175427 A CN112175427 A CN 112175427A CN 202010939465 A CN202010939465 A CN 202010939465A CN 112175427 A CN112175427 A CN 112175427A
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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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Abstract
The invention discloses a wear-resistant hybrid polyester acrylate UV coating, which comprises the following components: polyester acrylate oligomer, modified silicon dioxide, reactive diluent, photoinitiator, leveling agent and defoaming agent or hybrid polyester acrylate oligomer, reactive diluent, photoinitiator, leveling agent and defoaming agent; the hybrid polyester 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 a polyester 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 polyester 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 wear-resistant hybrid polyester acrylate UV paint, and particularly relates to wear-resistant hybrid polyester acrylate resin UV paint with high surface hardness, which is prepared by using modified silicon dioxide nanoparticles and photocuring polyester 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-cured acrylate groups and polyurethane, polyester 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 polyester 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 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, and the following three problems exist: firstly, the inorganic filler generally has a larger particle size and a density larger than that of the light-cured resin, so that the inorganic particles are rapidly settled in a resin system, and if the inorganic filler is directly added, the hardness and the wear resistance of the light-cured coating cannot be increased; secondly, theoretically, the sedimentation rate of the nano inorganic filler in a 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 to form aggregates, thereby causing the instability of the system; thirdly, a large amount of inorganic components are generally required to be added into a photocuring resin system to obtain a photocuring coating with better hardness and wear resistance, which generally causes the problems of increased system viscosity, 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 provides an ultraviolet-curable nano hybrid polyester acrylate system aiming at the problems of dispersibility and sedimentation of inorganic filler in a photocuring resin system, the ultraviolet-curable nano hybrid polyester acrylate system has lower viscosity and lower inorganic component addition, a coating film is prepared by blade coating, roll coating, spraying and the like, and a coating with extremely high surface hardness and wear resistance can be obtained after photocuring.
The purpose of the invention is realized by the following technical scheme:
the wear-resistant hybrid polyester acrylate UV coating comprises 40-75 wt%, 5-20 wt% and 10-40 wt% of polyester acrylate oligomer, 5-20 wt% and 10-40 wt% of reactive diluent, the sum of the polyester acrylate oligomer, the modified silicon dioxide and the reactive diluent is 100%, and the photoinitiator, the leveling agent and the defoaming agent are respectively 2-6 wt%, 0.2-2 wt% and 0.2-2 wt% of the total amount of the polyester acrylate oligomer, the modified silicon dioxide and the reactive diluent;
or the composition comprises 60-90 wt% of hybrid polyester acrylate oligomer and 10-40 wt% of reactive diluent, the sum of the hybrid polyester acrylate oligomer and the reactive diluent is 100%, and the photoinitiator, the leveling agent and the defoaming agent are 2-6 wt%, 0.2-2 wt% and 0.2-2 wt% of the total amount of the hybrid polyester acrylate oligomer and the reactive diluent.
The molecular weight of the polyester acrylate oligomer is 100-5000.
The polyester acrylate oligomer is prepared by one-step or two-step reaction of at least one of dihydric alcohol or polyhydric alcohol, organic acid (anhydride) and acrylic acid or methacrylic acid under the action of a catalyst and a polymerization inhibitor. Wherein the dihydric alcohol includes but is not limited to ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, methyl propylene glycol, 1, 4-butanediol, 1, 6-hexanediol; the polyhydric alcohol includes but is not limited to trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol; the binary organic acid (anhydride) includes but is not limited to one or a combination of two or more of succinic acid (anhydride), adipic acid (anhydride), phthalic acid (anhydride), maleic acid (anhydride), trimellitic acid (anhydride) and pyromellitic acid (anhydride), and acrylic acid or methacrylic acid is selected from any one of acrylic acid and methacrylic acid; the catalyst is p-toluenesulfonic acid; the polymerization inhibitor is at least one of hydroquinone, BHT (2, 6-di-tert-butyl-4-methylphenol) and p-hydroxyanisole; the reaction solvent is one or the combination of more than two of benzene, toluene, normal hexane, cyclohexane, methylcyclohexane and heptane.
When the polyester acrylate oligomer is subjected to the two-step reaction, at least one of dihydric alcohol or polyhydric alcohol is reacted with organic acid (anhydride) under the action of a catalyst; then adding acrylic acid or methacrylic acid, and reacting under the action of a catalyst and a polymerization inhibitor.
The preparation of the polyester acrylate oligomer can be referred to the Properties and application handbook of photo-curing materials, Jinyangzhi, chemical industry Press, 2010.5, pp 99-100, the synthesis of polyester acrylate. The polyester acrylate oligomers of the present invention may also be prepared by other methods known to those skilled in the art.
The modified silicon dioxide is prepared by a silicon dioxide precursor by adopting a nano dispersion method; the hybrid polyester 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 a polyester 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 polyester 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 modified silicon dioxide is generated by in-situ hydrolytic polymerization by adopting an in-situ sol-gel 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. The modified silicon dioxide prepared by the nano-dispersion method is mixed with the polyester oxyacrylate oligomer in the form of dispersion liquid, the modified silicon dioxide dispersion liquid and the polyester oxyacrylate 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 occurs when the dry inorganic nanoparticles are directly added into an ultraviolet curing resin system to influence the final performance of a coating film is avoided.
The lower alcohol is selected from C1-C6 monohydric alcohol, and can be methanol, ethanol or isopropanol.
The weight percentage of the tetraethyl orthosilicate in the lower alcohol solution is 10-55 wt%.
The modifying agent is at least one of gamma-methacryloxypropyltrimethoxysilane (MPTMS) and 3-mercaptopropyltriethoxysilane. The dosage of the modifying reagent is 1-10 wt% of tetraethyl orthosilicate. The invention introduces allyl double bond through gamma-methacryloxypropyltrimethoxysilane and introduces sulfydryl through 3-mercaptopropyltriethoxysilane, and the groups can effectively improve the compatibility of the silicon dioxide nano particles and a resin system.
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 polyester 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 polyester 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.
Considering that the dispersion of the silicon dioxide usually needs instruments such as a high-speed homogenizer and high-power ultrasound, and more energy is consumed to disperse the silicon dioxide to an ideal state. Dispersing modified silica nanoparticles into polyester acrylate resin and reactive diluent systems, the dispersion process involving separation and re-dispersion 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. Therefore, the inventor further provides an in-situ sol-gel method by reasonably designing a dispersion system, and obtains modified silicon dioxide nano particles by in-situ self-preparation and in-situ modification in an ultraviolet light curing resin system to obtain the ultraviolet light curing nano hybrid polyester acrylate resin.
The hybrid polyester acrylate oligomer is prepared by adopting an in-situ sol-gel method: mixing polyester acrylate oligomer, an organic solvent and tetraethyl orthosilicate, carrying out hydrolysis and condensation reaction under the action of an alkali or acid catalyst, after the reaction is carried out for at least 2 hours, adding siloxane with double bonds to modify the generated silicon dioxide when the gel phenomenon caused by the condensation of the silicon dioxide nanoparticles is observed, wherein the double bonds are on the surfaces of the silicon dioxide nanoparticles, so that the compatibility of an inorganic component and an organic component is improved, and simultaneously, the bonding force between the organic component and the inorganic component in the coating after curing is 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 polyester acrylate oligomer.
The mass ratio of the polyester acrylate oligomer to the organic solvent to the tetraethyl orthosilicate is 1-10: 1-8: 1.
The organic solvent is at least one of alcohol, ketone and tetrahydrofuran; the alcohol is isopropanol, and the ketone is acetone or butanone. The polyester 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 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 siloxane with double bonds is gamma-methacryloxypropyltrimethoxysilane.
In the process of preparing the hybrid polyester acrylate oligomer by adopting an in-situ sol-gel method, the reaction temperature is 30-80 ℃.
Preparing a hybrid polyester acrylate oligomer by using an in-situ sol-gel method, comprising the following steps: mixing polyester acrylate oligomer, an organic solvent and tetraethyl orthosilicate, and stirring to obtain a 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; after the reaction is finished, carrying out reduced pressure distillation to remove more organic solvent and trace moisture in the dispersion system, thus obtaining the uniform and transparent organic/inorganic hybrid polyester 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 polyester 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. Compared with epoxy acrylate and polyurethane acrylate, the curing speed or the reaction activity of the polyester acrylate is relatively low, so that in order to ensure the curing speed, the photoinitiator is properly increased, and the photoinitiator is 4-6 wt% of the total amount of the polyester acrylate oligomer, the modified silicon dioxide and the reactive diluent or the total amount of the hybrid polyester acrylate oligomer and the reactive diluent.
The reactive diluent is selected from difunctional acrylates such as 1, 4-butanediol diacrylate (BDDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), etc., multifunctional acrylates such as trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), ditrimethylolpropane tetraacrylate (Di-TMPTA), dipentaerythritol hexaacrylate (DPHA), etc.
The leveling agent includes, 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 polyester acrylate oligomer in the hybrid polyester acrylate UV coating plays a role in binding agent and providing adhesion, and the inorganic component modified silicon dioxide nano particles play a role in improving hardness and wear resistance. The invention provides the modified silicon dioxide matched with the light-cured polyester acrylate resin system on the nanometer scale, 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 polyester 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 polyester 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 will further illustrate the technical solution of the present invention in detail.
Example 1
In the embodiment, modified silica nanoparticles are prepared by a nano-dispersion method and are dispersed into a polyester acrylate system in the form of dispersion liquid to obtain a hybrid polyester acrylate UV coating, wherein the hybrid polyester acrylate UV coating comprises the following components in percentage by weight:
wherein the sum of the polyester acrylate oligomer, the modified silicon dioxide particles and the reactive diluent is 100 percent, and the dosage of the photoinitiator, the leveling agent and the defoaming agent is based on the total amount of the polyester acrylate oligomer, the modified silicon dioxide particles and the reactive diluent.
The polyester acrylate oligomer described in this example is aliphatic polyester hexaacrylate, and has a structure shown in the following formula, and a molecular weight of 710.
The aliphatic polyester hexaacrylate is prepared by the following method:
1360 g of pentaerythritol, 730 g of adipic acid, 2300 g of acrylic acid, 120g of p-toluenesulfonic acid, 5 g of hydroquinone, 2g of BHT and 4500 g of toluene are put into a 15L reaction kettle, stirred, heated to 105-120 ℃, refluxed to produce water, reacted for 4-8 hours until no water flows out, cooled to below 50 ℃, subjected to post-treatment, decompressed distillation to recover toluene, and filtered by a 400-mesh filter screen to obtain the aliphatic polyester hexa-propylene ester.
The active diluent is BDDA.
The photoinitiator is 1173.
The leveling agent is a leveling agent BYK-3455.
The defoaming agent is a defoaming agent BYK-1719.
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 36g of tetraethyl orthosilicate in 60g of ethanol, and magnetically stirring to form a uniform solution; the solution is placed in a three-neck flask, heated to 60 ℃, and dropwise added with 24mL of 1N dilute hydrochloric acid through a constant pressure funnel while stirring, and the dropwise addition is completed within 1 hour. After the dropwise addition, reacting for 5 hours, dropwise adding an ethanol solution of gamma-methacryloxypropyltrimethoxysilane (prepared by dissolving 1.2g of gamma-methacryloxypropyltrimethoxysilane in 24mL 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 polyester acrylate oligomer, BDDA, the flatting agent BYK-3455 and the defoaming agent BYK-1719, and adding the photoinitiator 1173 before ultraviolet light initiation to obtain the hybrid polyester acrylate UV coating.
Example 2
On the basis of the hybrid polyester acrylate UV coating of example 1, the content of modified silica was increased to 20 wt%. The formula is as follows:
the polyester acrylate oligomer, the modified silica, the reactive diluent, the photoinitiator, the leveling agent and the defoaming agent of the present example were the same as those of example 1.
Example 3
In the embodiment, an in-situ sol-gel method is adopted to obtain a uniformly dispersed hybrid polyester acrylate oligomer, the hybrid polyester 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 polyester acrylate UV coating. The hybrid polyester acrylate UV coating comprises the following components in percentage by weight:
the reactive diluent, photoinitiator, leveling agent and defoamer were the same as in example 1.
The preparation method of the hybrid polyester acrylate oligomer comprises the following steps:
60g of tetraethyl orthosilicate was dispersed in 108g of an isopropanol/tetrahydrofuran mixed solution (the volume ratio of isopropanol to tetrahydrofuran was 1:1), and then mixed with 120g of a polyester acrylate resin oligomer (same as in example 1), and the polyester 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 24mL of 1N dilute hydrochloric acid through a constant-pressure funnel while stirring, and finishing dropping within 1 hour. After the dropwise addition, the temperature is raised to 60 ℃, the reaction is carried out for 5 hours, at the moment, the gelation phenomenon is observed, then an ethanol solution of gamma-methacryloxypropyltrimethoxysilane (prepared by dissolving 1.2g of gamma-methacryloxypropyltrimethoxysilane in 24mL of ethanol) is dropwise added into the reaction system, the dropwise addition is finished within 1 hour, and the reaction is carried out for 3 hours under the condition of keeping the temperature at 60 ℃. After the reaction is finished, removing water and organic solvent in the system through reduced pressure distillation to obtain the organic-inorganic nano hybrid polyester acrylate oligomer, wherein the hybrid polyester acrylate oligomer contains modified silica nanoparticles with the particle size of about 30 nm.
Example 4
The hybrid polyester acrylate UV coating comprises the following components in percentage by weight:
the hybrid polyester acrylate oligomer of the present example is an in-situ hydrolysis polymerization product obtained by using an in-situ sol-gel method to prepare tetraethyl orthosilicate in an aromatic polyester tetraacrylate system, and is prepared by replacing aliphatic polyester hexaacrylate with aromatic polyester tetraacrylate (molecular weight 614) having an equivalent structure as shown in the following formula, referring to the preparation method of the hybrid polyester acrylate oligomer of example 3.
The aromatic polyester tetrapropylene ester is prepared by the following method:
the first step is as follows: 1340 g of trimethylolpropane, 740 g of phthalic anhydride, 40 g of p-toluenesulfonic acid, 800 g of toluene and 800 g of cyclohexane are put into a 10L reaction kettle, stirred, heated to 90-110 ℃, refluxed to discharge water, reacted for 2-6 hours until no water flows out, and then cooled to below 50 ℃ to prepare the next reaction;
the second step is that: and (2) continuing adding 1550 g of acrylic acid, 50 g of p-toluenesulfonic acid, 4 g of hydroquinone, 1.5 g of BHT, 1000 g of toluene and 1000 g of cyclohexane into the reaction kettle, starting stirring, heating to 90-110 ℃, refluxing to obtain water, reacting for 5-10 hours until no water flows out, cooling to below 50 ℃, performing post-treatment, performing reduced pressure distillation to recover toluene and cyclohexane, and filtering by using a 400-mesh filter screen to obtain the aromatic polyester tetrapropylene maleate.
The active diluent is a mixture of DPGDA and Di-TMPTA according to the weight ratio of 2: 1.
The photoinitiator is 1173.
The leveling agent is a leveling agent BYK-3455.
The defoaming agent is a defoaming agent BYK-1719.
Example 5
The hybrid polyester acrylate UV coating comprises the following components in percentage by weight:
the hybrid polyester acrylate oligomer of this example is an in-situ hydrolysis polymerization product prepared by using an in-situ sol-gel method to prepare tetraethyl orthosilicate in an aliphatic polyester tripropionate system, and referring to the preparation method of the hybrid polyester acrylate oligomer of example 3, the aliphatic polyester hexaacrylate is replaced by an equivalent amount of aliphatic polyester tripropionate.
The aliphatic polyester tripropylene ester of the embodiment is prepared by the following method:
the first step is as follows: putting 670 g of trimethylolpropane, 1040 g of neopentyl glycol, 1460 g of adipic acid, 40 g of p-toluenesulfonic acid, 900 g of toluene and 900 g of cyclohexane into a 10L reaction kettle, starting stirring, heating to 90-110 ℃, refluxing to discharge water, reacting for 2-6 hours until no water flows out, and then cooling to below 50 ℃ to prepare the next reaction;
the second step is that: 1090 g of acrylic acid, 45 g of p-toluenesulfonic acid, 3.5 g of hydroquinone, 1.2g of BHT, 1000 g of toluene and 1000 g of cyclohexane are continuously added into the reaction kettle, stirring is started, the temperature is raised to 90-110 ℃, water is refluxed and discharged, the reaction lasts for 5-10 hours until no water flows out, then the reaction is cooled to below 50 ℃, after post-treatment, the toluene and the cyclohexane are recovered by reduced pressure distillation, and the mixture is filtered by a 400-mesh filter screen to obtain the aliphatic polyester tripropyl acrylate (with the molecular weight of 724), which is a mixture of polyester acrylates with the structure shown in the following formula.
The active diluent is a mixture of TPGDA and DPHA according to a weight ratio of 3: 1.
The photoinitiator is 1173.
The leveling agent is a leveling agent BYK-3455.
The defoaming agent is a defoaming agent BYK-1719.
Comparative example 1
On the basis of example 1, the polyester acrylate UV coating formulation was adjusted without the addition of modified silica.
The polyester acrylate UV coating consists of a polyester acrylate oligomer, a reactive diluent, a photoinitiator and an auxiliary agent: the weight ratio of the polyester acrylate oligomer to the reactive diluent is 60:30, and the dosage of the photoinitiator, the leveling agent and the defoaming agent is respectively 4 wt%, 0.8 wt% and 0.7 wt% of the total amount of the polyester acrylate oligomer and the reactive diluent.
The polyester acrylate oligomer, the reactive diluent, the photoinitiator, the leveling agent and the defoaming agent are the same as those in example 1.
The hybrid polyester acrylate UV coatings of examples 1-3 and the polyester 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 polyester acrylate UV coating without the inorganic component, the hardness and wear resistance of the coating prepared from the hybrid polyester acrylate UV coating are greatly improved, and especially, the silica nanoparticles are prepared and modified by the in-situ sol-gel method, so that the coating prepared by the method has more excellent hardness and wear resistance compared with the method of directly adding and blending in the form of modified silica dispersibility.
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 wear-resistant hybrid polyester acrylate UV coating is characterized by comprising 40-75 wt%, 5-20 wt% and 10-40 wt% of polyester acrylate oligomer, 5-20 wt% and 10-40 wt% of active diluent, wherein the sum of the polyester acrylate oligomer, the modified silicon dioxide and the active diluent is 100%, and the photoinitiator, the leveling agent and the defoaming agent are respectively 2-6 wt%, 0.2-2 wt% and 0.2-2 wt% of the total amount of the polyester acrylate oligomer, the modified silicon dioxide and the active diluent;
or the composition comprises a hybrid polyester acrylate oligomer, a reactive diluent, a photoinitiator, a leveling agent and an antifoaming agent, wherein the weight percentages of the hybrid polyester acrylate oligomer and the reactive diluent are respectively 60-90 wt% and 10-40 wt%, the sum of the hybrid polyester acrylate oligomer and the reactive diluent is 100%, and the photoinitiator, the leveling agent and the antifoaming agent are respectively 2-6 wt%, 0.2-2 wt% and 0.2-2 wt% of the total weight of the hybrid polyester acrylate oligomer and the reactive diluent; the hybrid polyester 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 a polyester acrylate oligomer system.
2. The hybrid polyester acrylate UV coating of claim 1, wherein the molecular weight of the polyester acrylate oligomer is 100 to 5000.
3. The hybrid polyester acrylate UV coating according to claim 1, characterized in that the modified silica is prepared by nano-dispersion method: tetraethyl orthosilicate and lower alcohol are mixed and dissolved, silicon dioxide sol is obtained through hydrolysis and condensation under the action of an alkali or acid catalyst, a modifying reagent is added into the silicon dioxide sol to modify the silicon dioxide, after the reaction is finished, water and the lower alcohol in a 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.
4. The hybrid polyester acrylate UV coating according to claim 3, characterized in that the weight fraction of tetraethyl orthosilicate in its lower alcohol solution is 10-55 wt%; the lower alcohol is selected from C1-C6 monohydric alcohol;
the modifying reagent is at least one of gamma-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane; the dosage of the modifying reagent is 1-10 wt% of tetraethyl orthosilicate.
5. The hybrid polyester acrylate UV coating of claim 3, wherein the amount of the water-miscible organic solvent in the modified silica dispersion is 5-20 wt% of the modified silica; the organic solvent miscible with water is tetrahydrofuran, acetone and 1-butanone.
6. The hybrid polyester acrylate UV coating of claim 1, characterized in that the hybrid polyester acrylate oligomer is prepared by an in-situ sol-gel process: mixing polyester 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 when the gel phenomenon is observed, and carrying out reduced pressure distillation after the reaction is finished to remove the organic solvent and moisture in a dispersion system to obtain the organic/inorganic hybrid polyester acrylate oligomer.
7. The hybrid polyester acrylate UV coating of claim 6, wherein the mass ratio of the polyester acrylate oligomer, the organic solvent and the tetraethyl orthosilicate is 1-10: 1-8: 1; the using amount of the siloxane with the double bonds is 1-10 wt% 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 butanone;
the siloxane with double bonds is gamma-methacryloxypropyltrimethoxysilane.
8. The hybrid polyester acrylate UV coating of claim 3 or 6, characterized in that the amount of the alkali or acid catalyst is 1-20 wt%, preferably 1.0-5.0 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.
9. The hybrid polyester 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 1, 4-butanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate and dipentaerythritol hexaacrylate;
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.
10. Use of the hybrid polyester acrylate UV coating according to claim 1 for the preparation of wear resistant coatings in the field of furniture, 3C products or other wear resistant applications, preferably for the preparation of coatings on wood, metal or plastic substrates.
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