CN112175507A - Hybrid polyurethane acrylate UV (ultraviolet) coating with high surface hardness - Google Patents
Hybrid polyurethane acrylate UV (ultraviolet) coating with high surface hardness Download PDFInfo
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- CN112175507A CN112175507A CN202010920912.6A CN202010920912A CN112175507A CN 112175507 A CN112175507 A CN 112175507A CN 202010920912 A CN202010920912 A CN 202010920912A CN 112175507 A CN112175507 A CN 112175507A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- 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 hybrid polyurethane acrylate UV coating with high surface hardness, which comprises the following components: urethane acrylate oligomer, modified silicon dioxide, reactive diluent, photoinitiator, auxiliary agent or hybrid urethane acrylate oligomer, reactive diluent, photoinitiator and auxiliary agent; the hybrid polyurethane 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 polyurethane 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 polyurethane acrylate UV coating has lower viscosity and lower 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 and the like and other wear-resistant fields.
Description
Technical Field
The invention belongs to the field of photocuring resin and paint, relates to a hybrid polyurethane acrylate UV paint with high surface hardness, and particularly relates to a hybrid polyurethane acrylate resin UV paint with high surface hardness, which is prepared by using modified silicon dioxide nanoparticles and photocuring polyurethane 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 flooring, conventional urethane acrylates have low hardness and abrasion resistance, so that gloss and texture of the floor surface are quickly lost, and the service life of the wood flooring is reduced.
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 photocuring system, and the crosslinking density of the photocuring resin is increased, so that 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. Generally, the hardness and wear resistance of the coating can be improved by directly adding the inorganic filler into the light-cured resin system, but the dispersibility and sedimentation of the inorganic filler in the light-cured resin system are difficult to solve. This causes the following three problems. Firstly, the filler system generally has a larger particle size and a higher density than the light-cured resin, so that the inorganic particles are rapidly settled in the 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, in general, the addition of large amounts of inorganic components to a photocurable resin system to obtain a photocurable coating with better hardness and abrasion resistance usually results in increased viscosity of the system and phase separation of the inorganic filler in the system, resulting in coating defects and reduced adhesion of the coating. 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 fillers in a light-cured resin system, and provides an ultraviolet-curable nano hybrid polyurethane acrylate system, which has lower viscosity and lower inorganic component addition amount, and after full light curing, a coating has extremely high surface hardness and wear resistance.
The purpose of the invention is realized by the following technical scheme:
a hybrid polyurethane acrylate UV coating with high surface hardness comprises the following components in percentage by weight:
the sum of the urethane acrylate oligomer, the modified silicon dioxide and the reactive diluent is 100 percent, and the photoinitiator and the auxiliary agent are added based on the total amount of the urethane acrylate oligomer, the modified silicon dioxide and the reactive diluent.
Or
The sum of the hybrid polyurethane acrylate oligomer and the reactive diluent is 100 percent, and the photoinitiator and the auxiliary agent are added based on the total amount of the hybrid polyurethane acrylate oligomer and the reactive diluent.
The molecular weight of the urethane acrylate oligomer is 500-20000.
Specifically, the urethane acrylate oligomer is prepared by using 2, 2-dimethylolpropionic acid and anhydrous citric acid as raw materials, reacting with ethylene oxide or propylene oxide under the action of a catalyst to prepare polyether ester, and reacting the polyether ester with diisocyanate and hydroxyethyl acrylate or hydroxypropyl acrylate or trimethylolpropane diacrylate or pentaerythritol triacrylate or ditrimethylolpropane triacrylate or pentaerythritol tri (meth) acrylate or ditrimethylolpropane tri (meth) acrylate; or the polyurethane acrylate oligomer is prepared by taking ditrimethylolpropane, anhydrous citric acid, glycerol, pentaerythritol, trimethylolethane or trimethylolpropane as raw materials, reacting with ethylene oxide or propylene oxide under the action of a catalyst to prepare polyether, and reacting the polyether with isocyanate ethyl acrylate; or a polyurethane acrylate oligomer prepared by the reaction of polycaprolactone diol or polycaprolactone tetraol and isocyanate ethyl acrylate.
Reference may be made to CN103274967A, CN103242508A, CN103224603A, CN103242507A, CN103214649A, CN103193953A, CN105884655A, CN105820063A, CN105801829A, CN105859588A, CN105859585A, CN105859587A, CN105859584A for the preparation of urethane acrylate oligomers. The urethane 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, and is added in a modified silicon dioxide dispersion liquid; the hybrid polyurethane 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 polyurethane 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 resin system capable of being cured by ultraviolet light. Wherein, the in-situ hydrolysis polymerization to generate the modified silicon dioxide by adopting an 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. The modified silicon dioxide dispersion liquid is prepared by a nano-dispersion method, has good compatibility and stability with urethane acrylate oligomer, solves the problem that dry inorganic nanoparticles are difficult to disperse, and avoids the phenomenon that aggregates or incomplete dispersion cannot occur when the dry inorganic nanoparticles are directly added into an ultraviolet curing resin system to influence the final performance of a coating film.
The weight percentage of the tetraethyl orthosilicate in the lower alcohol solution is 10-50 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 modified silicon dioxide. The content of the organic solvent miscible with water in the hybrid polyurethane 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 polyurethane acrylate oligomer, the reactive diluent and the auxiliary agent.
The organic solvent miscible with water is tetrahydrofuran, acetone, 1-butanone and the like.
In the process of preparing the modified silicon dioxide by the nano-dispersion method, the system is kept uniform, and the system can be ensured to be uniform by stirring at a speed of 50-1000 rpm, 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: 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 reasonably designs a dispersion system, provides 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 curing resin system to obtain the ultraviolet curing nano hybrid resin.
The hybrid polyurethane acrylate oligomer is prepared by adopting an in-situ sol-gel method: mixing urethane 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 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 an inorganic component and an organic component is improved, and the bonding force between the organic component and the inorganic component 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 polyurethane acrylate oligomer.
The particle size of the modified silica in the hybrid urethane acrylate oligomer is 100nm or less, preferably 50nm or less.
The mass ratio of the polyurethane acrylate oligomer to the organic solvent to the tetraethyl orthosilicate is (30-80): (10-40): (5-30); the using amount of the siloxane with the double bonds is 1-10 wt% of tetraethyl orthosilicate, and preferably 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 acetone or butanone. Because of the presence of alcohol/ketone/tetrahydrofuran, no phase separation occurs in the system.
The siloxane with double bonds is gamma-methacryloxypropyltrimethoxysilane (MPTMS).
In the process of preparing the hybrid polyurethane acrylate oligomer by adopting an in-situ sol-gel method, the reaction temperature is 30-80 ℃.
More specifically, the hybrid urethane acrylate oligomer is prepared by adopting an in-situ sol-gel method: mixing polyurethane 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; and after the reaction is finished, carrying out reduced pressure distillation to remove more organic solvent and trace moisture in the dispersion system, thereby obtaining the uniform and transparent organic/inorganic hybrid urethane acrylate oligomer. Generally, the catalyst is added dropwise with stirring at a stirring speed of 300 to 1000 rpm.
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 the group consisting of self-difunctional glycol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), etc., polyfunctional acrylates such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc.
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 polyurethane acrylate UV coating plays a role in binding agent and providing adhesion, and the inorganic component plays a role in improving hardness and wear resistance. The invention provides the inorganic component matched with the light-cured resin system on the nano scale, so that the whole system is stable in composition, and the comprehensive performance of the final coating film is improved.
The invention also aims to provide application of the hybrid polyurethane acrylate UV coating with high surface hardness in preparing wear-resistant coating films in the furniture field and other wear-resistant fields, preferably application in preparing coating films on wood, steel or plastic substrates and the like.
The steel is a galvanized plate or a tinplate base plate.
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. compared with a method of directly adding and blending, the method has better uniformity and better dispersibility, and the prepared coating has more excellent hardness and wear resistance;
3. the hybrid polyurethane 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 and the like 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 dispersed in a polyurethane acrylate system to obtain a hybrid polyurethane acrylate UV coating, wherein the hybrid polyurethane acrylate UV coating comprises the following components in percentage by weight:
wherein the sum of the urethane 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 urethane acrylate oligomer, the modified silica particles and the reactive diluent.
The molecular weight of the polyurethane acrylate oligomer is 1282, and the polyurethane acrylate oligomer is prepared by the following steps:
500 g of polycaprolactone diol (Tetto CAPA2100, molecular weight 1000), 141 g (1mol) of isocyanate ethyl acrylate, 0.1 g of dibutyltin dilaurate serving as a catalyst, 0.7 g of p-hydroxyanisole serving as a polymerization inhibitor are put into a 1000mL four-neck flask, the temperature is slowly increased to 80-85 ℃ within 0.5-4 hours, the temperature is kept and the stirring reaction is carried out for 3-5 hours, and the discharging is carried out, so that the 2-functionality polycaprolactone polyurethane acrylate with the structure shown in the following formula is obtained.
R is:
namely neopentyl glycol is used as a dihydric alcohol initiator in polycaprolactone diol;
a+b＝(1000-104)/114＝7.8596。
the active diluent is HDDA.
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 15g of tetraethyl orthosilicate in 25g 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 10mL 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 0.5g of gamma-methacryloxypropyltrimethoxysilane in 10mL 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 centrifugation mode to obtain a modified silica dispersoid (the water content is less than or equal to 3 percent, and the particle size of the modified silica particles is about 30nm through dynamic light scattering representation), and mixing the modified silica particles with 5wt percent (compared with the mass of the modified silica particles) of tetrahydrofuran to obtain uniform modified silica dispersion liquid.
And (2) mixing the modified silicon dioxide dispersion liquid (based on the mass of the modified silicon dioxide) with the polyurethane acrylate oligomer, the reactive diluent and the auxiliary agent, and adding the photoinitiator before ultraviolet light initiation to obtain the hybrid polyurethane acrylate UV coating.
Example 2
On the basis of the hybrid polyurethane acrylate UV coating of example 1, the content of inorganic component modified silica was increased to 20 wt.%. The formula is as follows:
the urethane 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 resin and reactive diluent systems involves separation and redispersion of the nanoparticles, increasing operating costs and the risk of particle aggregation upon dispersion. In general, re-dispersion of colloidal systems after destabilization presents a significant challenge.
In this embodiment, an in-situ sol-gel method is adopted to obtain a uniformly dispersed hybrid urethane acrylate oligomer, the hybrid urethane acrylate oligomer is then mixed with a reactive diluent and an auxiliary agent, and a photoinitiator is added before ultraviolet light initiation, so as to obtain the hybrid urethane acrylate UV coating. The hybrid polyurethane 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 polyurethane acrylate oligomer comprises the following steps:
25g of tetraethyl orthosilicate was dispersed in 45g of an isopropanol/tetrahydrofuran mixed solution in a volume ratio of 1:1 and mixed with 50g of urethane acrylate resin oligomer (same as in example 1), and since both isopropanol and tetrahydrofuran can dissolve the oligomer, a homogeneous mixed system can be obtained. And (3) placing the mixed system in a reflux device provided with a condenser pipe, dropwise adding 10mL 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 0.5g of gamma-methacryloxypropyltrimethoxysilane in 10mL 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 polyurethane acrylate oligomer, wherein the hybrid polyurethane acrylate oligomer contains modified silica nanoparticles with the particle size of about 30 nm.
Comparative example 1
Based on example 1, the urethane acrylate UV coating formulation was adjusted without the addition of modified silica.
The polyurethane acrylate UV coating consists of a polyurethane acrylate oligomer, a reactive diluent, a photoinitiator and an auxiliary agent: the weight ratio of the urethane acrylate oligomer to the reactive diluent is 6:4, and the dosage of the photoinitiator and the auxiliary agent is respectively 2 wt% and 1.5 wt% of the total amount of the urethane acrylate oligomer and the reactive diluent.
The urethane acrylate oligomer, the reactive diluent, the photoinitiator and the auxiliary agent are the same as those in example 1.
The hybrid urethane acrylate UV coatings of examples 1-3 and the urethane 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 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 polyurethane acrylate UV coating is characterized by comprising the following components in percentage by weight:
or
The hybrid polyurethane 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 polyurethane acrylate oligomer system.
2. The hybrid polyurethane acrylate UV coating according to claim 1, wherein the molecular weight of the polyurethane acrylate oligomer is 500-20000.
3. The hybrid polyurethane 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 polyurethane acrylate UV coating according to claim 3, characterized in that the weight fraction of tetraethyl orthosilicate in the lower alcohol solution thereof is 10-50 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 polyurethane 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 urethane acrylate UV coating according to claim 1, characterized in that the hybrid urethane acrylate oligomer is prepared by an in-situ sol-gel method: mixing the polyurethane acrylate oligomer, an organic solvent and tetraethyl orthosilicate, carrying out hydrolysis and condensation reaction under the action of an alkali or acid catalyst, after at least 2 hours of reaction, adding siloxane with double bonds to modify the generated silicon dioxide when 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 the organic/inorganic hybrid polyurethane acrylate oligomer.
7. The hybrid polyurethane acrylate UV coating according to claim 6, wherein the mass ratio of the polyurethane acrylate oligomer to the organic solvent to the tetraethyl orthosilicate is 30-80: 10-40: 5-30; the using amount of the siloxane with the double bonds is 1-10 wt% of tetraethyl orthosilicate, and preferably 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.
8. The hybrid polyurethane acrylate UV coating according to 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 polyurethane 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 glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol 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.
10. Use of the hybrid polyurethane acrylate UV coating according to claim 1 for the production of wear resistant coatings in the field of furniture or wear resistance, preferably for the production of coatings on wood, steel or plastic substrates.
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| CN113416280A (en) * | 2021-05-28 | 2021-09-21 | 华南理工大学 | Ultraviolet-cured silicon-containing organic-inorganic hybrid resin and preparation method thereof |
| CN114773982A (en) * | 2021-12-13 | 2022-07-22 | 华东理工大学 | UV-cured polyurethane acrylate coating and preparation method thereof |
| CN115595039A (en) * | 2022-10-18 | 2023-01-13 | 佛山市海而斯涂料有限公司（Cn） | UV (ultraviolet) hardening primer and preparation method thereof |
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| CN115595039A (en) * | 2022-10-18 | 2023-01-13 | 佛山市海而斯涂料有限公司（Cn） | UV (ultraviolet) hardening primer and preparation method thereof |
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| CN115785798B (en) * | 2022-12-30 | 2024-05-24 | 苏州赛伍应用技术股份有限公司 | Anti-fouling wear-resistant coating, coating stock solution and preparation method thereof |
| CN116063647A (en) * | 2023-02-01 | 2023-05-05 | 惠州市惠阳聚晟化工涂料有限公司 | Hardening liquid for mobile phone rear shell and application thereof |
| CN116063647B (en) * | 2023-02-01 | 2024-01-05 | 惠州市惠阳聚晟化工涂料有限公司 | Hardening liquid for mobile phone rear shell and application thereof |
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| CN116875180A (en) * | 2023-06-21 | 2023-10-13 | 广东希贵光固化材料有限公司 | Easy-to-clean paint applied to napped leather |
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