CN114133572B - Photosensitive organic silicon resin, preparation method and application - Google Patents

Abstract

The invention provides a photosensitive organic silicon resin, a preparation method and application, and belongs to the technical field of photosensitive molecular materials. Dissolving a photoinitiator and a catalyst I in a solvent I, adding isocyanate siloxane, heating, stirring for reaction, washing n-hexane, and distilling under reduced pressure to obtain a siloxane photoinitiator; mixing hydroxyl-terminated PDMS, isocyanate siloxane, a catalyst I and a solvent II, heating, stirring, reacting, washing with acetonitrile, and distilling under reduced pressure to obtain siloxane PDMS; mixing a siloxane photoinitiator, siloxane PDMS, alkyl siloxane and a solvent III, heating to 40-60 ℃, adding a mixture of a catalyst II and deionized water, adding hexamethyldisiloxane, standing for layering, taking down the layer, and carrying out reduced pressure distillation to obtain the photosensitive organic silicon resin. The preparation method is simple and easy to control, and the photosensitive organic silicon resin has low surface energy and high hardness, and is used for preparing coatings, antifouling and fingerprint resistance.

Description

A kind of photosensitive silicone resin, preparation method and application

technical field

The invention belongs to the technical field of photosensitive molecular materials, and in particular relates to a photosensitive organosilicon resin, a preparation method and an application.

Background technique

UV curing technology has attracted more and more attention due to its unique advantages such as room temperature curing, wide adaptability, low energy consumption, high efficiency and environmental protection, and is widely used in coatings, inks, adhesives, microelectronics and dental restoration.

UV-cured coatings tend to have poor stain resistance, are easily stained by water-based and oil-based stains, and are difficult to clean. Often a fluorine- or silicon-containing component is grafted into the polymer to improve the stain resistance durability of the coating. Although fluorine-containing components have excellent antifouling effects, their high cost, high toxicity, and bioaccumulation limit their applications. The antifouling coating prepared by combining the substrates has the characteristics of high light transmittance and excellent hydrophobic and oleophobic properties, so it is more suitable for practical applications. The molecular chain of PDMS has very good flexibility, but the hardness of the coating obtained after curing is often not very high.

Silicone resin prepared by acid hydrolysis condensation method has many excellent physical and chemical properties, such as high hardness, high and low temperature resistance, oxidation resistance, weather resistance, etc. than has more excellent wear resistance.

SUMMARY OF THE INVENTION

The object of the present invention is to overcome the deficiencies of the prior art, provide a photosensitive organosilicon resin, a preparation method and an application, the preparation method is simple and easy to control, the prepared photosensitive organosilicon resin has the characteristics of low surface energy and high hardness, and is compatible with Coatings prepared by compounding multifunctional acrylate resins have high hardness, as well as anti-fouling and fingerprint-resistant properties.

As a first aspect of the present invention, a preparation method of a photosensitive silicone resin is provided, and the technical problem to be solved is how to prepare a photosensitive silicone resin that can be applied to coating technology. The preparation method is simple and easy to control, including: The following steps:

(1) Preparation of siloxane photoinitiator

The photoinitiator and catalyst I were dissolved in solvent I and then the isocyanatosiloxane was added dropwise. The temperature is raised to 40°C to 60°C, and the stirring reaction is continued for 5 to 8 hours. After washing with n-hexane, the siloxane photoinitiator is obtained by distillation under reduced pressure;

(2) Preparation of siloxane PDMS

The hydroxyl-terminated PDMS, isocyanate-based siloxane, catalyst I and solvent II are mixed, the temperature is raised to 50°C to 70°C, and the reaction is stirred for 5 to 10 hours. After washing with acetonitrile, the siloxane PDMS is obtained by distillation under reduced pressure;

(3) Preparation of photosensitive silicone resin

Mix the siloxane photoinitiator, siloxane PDMS, alkane siloxane and solvent III, raise the temperature to 40℃～60℃, add the mixture of catalyst II and deionized water dropwise, dropwise dropwise within 0.5～1 hour After completion, the temperature is raised to 50°C to 60°C, the reaction is stirred for 5 to 10 hours, hexamethyldisiloxane is added, the temperature is raised to 60°C to 80°C, and the reaction is stirred for 1 to 3 hours. Press distillation to obtain photosensitive silicone resin;

Wherein, catalyst I is one or more in dibutyltin dilaurate, stannous octoate, butyltin diacetate; solvent I is one or more in chloroform, tetrahydrofuran and methyl ethyl ketone; solvent II is methyl ethyl ketone One or more of ethyl ketone, ethyl acetate, acetone, toluene, xylene and tetrahydrofuran; Catalyst II is one or more of glacial acetic acid, formic acid, hydrochloric acid, oxalic acid and sulfuric acid; Solvent III It is one or more of methanol, ethanol, isopropanol, ethyl formate, ethyl acetate, toluene, xylene and tetrahydrofuran;

In one or more implementation cases, the siloxane-based photoinitiator in step (1) has the following structure:

Wherein, X is a small molecule photoinitiator with hydroxyl or amino group, namely benzoin and its derivatives with hydroxyl or amino group, benzil, alkyl phenone, benzophenone and thia Anthrone compound, R ₁ is -CH ₃ or -CH ₂ CH ₃ .

In one or more implementation cases, the molar ratio of the photoinitiator described in step (1) to the isocyanatosiloxane is 1:(1-1.5); 0.1% to 3% of the total mass of the initiator and the isocyanate-based siloxane.

In one or more implementation cases, the siloxane PDMS in step (2) has the following structure:

Wherein, R ₁ is -CH ₃ or -CH ₂ CH ₃ , and R ₃ is

n为8～64的自然数；

n is a natural number from 8 to 64;

The hydroxyl-terminated PDMS described in step (2) has a weight-average molecular weight of 1000-5000 g/mol;

The molar ratio of the hydroxyl-terminated PDMS described in the step (2) and the isocyanate-based siloxane is 1: (1-5); the consumption of the catalyst I is the total mass of the hydroxyl-terminated PDMS and the isocyanate-based siloxane. 0.1%～3%.

In one or more implementation cases, the alkane-based siloxane in step (3) has the following structure:

R ₃ -Si(OR ₁ ) ₃

Wherein, R ₁ is -CH ₃ or -CH ₂ CH ₃ , and R ₃ is -CH ₃ , -CH ₂ CH ₃ or -CH ₂ CH ₂ CH ₃ .

In one or more implementation cases, the molar amount of deionized water in step (3) is the total molar amount of the siloxane photoinitiator, long-chain PDMS-containing siloxane and alkane siloxane 3 to 9 times the number;

The amount of catalyst II described in step (3) is 0.1% to 5% of the water quality;

The molar ratio of the siloxane photoinitiator, siloxane PDMS, alkane siloxane and hexamethyldisiloxane described in step (3) is 1:(0.01～1):(1～ 5): (0.5～2).

In one or more implementation cases, the isocyanatosiloxanes described in steps (1) and (2) are 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane one or more of them.

As a second aspect of the present invention, a photosensitive silicone resin is provided, which is prepared by the above-mentioned preparation and has the following structure:

Wherein, X is a small molecule photoinitiator with hydroxyl or amino group, R ₁ is -CH ₃ or -CH ₂ CH ₃ , R ₂ is

R₃为-CH₃、-CH₂CH₃或

R ₃ is -CH ₃ , -CH ₂ CH ₃ or

As the third aspect of the present invention, an application of a photosensitive silicone resin is provided. After mixing the above-mentioned photosensitive silicone resin, multifunctional acrylate resin and photoinitiator, a film is applied on the substrate, and then ultraviolet light is applied. Light irradiation, curing into a film;

Wherein, the photoinitiator is selected from diethyl 2,4,6-trimethylbenzoylphosphonate, 2-phenyl-2,2-dimethylamino-1-(4-morpholinephenyl) )-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, α,α-diethoxyacetophenone, 1-hydroxy-cyclohexylbenzophenone and 2,4 , one or more in 6-trimethylbenzoyl diphenyl phosphine oxide;

The dosage of the photoinitiator is 1% to 5% of the total mass of the multifunctional acrylate resin and the photoinitiable polymerizable silicon-containing resin;

The multifunctional acrylate resin is selected from one or more of polyurethane acrylate resin, epoxy acrylate resin and polyester acrylate resin;

The base material is selected from one or more of PC board, PMMA board, wood board, steel plate and glass board.

In one or more implementation cases, the amount of the photosensitive silicone resin is 1% to 15% of the mass of the multifunctional acrylate resin.

The present invention contains at least the following beneficial effects:

In the present invention, siloxane-based photoinitiator and siloxane-based PDMS are prepared by reacting isocyanate-based siloxane with small molecular photoinitiator and PDMS respectively, and then reacted with alkane-based siloxane and hexamethyldisiloxane. The photosensitive organosilicon resin is synthesized through hydrolysis and condensation, and the method is simple and easy to control. Siliconized PDMS is used to provide excellent high contact angle and low sliding angle to obtain excellent antifouling performance; under ultraviolet light irradiation, the siliconeized photoinitiator will be cleaved to generate free radicals, which will interact with The multifunctional acrylate reacts, and the PDMS component with low surface energy in the photosensitive silicone resin will undergo surface migration during the UV curing process, increase the free radical concentration on the surface of the coating, and reduce oxygen to a certain extent. Inhibition of polymerization. After compounding photosensitive silicone resin and multifunctional acrylate resin, the coating prepared by UV curing has excellent wear resistance, pencil hardness can reach 4H; anti-fingerprint, easy to wipe, and good durability , it still has good effect after 5000 friction cycle tests; the cured film has good hydrophobic and oleophobic properties, the water contact angle can reach more than 110°, the hexadecane contact angle can reach more than 37°; the double bond conversion rate is more than 94% .

Detailed ways

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

In the present invention, the application of the photoinitiable polymerizable silicon-containing resin in the coating, the basic properties of the coating are tested and evaluated with reference to Table 1:

Table 1 Coating performance test method

The raw materials and sources used in Examples 1 to 5 of the present invention and Comparative Examples 1 to 3 are shown in Table 2:

The raw materials and sources used in the examples and comparative examples of table 2

raw material name Source of raw materials Photoinitiator 2959 Maclean's reagent Catalyst I: Dibutyltin dilaurate Sinopharm Group Chemical Co., Ltd. 3-Isocyanatopropyltrimethoxysilane aladdin co., ltd. Solvent I: methyl ethyl ketone aladdin co., ltd. Monohydroxyl-terminated PDMS (M_w=1000) Shanghai Merrill Chemical Technology Co., Ltd. n-hexane Sinopharm Group Chemical Co., Ltd. Acetonitrile Sinopharm Group Chemical Co., Ltd. Propyltrimethoxysilane Maclean's reagent Solvent II: Isopropanol Sinopharm Group Chemical Co., Ltd. Catalyst II: Hydrochloric acid Sinopharm Group Chemical Co., Ltd. Hexamethyldisiloxane Sinopharm Group Chemical Co., Ltd. Urethane acrylate resin Jiangsu Litian Technology Co., Ltd. epoxy acrylate resin Jiangsu Litian Technology Co., Ltd. polyester acrylate resin Jiangsu Litian Technology Co., Ltd. 3-Isocyanatopropyltriethoxysilane Maclean's reagent Catalyst I: stannous octoate Sinopharm Group Chemical Co., Ltd. Dihydroxyl-terminated PDMS (M_w=1000) Shanghai Merrill Chemical Technology Co., Ltd. Ethyltrimethoxysilane Maclean's reagent Catalyst II: Oxalic acid Sinopharm Group Chemical Co., Ltd. Monohydroxyl-terminated PDMS (M_w=2000) Shanghai Merrill Chemical Technology Co., Ltd. Photoinitiator 1173 Maclean's reagent Photoinitiator 184 Maclean's reagent Propyltrimethoxysilane Sinopharm Group Chemical Co., Ltd. Solvent II: Acetone Sinopharm Group Chemical Co., Ltd. Photoinitiator HMBP Maclean's reagent Methyltrimethoxysilane Maclean's reagent Photoinitiator ABP Maclean's reagent Ethyltriethoxysilane aladdin co., ltd.

Example 1

(1) Preparation of siloxane photoinitiator 2959-IPTES

11.21 g (0.05 mol) of 2959 (2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl-1-propanone) and 0.15 g of dibutyltin dilaurate were dissolved in 4 g of methyl ethyl ketone, then 10.27 g (0.05 mol) of IPTES (3-isocyanatopropyltrimethoxysilane) were added dropwise. The temperature was raised to 50° C., and the stirring reaction was continued for 6 hours. After washing with n-hexane, the siloxane photoinitiator 2959-IPTES was obtained by distillation under reduced pressure.

(2) Preparation of siloxane PDMS-1-1000-IPTES

To a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 16.422 g (0.08 mol) of IPTES, 50 g (0.05 mol) of monohydroxy-terminated PDMS (M _w = 1000), 0.061 g of dibutyltin dilaurate and 10 g of methyl ethyl ketone was stirred and reacted in an oil bath at 70° C. for 6 hours. After that, it was washed three times with acetonitrile and distilled under reduced pressure to obtain siloxane PDMS-1-1000-IPTES.

(3) Preparation of photosensitive silicone resin

Mix 4.30g (0.01mol) 2959-IPTES, 6.03g (0.005mol) PDMS-1-1000-IPTES, 6.57g (0.04mol) propyltrimethoxysilane and 5g isopropanol, stir well and heat up to 50 °C. A mixture of 0.041 g concentrated hydrochloric acid and 2.97 g (0.165 mol) deionized water was then added dropwise to the flask over 1 h. Then, the temperature of the reaction mixture was increased to 60°C for 6 hours. Then, 1.461 g (0.009 mol) of hexamethyldisiloxane was added to the flask, the temperature was raised to 70° C., and the reaction was carried out at a temperature of 3 hours. After the completion of the reaction, stand for layering to remove the lower layer solution, and then remove the solvent and low-boiling point residues in the organic phase at 50° C./130 mmHg to obtain a photosensitive silicone resin (A1,

R₁为-CH₃，R₂为

，R₃为-CH₂CH₂CH₃)。where X is

R ₁ is -CH ₃ and R ₂ is

, R ₃ is -CH ₂ CH ₂ CH ₃ ).

(4) Curing of photosensitive silicone resin

After mixing 100 parts by mass of urethane acrylate resin, 1 part by mass of photosensitive silicone resin (A1) and 3 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, put it on a PMMA plate The coating film is then irradiated with ultraviolet light to cure to form a film.

Example 2

(1) Preparation of siloxane photoinitiator 1173-IPTMS

8.21g (0.05mol) of 1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone) and 0.14g of stannous octoate were dissolved in 4g of chloroform, and then 12.35g (0.05mol) of IPTMS ( 3-isocyanatopropyltriethoxysilane). The temperature was raised to 55° C., and the reaction was continued for 5 hours. After washing with n-hexane, the siloxane photoinitiator 1173-IPTMS was obtained by distillation under reduced pressure.

(2) Preparation of siloxane PDMS-2-1000-IPTMS

To a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, add 39.52g (0.16mol) IPTMS, 50g (0.05mol) dihydroxy-terminated PDMS ( _Mw =1000), 0.063g stannous octoate and 10g toluene , and the reaction was stirred in an oil bath at 70 °C for 8 hours. After that, it was washed three times with acetonitrile and distilled under reduced pressure to obtain siloxane PDMS-2-1000-IPTES.

(3) Preparation of photosensitive silicone resin

4.12g (0.01mol) of 1173-IPTMS, 4.48g (0.003mol) of PDMS-1-1000-IPTMS, 3.76g (0.025mol) of ethyltrimethoxysilane and 5g of toluene were mixed, stirred uniformly and heated to 45°C. A mixture of 0.043 g of oxalic acid and 2.05 g (0.114 mol) of deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then increased to 55°C for 8 hours. Then, 1.79 g (0.011 mol) of hexamethyldisiloxane was added to the flask, the temperature was raised to 70° C., and the reaction was carried out at a temperature of 2 hours. After the completion of the reaction, stand for layering to remove the lower layer solution, and then remove the solvent and low-boiling point residues in the organic phase at 50° C./130 mmHg to obtain a photosensitive silicone resin (A2,

R₁为-CH₃和-CH₂CH₃，R₂为

，R₃为-CH₂CH₃)。where X is

R ₁ is -CH ₃ and -CH ₂ CH ₃ , R ₂ is

, R ₃ is -CH ₂ CH ₃ ).

(4) Curing of photosensitive silicone resin

After mixing 100 parts by mass of polyester acrylate resin, 1.5 parts by mass of photosensitive silicone resin (A2) and 4 parts by mass of photoinitiator α,α-diethoxyacetophenone UV light irradiation, curing into a film.

Example 3

(1) Preparation of siloxane photoinitiator 184-IPTMS

10.22 g (0.05 mol) of 184 (1-hydroxy-cyclohexyl-phenyl ketone) and 0.14 g of dibutyltin dilaurate were dissolved in 7 g of methyl ethyl ketone, followed by dropwise addition of 14.82 g (0.06 mol) of IPTMS. The temperature was raised to 60° C., and the reaction was continued for 6 hours. After washing with n-hexane, the siloxane photoinitiator 184-IPTMS was obtained by distillation under reduced pressure.

(2) Preparation of siloxane PDMS-2-1000-IPTMS

24.70g (0.10mol) IPTMS, 100g (0.05mol) monohydroxyl-terminated PDMS ( _Mw =2000), 0.081g stannous octoate and xylene were added to a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer 20 g, stirred and reacted in an oil bath at 70°C for 10 hours. After that, it was washed three times with acetonitrile and distilled under reduced pressure to obtain siloxane PDMS-1-2000-IPTES.

(3) Preparation of photosensitive silicone resin

4.51 g (0.01 mol) of 184-IPTMS, 4.49 g (0.002 mol) of PDMS-1-2000-IPTMS, 4.93 g (0.03 mol) of propyltrimethoxysilane and 6 g of acetone were mixed, stirred uniformly and heated to 45°C. A mixture of 0.043 g of oxalic acid and 2.05 g (0.114 mol) of deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then increased to 55°C for 9 hours. Then, 1.95 g (0.012 mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 75° C., and the reaction was carried out at a temperature of 3 hours. After the reaction, the solution was left to stand for layering and the lower layer solution was removed, and then the solvent and low-boiling residues in the organic phase were removed at 50° C./130 mmHg to obtain a photosensitive silicone resin (A3,

R₁为-CH₃和-CH₂CH₃，R₂为

，R₃为-CH₂CH₃)。where X is

R ₁ is -CH ₃ and -CH ₂ CH ₃ , R ₂ is

, R ₃ is -CH ₂ CH ₃ ).

(4) Curing of photosensitive silicone resin

After mixing 100 parts by mass of epoxy acrylate resin, 2 parts by mass of photosensitive silicone resin (A3) and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone, film was applied on a wooden board, and then irradiated with ultraviolet light , cured into a film.

Example 4

(1) Preparation of siloxane photoinitiator HMBP-IPTES

10.61 g (0.05 mol) of HMBP (4-hydroxymethyl benzophenone) and 0.16 g of dibutyltin dilaurate were dissolved in 5 g of methyl ethyl ketone, and then 12.32 g (0.06 mol) of IPTES were added dropwise. The temperature was raised to 60° C., and the reaction was continued for 7 hours. After washing with n-hexane, the siloxane-based photoinitiator HMBP-IPTES was obtained by distillation under reduced pressure.

(2) Preparation of siloxane PDMS

Siliconized PDMS-1-1000-IPTES was prepared using the procedure in Example 1.

(3) Preparation of photosensitive silicone resin

4.18g (0.01mol) HMBP-IPTMS, 3.62g (0.003mol) PDMS-1-1000-IPTMS, 4.77g (0.035mol) methyltrimethoxysilane and 4g acetone were mixed, stirred uniformly and heated to 45°C. A mixture of 0.051 g of glacial acetic acid and 2.52 g (0.144 mol) of deionized water was then added dropwise to the flask over 1 h. Then, the temperature of the reaction mixture was increased to 60°C for 6 hours. Then, 2.11 g (0.013 mol) of hexamethyldisiloxane was added to the flask, the temperature was raised to 70° C., and the reaction was carried out at a temperature of 2 hours. After the reaction, the solution was left to stand for layering and the lower layer solution was removed, and then the solvent and low-boiling residue in the organic phase were removed at 50° C./130 mmHg to obtain a photosensitive silicone resin (A4,

R₁为-CH₃，R₂为

，R₃为-CH₃)。where X is

R ₁ is -CH ₃ and R ₂ is

, R ₃ is -CH ₃ ).

(4) Curing of photosensitive silicone resin

After mixing 100 parts by mass of urethane acrylate resin, 1 part by mass of photosensitive silicone resin (A4) and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone, coating a film on a wooden board, and then irradiating with ultraviolet light, Cure to form a film.

Example 5

(1) Preparation of siloxane photoinitiator ABP-IPTES

9.91 g (0.05 mol) of ABP (4-aminodiphenyl ketone) and 0.03 g of dibutyltin dilaurate were dissolved in 5 g of methyl ethyl ketone, and then 10.27 g (0.05 mol) of IPTES were added dropwise. The temperature was raised to 40°C, and the reaction was continued for 5 hours. After washing with n-hexane, the siloxane photoinitiated ABP-IPTES was obtained by distillation under reduced pressure.

(2) Preparation of siloxane PDMS

Siliconized PDMS-2-1000-IPTES was prepared using the procedure in Example 2.

(3) Preparation of photosensitive silicone resin

Mix 4.04g (0.01mol) ABP-IPTES, 4.48g (0.003mol) PDMS-1-1000-IPTMS, 3.85g (0.02mol) ethyltriethoxysilane and 5g isopropanol, stir well and heat up to 50°C. A mixture of 0.051 g concentrated hydrochloric acid and 1.78 g (0.099 mol) deionized water was then added dropwise to the flask over 1 h. Then, the temperature of the reaction mixture was raised to 60°C for 5 hours. Then, 1.63 g (0.01 mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70° C., and the reaction was carried out at a temperature of 2.5 hours. After the completion of the reaction, stand for layering to remove the lower layer solution, and then remove the solvent and low-boiling residues in the organic phase at 50° C./130 mmHg to obtain a photosensitive silicone resin (A5,

R₁为-CH₃和-CH₃，R₂为

，R₃为-CH₂CH₃)。where X is

R ₁ is -CH ₃ and -CH ₃ , and R ₂ is

, R ₃ is -CH ₂ CH ₃ ).

(4) Curing of photosensitive silicone resin

After mixing 100 parts by mass of polyester acrylate resin, 1 part by mass of photosensitive silicone resin (A5), and 3 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, on a steel plate The coating film is then irradiated with ultraviolet light to cure to form a film.

Comparative Example 1

(1) Curing of urethane acrylate resin

After mixing 100 parts by mass of urethane acrylate resin and 3 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, coating a film on the PMMA plate, and then irradiating with ultraviolet light, Cure to form a film.

Comparative Example 2

(1) Curing of epoxy acrylate resin

After mixing 100 parts by mass of epoxy acrylate resin and 4 parts by mass of photoinitiator α,α-diethoxyacetophenone, a film was coated on the PVC sheet, and then irradiated with ultraviolet light to cure to form a film.

Comparative Example 3

(1) Curing of polyester acrylate resin

After mixing 100 parts by mass of polyester acrylate resin and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone, the PC board was coated with a film, and then irradiated with ultraviolet light to cure to form a film.

With reference to the test method and test standard of Table 1, the following technical performance tests are carried out to the paint films of above-mentioned Examples 1 to 5 and Comparative Examples 1 to 3, and the results of each performance test are as follows: The test results are shown in Table 3:

From the performance test results of Examples 1 to 5 and Comparative Examples 1 to 3 in Table 3, it can be seen that the photosensitive silicone resins prepared in Examples 1 to 5 of the present invention can be used as light-curing antifouling coatings, and the hardness can reach 4H; The initial water drop angle of 110° or more, and the initial hexadecane contact angle of 37° or more, has a very good anti-fingerprint and anti-staining effect. After 3000 and 5000 friction cycle tests, it still has high water and hexadecane Alkane contact angle can maintain long-term antifouling effect; Comparative Examples 1 to 3 have poor wear resistance, no antifouling, fingerprint resistance, and low double bond conversion without adding photosensitive silicone resin.

The technical solutions of the present invention are only introduced with preferred embodiments above, but for those skilled in the art, based on the idea of the embodiments of the present invention, changes should be made in the specific implementation manner and application scope. Therefore, in summary, Said, the content of this specification should not be construed as a limitation of the present invention, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included within the scope of the claims of the present invention.

Claims (7)

1. a preparation method of photosensitive organosilicon resin, is characterized in that, comprises the following steps: (1) Preparation of siloxane photoinitiator Dissolve the photoinitiator and the catalyst I in the solvent I, then add dropwise isocyanatosiloxane, raise the temperature to 40°C to 60°C, and continue to stir the reaction for 5 to 8 hours. After washing with n-hexane, distillation under reduced pressure A siloxane photoinitiator is obtained; (2) Preparation of siloxane PDMS The hydroxyl-terminated PDMS, isocyanate-based siloxane, catalyst I and solvent II are mixed, the temperature is raised to 50°C to 70°C, and the reaction is stirred for 5 to 10 hours. After washing with acetonitrile, the siloxane PDMS is obtained by distillation under reduced pressure; (3) Preparation of photosensitive silicone resin Mix the siloxane photoinitiator, the siloxane PDMS, the alkane siloxane and the solvent III, raise the temperature to 40°C to 60°C, dropwise add the mixture of catalyst II and deionized water, at 0.5～ The dripping is completed within 1 hour, the temperature is raised to 50°C to 60°C, the reaction is stirred for 5 to 10 hours, hexamethyldisiloxane is added, the temperature is raised to 60°C to 80°C, the reaction is stirred for 1 to 3 hours, and the layers are allowed to stand for stratification. The lower layer is taken out, and the photosensitive silicone resin is obtained by distillation under reduced pressure; Wherein, catalyst I is at least one of dibutyltin dilaurate, stannous octoate and butyltin diacetate; solvent I is at least one of chloroform, tetrahydrofuran and methyl ethyl ketone; solvent II is methyl ethyl ketone , at least one of ethyl acetate, acetone, toluene, xylene and tetrahydrofuran; catalyst II is at least one of glacial acetic acid, formic acid, hydrochloric acid, oxalic acid and sulfuric acid; solvent III is methanol, ethanol, isopropanol , at least one of ethyl formate, ethyl acetate, toluene, xylene and tetrahydrofuran; The siloxane photoinitiator described in step (1) has the following structure:

Wherein, X is derived from a small molecule photoinitiator with hydroxyl or amino group, namely benzoin, benzil, alkylphenone, benzophenone and thioxanthone with hydroxyl or amino group compound; R ₁ is -CH ₃ or -CH ₂ CH ₃ ; The siloxane PDMS described in step (2) has the following structure:

Wherein, R ₁ is -CH ₃ or -CH ₂ CH ₃ , and R ₂ is

is a natural number from 8 to 64; when R ₂ is the latter, its two ends are connected

The alkane-based siloxane described in step (3) has the following structure: R ₃ -Si(OR ₁ ) ₃ Wherein, R ₁ is -CH ₃ or -CH ₂ CH ₃ , and R ₃ is -CH ₃ , -CH ₂ CH ₃ or -CH ₂ CH ₂ CH ₃ ; The isocyanatosiloxane described in steps (1) and (2) is at least one of 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane. 2. the preparation method of photosensitive silicone resin as claimed in claim 1, is characterized in that, the mol ratio of the photoinitiator described in step (1) and described isocyanatosiloxane is 1:(1～1.5 ); the dosage of the catalyst I is 0.1% to 3% of the total mass of the photoinitiator and the isocyanate-based siloxane. 3. the preparation method of photosensitive silicone resin as claimed in claim 1, is characterized in that, The hydroxyl-terminated PDMS described in step (2) has a weight-average molecular weight of 1000-5000 g/mol; The molar ratio of the hydroxyl-terminated PDMS described in the step (2) and the isocyanate-based siloxane is 1: (1～5); the consumption of catalyst I is the total mass of the hydroxyl-terminated PDMS and the isocyanate-based siloxane. 0.1%～3%. 4. the preparation method of photosensitive silicone resin as claimed in claim 1, the deionized water molar dosage described in step (3) is described siloxane photoinitiator, siloxane PDMS and alkane silicon 3 to 9 times the total moles of oxane; The amount of catalyst II described in step (3) is 0.1% to 5% of the mass of the deionized water; The molar ratio of the siloxane photoinitiator, siloxane PDMS, alkane siloxane and hexamethyldisiloxane described in step (3) is 1:(0.01～1):(1～ 5): (0.5～2). 5. A photosensitive silicone resin, characterized in that it is prepared by the preparation method according to any one of claims 1 to 4. 6. the application of a kind of photosensitive organosilicon resin, it is characterized in that, after the photosensitive organosilicon resin described in claim 5, multifunctional acrylate resin and photoinitiator are mixed, carry out coating film on base material, carry out ultraviolet ray again Light irradiation, curing into a film; Wherein, the photoinitiator is selected from diethyl 2,4,6-trimethylbenzoylphosphonate, 2-phenyl-2,2-dimethylamino-1-(4-morpholinephenyl) )-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, α,α-diethoxyacetophenone, 1-hydroxy-cyclohexylbenzophenone, and 2,4 , one or more of 6-trimethylbenzoyl diphenyl phosphine oxide; The dosage of the photoinitiator is 1% to 5% of the total mass of the multifunctional acrylate resin and the photosensitive organosilicon resin; The multifunctional acrylate resin is selected from one or more of polyurethane acrylate resin, epoxy acrylate resin and polyester acrylate resin; The base material is selected from one or more of PC board, PMMA board, wood board, steel plate and glass board. 7 . The application according to claim 6 , wherein the amount of the photosensitive organosilicon resin is 1% to 15% of the mass of the multifunctional acrylate resin. 8 .