阅读说明：本技术 一种紫外光固化涂料、制备方法及应用 (Ultraviolet curing coating, preparation method and application ) 是由 李小杰 顾正明 徐健 于 2021-10-15 设计创作，主要内容包括：本发明公开了一种紫外光固化涂料,属于化工涂料加工技术领域,按重量份数计,由如下组分制成：多官能度丙烯酸酯树脂50-70份,活性稀释剂20-50份,哑光粉10-15份,光引发剂1-5份,酯环环氧丙烯酸酯改性硅树脂5-20份,助剂1-2份。本发明利用的酯环环氧丙烯酸酯改性硅树脂可充当无机填料润湿分散剂的作用,配合有机硅树脂既有的优异性能,可有效提升涂层的硬度,使涂层具有较好的耐磨性能。同时,固化后的涂层具有较好的耐高温性能,能有效避免烟烫等高温条件对涂层的影响；而且涂层表面不易出现缺陷,与基材间的附着力好。本发明制备的紫外光固化涂料可广泛应用于PVC塑胶地板、电子器件、医用材料等领域。(The invention discloses an ultraviolet curing coating, which belongs to the technical field of chemical coating processing and is prepared from the following components in parts by weight: 50-70 parts of polyfunctional acrylate resin, 20-50 parts of reactive diluent, 10-15 parts of matte powder, 1-5 parts of photoinitiator, 5-20 parts of ester ring epoxy acrylate modified silicon resin and 1-2 parts of auxiliary agent. The ester epoxy acrylate modified silicone resin utilized by the invention can be used as an inorganic filler wetting dispersant, and the hardness of the coating can be effectively improved by matching the excellent performance of the silicone resin, so that the coating has better wear resistance. Meanwhile, the cured coating has better high-temperature resistance, and can effectively avoid the influence of high-temperature conditions such as smoke and scald on the coating; and the surface of the coating is not easy to have defects, and the adhesive force between the coating and the base material is good. The ultraviolet curing coating prepared by the invention can be widely applied to the fields of PVC plastic floors, electronic devices, medical materials and the like.)

1. The ultraviolet curing coating is characterized by being prepared from the following components in parts by weight:

wherein, the ester ring epoxy acrylate modified silicone resin is prepared by the following method:

s1: adding epoxy cyclohexyl siloxane, acrylic acid, triphenylphosphine, hydroquinone and methyl ethyl ketone into a reaction vessel, heating to 80-90 ℃, stirring for reaction for 5-7 hours, washing by n-hexane, and carrying out reduced pressure distillation to obtain ester epoxy acrylate siloxane containing acryloyloxy;

s2: mixing ester epoxy acrylate siloxane containing acryloyloxy, difunctional siloxane, trifunctional siloxane, isopropanol and hydroquinone, heating to 30-50 ℃, dropwise adding a mixture of hydrochloric acid and deionized water, completing dropwise adding within 0.5-1 hour, heating to 50-70 ℃, stirring for reacting for 2-8 hours, adding hexamethyldisiloxane, heating to 70-80 ℃, and stirring for reacting for 2-5 hours; and then standing for layering, washing an oil layer to be neutral, and finally distilling under reduced pressure to remove small molecular substances to obtain the ester epoxy acrylate modified silicone resin.

2. The UV-curable coating according to claim 1, wherein the ester ring epoxy acrylate modified silicone resin has the following structure:

wherein R is₁is-CH₃or-CH₂CH₃，R₂is-CH₃、-CH2CH₃or-CH₂CH₂CH₃；

The epoxycyclohexylsiloxane is one or more of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane;

the difunctional siloxane is one or more of dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane and diethyldimethoxysilane;

the tri-functionality siloxane is one or more of ethyl trimethoxy silane, methyl triethoxy silane, propyl triethoxy silane, ethyl triethoxy silane, propyl trimethoxy silane and methyl trimethoxy silane.

3. The UV-curable coating material according to claim 1, wherein the molar ratio of the acrylic acid to the epoxycyclohexylsiloxane in S1 is 1: 1 to 1.3; the dosage of the triphenylphosphine is 0.1 to 3 percent of the total mass of the epoxy cyclohexyl siloxane and the acrylic acid; the dosage of the hydroquinone is 0.1 to 5 percent of the total mass of the epoxy cyclohexyl siloxane and the acrylic acid.

4. The UV-curable coating according to claim 1, wherein the molar amount of the deionized water used in S2 is 3 to 9 times the total molar number of the acryloxy group-containing ester ring epoxy acrylate siloxane, difunctional siloxane and trifunctional siloxane; the dosage of the hydroquinone is 0.1 to 5 percent of the total mass of ester epoxy acrylate siloxane containing acryloxy, difunctional siloxane, trifunctional siloxane and hexamethyldisiloxane; the dosage of the hydrochloric acid is 0.1-5% of the mass of the deionized water; the molar ratio of the ester ring epoxy acrylate siloxane containing the acryloxy group to the difunctional siloxane to the trifunctional siloxane to the hexamethyldisiloxane is 1: 0.2-0.8: 1-5: 0.1-0.8.

5. The UV-curable coating according to claim 1, wherein the reactive diluent comprises one of isobornyl acrylate, hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate; the matte powder is Japanese east Cao E-1011; the photoinitiator is selected from one or more of 2, 4, 6-trimethyl benzoyl diethyl phosphonate, 2-phenyl-2, 2-dimethylamino-1- (4-morpholinyl phenyl) -1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, alpha-diethoxy acetophenone, 1-hydroxy-cyclohexyl benzophenone and 2, 4, 6-trimethyl benzoyl diphenyl phosphine oxide.

6. The UV-curable coating according to claim 1, wherein the multifunctional acrylate resin is selected from one or more of urethane acrylate resin, epoxy acrylate resin, and polyester acrylate resin.

7. The preparation method of the ultraviolet curing coating as claimed in any one of claims 1 to 6, characterized by comprising the following steps:

(1) stirring 20-50 parts of the reactive diluent, 0.5-1 part of the defoaming agent and 0.5-1 part of the leveling agent for 5-10 min at the rotating speed of 2000-2500 r/min by using a high-speed dispersion machine to uniformly disperse the components;

(2) adding 5-20 parts of the ester ring epoxy acrylate modified silicon resin and 10-15 parts of the matte powder in batches, and stirring for 20-30 min at the rotating speed of 3500-4000 r/min by using a high-speed dispersion machine after all the materials are added;

(3) adding 50-70 parts of multifunctional acrylate resin and 1-5 parts of photoinitiator, and uniformly stirring at the rotating speed of 2000-2500 r/min by using a high-speed dispersion machine to obtain the ultraviolet curing coating.

8. The application of the UV-curable coating of any one of claims 1 to 6 or the UV-curable coating obtained by the preparation method of claim 7, wherein the UV-curable coating is formed into a film on a substrate by a roller coating method, and the thickness of the film is controlled to be 8 to 10 g/m and is 600mJ/cm²Carrying out ultraviolet curing under the radiation condition to obtain the ultraviolet curing matte paint film.

Technical Field

The invention relates to the technical field of chemical coating processing, in particular to an ultraviolet curing coating, a preparation method and application thereof.

Background

Ultraviolet (UV) curing coating is a novel environment-friendly coating and is widely applied to the fields of PVC plastic floors, electronic devices, medical materials and the like. Compared with the traditional thermal curing, the UV light curing technology has the characteristics of high efficiency, rapidness, environmental protection, energy conservation and wide adaptability of '5E'. However, the existing ultraviolet curing coating is generally insufficient in wear resistance and high temperature resistance, and cannot meet the requirements of many severe application environments. It is necessary to prepare an ultraviolet-curable coating with high wear resistance and high temperature resistance to effectively improve the service life of a substrate with low hardness and poor high temperature resistance.

The existing developed UV coating has some problems in different degrees, such as larger shrinkage, poor adhesion, poor wear resistance and high temperature resistance and the like after photocuring. In addition, in order to improve the wear resistance of the existing UV coating, some inorganic fillers are often added, and the improper selection of some fillers often causes the unsatisfactory wear resistance, such as the problems of agglomeration, long-time storage delamination and the like of a coating system. In addition, when pure epoxy acrylate, urethane acrylate or other acrylate resins are used as the photosensitive resin, the coating layer cannot easily obtain excellent comprehensive performance.

Thus, the incorporation of a silicone resin which can participate in curing in the coating is a viable approach. Currently, methacryloxypropyltrimethoxysilane (KH-570) is added in the process of synthesizing the silicon resin and then is compounded with polyfunctional acrylate resin to obtain the ultraviolet curing coating with excellent performance. But the curing speed is slow, the surface drying time is long, the double bond conversion rate is low, the polarity of the coating components is often greatly different, the compatibility is poor, and the prepared coating surface is easy to generate defects such as shrinkage cavity and the like, so that the light transmittance, the wear resistance and the high temperature resistance of the coating are influenced.

Disclosure of Invention

Aiming at the problems in the prior art, the applicant of the present invention provides an ultraviolet light curing coating, a preparation method and an application thereof. According to the invention, acrylic acid and epoxycyclohexane silane are subjected to ring-opening reaction to prepare ester epoxy acrylate siloxane containing acryloxy, and then the ester epoxy acrylate siloxane, hexamethyldisiloxane, difunctional siloxane and trifunctional siloxane are subjected to hydrolytic condensation to synthesize the ester epoxy acrylate modified silicone resin. The ester epoxy acrylate modified silicone resin prepared by the invention can be used as an inorganic filler wetting dispersant, and is beneficial to the inorganic filler to obtain a sufficient and uniform dispersion effect in the ultraviolet curing coating. Meanwhile, by matching with the excellent performance of the organic silicon resin, the ultraviolet curing coating prepared by compounding the ester ring epoxy acrylate modified silicon resin and the multifunctional acrylate resin provided by the invention has excellent wear resistance, scratch resistance and high temperature resistance, and the coating surface is not easy to have defects, and has high light transmittance and good adhesive force.

The technical scheme of the invention is as follows:

the ultraviolet curing coating is characterized by being prepared from the following components in parts by weight:

the preparation method of the ester ring epoxy acrylate modified silicone resin comprises the following steps:

s1: adding epoxy cyclohexyl siloxane, acrylic acid, triphenylphosphine, hydroquinone and methyl ethyl ketone into a reaction vessel, heating to 80-90 ℃, stirring for reaction for 5-7 hours, washing by n-hexane, and carrying out reduced pressure distillation to obtain ester epoxy acrylate siloxane containing acryloyloxy;

s2: mixing ester epoxy acrylate siloxane containing acryloyloxy, difunctional siloxane, trifunctional siloxane, isopropanol and hydroquinone, heating to 30-50 ℃, dropwise adding a mixture of hydrochloric acid and deionized water, completing dropwise adding within 0.5-1 hour, heating to 50-70 ℃, stirring for reacting for 2-8 hours, adding hexamethyldisiloxane, heating to 70-80 ℃, and stirring for reacting for 2-5 hours; and then standing for layering, washing an oil layer to be neutral, and finally distilling under reduced pressure to remove small molecular substances to obtain the ester epoxy acrylate modified silicone resin.

In an alternative embodiment, the ester ring epoxy acrylate modified silicone resin has the following structure:

wherein R is₁is-CH₃or-CH₂CH₃，R₂is-CH₃、-CH₂CH₃or-CH₂CH₂CH₃；

The epoxycyclohexylsiloxane is one or more of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane; the difunctional siloxane is one or more of dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane and diethyldimethoxysilane; the tri-functionality siloxane is one or more of ethyl trimethoxy silane, methyl triethoxy silane, propyl triethoxy silane, ethyl triethoxy silane, propyl trimethoxy silane and methyl trimethoxy silane.

In alternative embodiments, the molar ratio of acrylic acid to epoxycyclohexylalkylsiloxane described in S1 is 1: (1-1.3); the dosage of the triphenylphosphine is 0.1 to 3 percent of the total mass of the epoxy cyclohexyl siloxane and the acrylic acid; the dosage of the hydroquinone is 0.1 to 5 percent of the total mass of the epoxy cyclohexyl siloxane and the acrylic acid.

In an alternative embodiment, the molar amount of the deionized water used in S2 is 3 to 9 times the total molar number of the acryloxy group-containing ester epoxy acrylate siloxane, difunctional siloxane and trifunctional siloxane; the dosage of the hydroquinone is 0.1 to 5 percent of the total mass of ester epoxy acrylate siloxane containing acryloxy, difunctional siloxane, trifunctional siloxane and hexamethyldisiloxane; the dosage of the hydrochloric acid is 0.1 to 5 percent of the mass of the water; the molar ratio of the ester ring epoxy acrylate siloxane containing the acryloxy group to the difunctional siloxane to the trifunctional siloxane to the hexamethyldisiloxane is 1: 0.2-0.8: 1-5: 0.1-0.8.

In an alternative embodiment, the reactive diluent comprises one of isobornyl acrylate, hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate (PETA); the matte powder is Japanese east Cao E-1011; the photoinitiator is selected from one or more of 2, 4, 6-trimethyl benzoyl diethyl phosphonate, 2-phenyl-2, 2-dimethylamino-1- (4-morpholinyl phenyl) -1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, alpha-diethoxy acetophenone, 1-hydroxy-cyclohexyl benzophenone and 2, 4, 6-trimethyl benzoyl diphenyl phosphine oxide.

In an alternative embodiment, the multifunctional acrylate resin is selected from one or more of urethane acrylate resin, modified urethane acrylate resin, epoxy acrylate resin and polyester acrylate resin.

As another aspect of the present invention, there is provided a method for preparing an ultraviolet curable coating, comprising the steps of:

(1) stirring 20-50 parts of the reactive diluent, 0.5-1 part of the defoaming agent and 0.5-1 part of the leveling agent for 5-10 min at the rotating speed of 2000-2500 r/min by using a high-speed dispersion machine to uniformly disperse the components;

(2) adding 5-20 parts of the ester ring epoxy acrylate modified silicon resin and 10-15 parts of the matte powder in batches, and stirring for 20-30 min at the rotating speed of 3500-4000 r/min by using a high-speed dispersion machine after all the materials are added;

(3) adding 50-70 parts of multifunctional acrylate resin and 1-5 parts of photoinitiator, and uniformly stirring at the rotating speed of 2000-2500 r/min by using a high-speed dispersion machine to obtain the ultraviolet curing coating.

The invention also provides an application of the ultraviolet curing coating, wherein the ultraviolet curing coating is formed on a base material by a roller coating method, the thickness is controlled to be 8-10 g/square meter and is 600mJ/cm²Is subjected to ultraviolet curing under the irradiation conditions of (1),obtaining the ultraviolet light curing matte paint film.

The invention has the beneficial technical effects that:

according to the invention, acrylic acid and epoxy cyclohexane silane are subjected to ring-opening esterification reaction under the action of a catalyst to prepare ester epoxy acrylate siloxane containing acryloxy, and then hexamethyldisiloxane, difunctional siloxane and trifunctional siloxane are subjected to hydrolytic condensation to synthesize the ester epoxy acrylate modified silicone resin. The synthesized ester epoxy acrylate modified silicon resin can be used as an inorganic filler wetting dispersant, silicon hydroxyl in the structure can generate physical adsorption with the surface of the inorganic filler, and can also be condensed with the hydroxyl on the surface of the inorganic filler to form chemical adsorption, so that inorganic filler particles can obtain a sufficient and uniform dispersion effect, and the comprehensive performance of a coating can be effectively improved by matching with the excellent performance of the organic silicon resin. The acryloxy in the ester ring epoxy acrylate modified silicon resin can provide fast photocuring speed, high double bond conversion rate and high coating crosslinking density and hardness; meanwhile, the cyclohexyl and the hydroxyl in the structure can also improve the polarity of the silicon resin, after the silicon resin is compounded with the multifunctional acrylate resin, the silicon resin does not have phase separation and has good compatibility, the prepared coating still has high light transmittance and good adhesive force, the wear resistance of the coating is further obviously improved, and the pencil hardness can reach 9H; the prepared coating has better high temperature resistance, and the smoke scalding resistance test is grade 5; the coating has higher water contact angle and certain antifouling performance.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In addition, the raw materials and sources used in examples 1 to 6 and comparative examples 1 to 2 of the present invention are all commercially available except that some of them are prepared by the method of the present invention.

The ester ring epoxy acrylate modified silicone resins (B1-B6) prepared in embodiments 1-6 of the invention all have the following structures:

example 1

(1) The ester ring epoxy acrylate modified silicone resin is prepared according to the following method:

24.6g (0.1mol) of 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 7.2g (0.1mol) of acrylic acid, 0.38g of triphenylphosphine, 0.16g of hydroquinone and 10g of methyl ethyl ketone are added into a reactor at one time, reacted for 6 hours at 80 ℃ under the protection of nitrogen, then washed with n-hexane for three times, and distilled under reduced pressure to obtain ester epoxy acrylate siloxane (A1) containing acryloyloxy.

31.8g (0.1mol) of acryloxy group-containing ester epoxy acrylate siloxane (A1), 4.8g (0.04mol) of dimethyldimethoxysilane, 30.1g (0.2mol) of ethyltrimethoxysilane, 10g of isopropanol and 0.9g of hydroquinone were then charged into the flask, and a mixture of a small amount of 0.19g of concentrated hydrochloric acid and 19.44g (1.08mol) of distilled water was added dropwise to the flask over 1 hour at 50 ℃ and the reaction was stirred while heating to 60 ℃ for 6 hours. Then, 1.62g (0.01mol) of hexamethyldisiloxane was added to the flask, the temperature was raised to 70 ℃, the mixture was stirred and reacted for 3 hours under heat preservation, then the mixture was allowed to stand for delamination, the oil layer was washed with water to neutrality, and then the distillation was carried out under reduced pressure, thereby obtaining an ester ring epoxy acrylate-modified silicone resin (B1).

(2) The ultraviolet curing coating is prepared according to the following method:

firstly, 5 parts of HDDA (high-density polyethylene) serving as a reactive diluent, 20 parts of PETA (polyethylene terephthalate) serving as a reactive diluent, 0.5 part of BYK-066 serving as a defoaming agent and 0.5 part of BYK-306 serving as a flatting agent are stirred for 10min by a high-speed dispersion machine at the rotating speed of 2000r/min to be uniformly dispersed. Secondly, 5 parts of ester ring epoxy acrylate modified silicone resin B1 and 15 parts of matte powder E-1011 are added in batches and stirred for 30min at the rotating speed of 3500 r/min. And finally, adding 60 parts of urethane acrylate resin and 3 parts of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, and uniformly stirring at the rotating speed of 2500r/min to obtain the ultraviolet curing coating.

Example 2

(1) The ester ring epoxy acrylate modified silicone resin is prepared according to the following method:

34.6g (0.12mol) of 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 7.2g (0.1mol) acrylic acid, 0.38g of triphenylphosphine, 0.16g of hydroquinone and 10g of methyl ethyl ketone are added into a reactor in one portion and reacted for 6.5h under the protection of nitrogen at 85 ℃, and then the mixture is washed with n-hexane for three times and distilled under reduced pressure to obtain ester ring epoxy acrylate siloxane (A2) containing acryloyloxy.

Subsequently, 36.0g (0.1mol) of acryloxy group-containing ester epoxy acrylate siloxane (A2), 8.9g (0.06mol) of diethyldimethoxysilane, 39.2g (0.22mol) of methyltriethoxysilane, 10g of isopropanol and 0.9g of hydroquinone were charged into a flask, and a mixture of 0.19g of a small amount of concentrated hydrochloric acid and 21.6g (1.2mol) of distilled water was added dropwise to the flask at 45 ℃ over 1 hour, and the mixture was heated to 55 ℃ and stirred for reaction for 7 hours. Then 4.87g (0.03mol) of hexamethyldisiloxane is added into the flask, the temperature is raised to 75 ℃, the mixture is kept warm and stirred for reaction for 4 hours, then the mixture is stood for layering, the oil layer is washed to be neutral by water, and then the pressure is reduced for distillation, so that the ester ring epoxy acrylate modified silicone resin (B2) is obtained.

(2) The ultraviolet curing coating is prepared according to the following method:

firstly, 5 parts of HDDA (high-density polyethylene) serving as a reactive diluent, 20 parts of PETA (polyethylene terephthalate) serving as a reactive diluent, 0.5 part of BYK-066 serving as a defoaming agent and 0.5 part of BYK-306 serving as a flatting agent are stirred for 10min by a high-speed dispersion machine at the rotating speed of 2000r/min to be uniformly dispersed. Secondly, 7 parts of ester ring epoxy acrylate modified silicone resin B2 and 15 parts of matte powder E-1011 are added in batches and stirred for 30min at the rotating speed of 3500 r/min. And finally, adding 60 parts of epoxy acrylate resin and 4 parts of photoinitiator alpha, alpha-diethoxyacetophenone, and uniformly stirring at the rotating speed of 2500r/min to obtain the ultraviolet curing coating.

Example 3

(1) The ester ring epoxy acrylate modified silicone resin is prepared according to the following method:

an acryloxy group-containing ester ring epoxy acrylate siloxane (a1) was prepared by the procedure of example 1. Subsequently, 31.8g (0.1mol) of acryloxy group-containing ester epoxy acrylate siloxane (A1), 8.8g (0.05mol) of diethyldiethoxysilane, 30.9g (0.15mol) of propyltriethoxysilane, 10g of isopropanol and 0.9g of hydroquinone were charged into the flask, and a mixture of a small amount of 0.19g of concentrated hydrochloric acid and 17.82g (0.99mol) of distilled water was added dropwise to the flask at 40 ℃ over 1 hour, and the reaction was stirred at 60 ℃ for 8 hours. Then 6.50g (0.04mol) of hexamethyldisiloxane is added into the flask, the temperature is raised to 70 ℃, the mixture is kept warm and stirred for reaction for 5 hours, then the mixture is stood for layering, an oil layer is washed to be neutral by water, and then the pressure is reduced for distillation, so that the ester ring epoxy acrylate modified silicone resin (B3) is obtained.

(2) The ultraviolet curing coating is prepared according to the following method:

firstly, 5 parts of HDDA (high-density polyethylene) serving as a reactive diluent, 20 parts of PETA (polyethylene terephthalate) serving as a reactive diluent, 0.5 part of BYK-066 serving as a defoaming agent and 0.5 part of BYK-306 serving as a flatting agent are stirred for 10min by a high-speed dispersion machine at the rotating speed of 2000r/min to be uniformly dispersed. Secondly, 8 parts of ester ring epoxy acrylate modified silicone resin B3 and 15 parts of matte powder E-1011 are added in batches and stirred for 30min at the rotating speed of 3500 r/min. And finally, adding 60 parts of polyester acrylate resin and 3 parts of photoinitiator 1-hydroxy-cyclohexyl benzophenone, and uniformly stirring at the rotating speed of 2500r/min to obtain the ultraviolet curing coating.

Example 4

(1) The ester ring epoxy acrylate modified silicone resin is prepared according to the following method:

an acryloxy group-containing ester ring epoxy acrylate siloxane (a2) was prepared by the procedure of example 2. Subsequently, 36.0g (0.1mol) of acryloxy group-containing ester epoxy acrylate siloxane (A2), 7.4g (0.05mol) of dimethyldiethoxysilane, 34.6g (0.18mol) of ethyltriethoxysilane, 10g of isopropanol and 0.8g of hydroquinone were charged into the flask, and a mixture of a small amount of 0.19g of concentrated hydrochloric acid and 18.9g (1.05mol) of distilled water was added dropwise to the flask at 50 ℃ over 1 hour, and the mixture was heated to 65 ℃ and stirred for reaction for 7 hours. Then 3.3g (0.02mol) of hexamethyldisiloxane is added into the flask, the temperature is raised to 70 ℃, the mixture is kept warm and stirred for reaction for 4 hours, then the mixture is stood for layering, the oil layer is washed to be neutral by water, and then the pressure is reduced for distillation, so that the ester ring epoxy acrylate modified silicone resin (B4) is obtained.

(2) The ultraviolet curing coating is prepared according to the following method:

firstly, 5 parts of HDDA (high-density polyethylene) serving as a reactive diluent, 20 parts of PETA (polyethylene terephthalate) serving as a reactive diluent, 0.5 part of BYK-066 serving as a defoaming agent and 0.5 part of BYK-306 serving as a flatting agent are stirred for 10min by a high-speed dispersion machine at the rotating speed of 2000r/min to be uniformly dispersed. Secondly, 15 parts of ester ring epoxy acrylate modified silicone resin B4 and 15 parts of matte powder E-1011 are added in batches and stirred for 30min at the rotating speed of 3500 r/min. And finally, adding 60 parts of polyester acrylate resin and 3 parts of photoinitiator 1-hydroxy-cyclohexyl benzophenone, and uniformly stirring at the rotating speed of 2500r/min to obtain the ultraviolet curing coating.

Example 5

(1) The ester ring epoxy acrylate modified silicone resin is prepared according to the following method:

an acryloxy group-containing ester ring epoxy acrylate siloxane (a1) was prepared by the procedure of example 1. 31.8g (0.1mol) of acryloxy group-containing ester epoxy acrylate siloxane (A1), 8.4g (0.07mol) of dimethyldimethoxysilane, 31.2g (0.19mol) of propyltrimethoxysilane, 15g of methyl ethyl ketone and 0.9g of hydroquinone were then charged into the flask, and a mixture of a small amount of 0.21g of concentrated hydrochloric acid and 21.06g (1.17mol) of distilled water was added dropwise to the flask at 45 ℃ over 0.5 hour, and the reaction was stirred at 60 ℃ for 8 hours. Then, 8.1g (0.05mol) of hexamethyldisiloxane was added to the flask, the temperature was raised to 70 ℃, the reaction was carried out with stirring under heat preservation for 5 hours, then the mixture was allowed to stand for delamination, the oil layer was washed with water to neutrality, and then the distillation was carried out under reduced pressure, thereby obtaining an ester ring epoxy acrylate-modified silicone resin (B5).

(2) The ultraviolet curing coating is prepared according to the following method:

firstly, 5 parts of HDDA (high-density polyethylene) serving as a reactive diluent, 20 parts of PETA (polyethylene terephthalate) serving as a reactive diluent, 0.5 part of BYK-066 serving as a defoaming agent and 0.5 part of BYK-306 serving as a flatting agent are stirred for 10min by a high-speed dispersion machine at the rotating speed of 2000r/min to be uniformly dispersed. Secondly, 16 parts of ester ring epoxy acrylate modified silicone resin B5 and 15 parts of matte powder E-1011 are added in batches and stirred for 30min at the rotating speed of 3500 r/min. And finally, adding 60 parts of modified urethane acrylate resin and 3 parts of photoinitiator alpha, alpha-diethoxyacetophenone, and uniformly stirring at the rotating speed of 2500r/min to obtain the ultraviolet curing coating.

Example 6

(1) The ester ring epoxy acrylate modified silicone resin is prepared according to the following method:

an acryloxy group-containing ester ring epoxy acrylate siloxane (a2) was prepared by the procedure of example 2. Subsequently, 36.0g (0.1mol) of acryloxy group-containing ester epoxy acrylate siloxane (A2), 8.9g (0.06mol) of dimethyldiethoxysilane, 28.6g (0.21mol) of methyltrimethoxysilane, 15g of methyl ethyl ketone and 0.9g of hydroquinone were charged into the flask, and a mixture of a small amount of 0.21g of concentrated hydrochloric acid and 21.06g (1.17mol) of distilled water was added dropwise into the flask at 50 ℃ over 1 hour, and the reaction was stirred at 70 ℃ for 5 hours. Then 4.87g (0.03mol) of hexamethyldisiloxane is added into the flask, the temperature is raised to 80 ℃, the mixture is kept warm and stirred for reaction for 2 hours, then the mixture is stood for layering, the oil layer is washed to be neutral by water, and then the pressure is reduced for distillation, so that the ester ring epoxy acrylate modified silicone resin (B6) is obtained.

(2) The ultraviolet curing coating is prepared according to the following method:

firstly, 5 parts of HDDA (high-density polyethylene) serving as a reactive diluent, 20 parts of PETA (polyethylene terephthalate) serving as a reactive diluent, 0.5 part of BYK-066 serving as a defoaming agent and 0.5 part of BYK-306 serving as a flatting agent are stirred for 10min by a high-speed dispersion machine at the rotating speed of 2000r/min to be uniformly dispersed. And secondly, adding 20 parts of ester ring epoxy acrylate modified silicon resin and 15 parts of matte powder E-1011 in batches, and stirring for 30min at the rotating speed of 3500 r/min. And finally, adding 60 parts of epoxy acrylate resin and 3 parts of photoinitiator 1-hydroxy-cyclohexyl benzophenone, and uniformly stirring at the rotating speed of 2500r/min to obtain the ultraviolet curing coating.

Comparative example 1

(1) The KH570 modified silicone resin was prepared as follows:

KH57024.8g (0.1mol), dimethyldimethoxysilane 4.8g (0.04mol), ethyltrimethoxysilane 30.1g (0.2mol), isopropanol 10g and hydroquinone 0.9g were charged into a flask, and a mixture of a small amount of concentrated hydrochloric acid 0.19g and distilled water 19.44g (1.08mol) was added dropwise to the flask at 50 ℃ over 1 hour, and the temperature was raised to 60 ℃ to react for 6 hours. Then, 1.62g (0.01mol) of hexamethyldisiloxane was added to the flask, the temperature was raised to 70 ℃ and the reaction was carried out for 3 hours while maintaining the temperature, and then, the reaction was carried out under reduced pressure to obtain KH 570-modified silicone resin (B7).

(2) The UV curable coating was prepared according to the method of example 1.

Comparative example 2

(1) The KH570 modified silicone resin was prepared as follows:

KH57024.8g (0.1mol), diethyldimethoxysilane 8.9g (0.06mol), methyltriethoxysilane 39.2g (0.22mol), isopropanol 10g and hydroquinone 0.9g were charged into a flask, and a mixture of a small amount of concentrated hydrochloric acid 0.19g and distilled water 21.6g (1.2mol) was added dropwise to the flask over 1 hour at 45 ℃ to raise the temperature to 55 ℃ for reaction for 7 hours. Thereafter, 4.87g (0.03mol) of hexamethyldisiloxane was added to the flask, the temperature was raised to 75 ℃ and the reaction was carried out under heat for 4 hours, followed by distillation under reduced pressure to obtain KH 570-modified silicone resin (B8).

(2) The UV curable coating was prepared according to the method of example 1.

Film coating Performance test

The coatings of examples 1 to 6 and comparative examples 1 to 2 were respectively roll-coated on PVC floor base materials with a thickness of 8 to 10 g/m and a thickness of 600mJ/cm²Carrying out ultraviolet curing under the energy of the ultraviolet light to obtain the ultraviolet curing matte paint film.

The properties of the resulting coating film were measured as shown in Table 1.

Table 1 coating performance test results

Note: the pencil hardness is measured according to GB/T6739-.

As can be seen from Table 1, compared with the coating performances of the comparative examples 1 to 2, the ultraviolet curing coating paint films prepared in the examples 1 to 6 of the invention have better comprehensive performances. The ester ring epoxy acrylate modified silicon resin can be used as an inorganic filler wetting dispersant, silicon hydroxyl in the structure can generate physical adsorption with the surface of the inorganic filler, and can also be condensed with the hydroxyl on the surface of the inorganic filler to form chemical adsorption, so that inorganic filler particles can obtain a sufficient and uniform dispersion effect, and the comprehensive performance of the coating can be effectively improved by matching with the excellent performance of the organic silicon resin. The acryloxy in the ester epoxy acrylate modified silicone resin can provide fast photocuring speed, high double bond conversion rate and high coating crosslinking density and hardness, so that the abrasion resistance and Martindale abrasion resistance of the coated film on the base material are both effectively improved; meanwhile, the cyclohexyl and the hydroxyl in the structure can also improve the polarity of the silicon resin, and after being compounded with the multifunctional acrylate resin, the silicon resin does not have phase separation, has good compatibility and is smooth in coating film appearance; the adhesion of the coating film on the base material is improved; the prepared coating has better high temperature resistance, and the smoke scalding resistance test is grade 5; the water contact angle of the coating is improved to a certain extent, and the anti-fouling performance is improved.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.