CN106927690A - A kind of method for making the antifouling anti-fingerprint of touch-screen glass surface - Google Patents

Abstract

The invention discloses a method for making the surface of touch screen glass antifouling and antifingerprint, the method comprises the synthesis of low surface energy hydrophobic and oleophobic component perfluoroalkyl substituted alkoxy siloxane oligomer, roughening the surface of touch screen glass Anti-fouling and anti-fingerprint treatment on the glass surface of the touch screen, in which the perfluoroalkyl-substituted alkoxysiloxane oligomer is a perfluoroalkyl-substituted α-olefin, vinyltrialkoxysilane and Si The hydrogen-containing siloxane oligomer with -H bond functionality ≥ 2 is prepared by hydrosilylation addition reaction. After diluting the perfluoroalkyl substituted alkoxysiloxane oligomer with a solvent, impregnate the glass surface roughened by aluminum heteroethylene modified nano-silica sol, and then cure it to endow the glass surface with antifouling and antifingerprint properties .

Description

A method of making the surface of touch screen glass antifouling and antifingerprint

technical field

The invention belongs to the field of fine chemical industry, and specifically relates to a method of treating touch screen glass with reactive perfluoroalkyl substituted alkoxysilane oligomer and nano-rough component aluminum-heteroethylene-modified nano-silica sol, so that the glass surface obtains anti-corrosion The method of anti-fingerprint performance of soiling.

Background technique

In today's society, electronic products such as mobile phones and tablet computers have become the necessities of people's life and travel. But how to prevent the touch screens of mobile phones and tablet computers from being polluted by sweat stains and fingerprints has become an urgent problem to be solved.

Treating the touch screen glass with low surface energy hydrophobic and oleophobic fluorine and siliconized (polymer) compound can endow the touch screen glass with waterproof, anti-fouling and anti-fingerprint properties. However, traditional fluorine and siliconized (polymeric) compounds are used for smooth touch screen glass surface treatment, with poor adhesion, low light transmittance, and unsatisfactory anti-fouling and anti-fingerprint effects; Combining with solid phase (CN103540183A), it can improve the effect of waterproof, anti-fouling and anti-fingerprint, but ordinary nanoparticles or powders are easy to fall off on the glass surface and affect the light transmission, so the effect is still not good. Based on this, the development of fluorosilicon compounds and related treatment methods suitable for glass surface treatment is not only necessary, but also has a good application prospect.

Long carbon chain perfluoroalkyl (R _f -), excellent water and oil repellency, combining R _f - with multifunctional alkoxysilane [R _f -C ₂ H ₄ Si(OR) ₃ ], not only can give The self-crosslinking reactivity of the target product can also effectively improve the adhesion and bonding fastness between perfluoroalkyl groups in the top coating film, the substrate, and nanoparticles, and improve the antifouling and antifingerprint effects.

It can also be seen from the literature that the raw materials used for the synthesis of fluorosilicone resins are currently mainly perfluoroalkylethyl trialkoxysilane and its derivatives, and no perfluoroalkyl-substituted-alkoxysiloxanes have been seen yet. ring body as raw material to synthesize hydrophobic and oleophobic perfluoroalkyl substituted-alkoxy siloxane oligomer, and then solidify it on the touch screen glass surface after rough treatment by aluminum heteroethylene modified nano-silica sol, thereby A report on anti-fouling and anti-fingerprint effects on glass surfaces.

Contents of the invention

In order to solve the problems of unsatisfactory anti-fouling and anti-fingerprint effects of fluorinated silicon (polymer) compounds on the surface of smooth touch screen glass, the invention provides a method for making the surface of touch screen glass anti-fouling and anti-fingerprint.

To achieve the above object, the present invention adopts the following technical solutions:

(1) Synthesis of low surface energy hydrophobic and oleophobic components - reactive perfluoroalkyl substituted alkoxysiloxane oligomers (R _f Si)

In a three-neck flask equipped with a reflux condenser, a thermometer, and a stirrer, the perfluoroalkyl-substituted α-olefin (R _f V), vinyltrialkoxysilane (VTS) and Si-H bond functionality Hydrogen-containing siloxane oligomers ≥2 are mixed in molar ratio n(R _f V):n(VTS):n(Si-H)=1-3:1-2:2-4, stirred and mixed, Heat up to 70-90°C, carry out hydrosilylation addition reaction at 70-90°C for 6-12 hours under the action of platinum catalyst, and then decompress and decompress under the conditions of absolute pressure of 60-260mmHg and temperature of 80-90°C Boil for 10-30min to obtain a colorless-light brown transparent liquid, i.e. a low surface energy hydrophobic and oleophobic component—a reactive perfluoroalkyl substituted alkoxysiloxane oligomer, denoted as R _f Si, the R _f Si is a single structural component or a mixture of multiple structural components, and the structures are shown in formulas (A)-(D).

In the formula, R=-CH ₃ ,-C ₂ H ₅ ; R _f is a perfluoroalkyl group or an organic group containing a perfluoroalkyl group, such as a perfluoroalkyl group containing 6-56 C atoms, a perfluoroaryl group group, perfluoroalkyl-substituted aromatic hydrocarbon group or perfluoropolyether group, preferably R _f =-C ₆ F ₁₃ ,-C ₈ F ₁₇ ,-C ₆ F ₅ ,-C ₆ H ₄ OCH ₂ C ₆ F ₁₃ ,-C ₆ H ₄ CH ₂ OC ₂ H ₄ C ₆ F ₁₃ ,-CH ₂ OC ₂ H ₄ C ₆ F ₁₃ ,-CH ₂ OC ₂ H ₄ C ₈ F ₁₇ ,-CH ₂ O(C ₃ F ₆ O) _6-18 CF ₃ etc.

(2) Pretreatment and roughening of touch screen glass

Etching the tempered touch screen glass surface with hydrofluoric acid can roughen the glass surface and generate abundant active Si-OH, which is beneficial to the substrate and nano-rough components and reactive perfluoroalkyl-substituted alkoxysiloxane The oligomer (R _f Si) undergoes a chemical reaction and produces a firm bond; in addition, modifying the etched touch screen glass with modified nano-silica sol (m-SiO ₂ ) can further roughen the glass surface and improve the hydrophobicity and oleophobicity. Effect. Based on this, the present invention adopts following pretreatment and roughening scheme:

Take the touch screen glass, immerse it in hydrofluoric acid with a mass fraction of 25-30%, etch it for 2-3s, rinse it with deionized water, dry it, and then immerse it into the aluminum-heteroethylene-modified nano-silica sol (m-SiO ₂ ) 3-5min, take it out, bake at 85-100°C for 5-15min, and then put it in a muffle furnace at 300-600°C for 0.5-4h. Then, cool to room temperature, clean with acetone and ultrasonic wave with a power of 90-150w for 3-5min at 25±2°C (that is, ultrasonically clean in acetone), and dry naturally to obtain aluminum-heteroethylene-modified nano-silica sol rough The chemically treated touch screen glass is referred to as m-SiO ₂ @glass.

(3) Anti-fouling and anti-fingerprint treatment on the glass surface of the touch screen

Dilute the accurately weighed R _f Si to a solid content of 0.1-0.3% with a good solvent for fluorosilicone resin (for example, a ketone solvent), and then immerse m-SiO ₂ @glass into the diluted R _f Si solution 3 -10s, take it out, bake at 80-100°C for 5-20min, and then cure at 120-150°C for 20-30min, the obtained sample is touch screen glass with anti-fouling and anti-fingerprint properties on the surface.

The perfluoroalkyl-substituted α-olefin (R _f V) is an alkene organic compound containing both a perfluoroalkyl group and an α-alkenyl group or a perfluoroaryl group and an α-alkenyl group in the molecular structure , mainly including perfluoroalkylethylene containing 6-56 carbon atoms, perfluoroalkyl allyloxyether, 4-perfluoroalkylstyrene, 4-perfluoroalkoxystyrene, pentafluorophenylethylene , for perfluoroalkoxymethylene styrene and allyloxy perfluoropolyether, etc., the preferred choice of perfluoroalkyl-substituted α-olefins is: perfluorohexylethylene (also known as trifluoro-1-octene) , Perfluorooctylethylene (also known as heptadecafluoro-1-decene), perfluorodecylethylene, perfluorodecyl allyloxyether, 2,3,4,5,6-pentafluorostyrene , Allyloxy perfluoropolyether with M _n of 1000-3000, 4-perfluorohexylstyrene, 4-tridecafluorohexyloxymethylenestyrene, 4-(1H,1H,2H,2H-perfluoro octyloxymethylene) styrene, etc.

The hydrogen-containing siloxane oligomers with Si-H bond functionality ≥ 2 are mainly tetramethyldisiloxane, 1,3,5,7-tetrahydro-1,3,5,7-tetrahydro Methylcyclotetrasiloxane (D ₄ ^H ) or a mixture of the two in any proportion;

The vinyltrialkoxysilane (VTS) mainly includes vinyltrimethoxysilane (MTMS) and vinyltriethoxysilane (MTES);

The platinum catalyst is mainly hexachloroplatinic acid, small molecule complex platinum catalyst such as KP22 (divinyltetramethyldisiloxane complex platinum, Shanghai Neutron Star Chemical Technology Co., Ltd.), KP23 (divinyltetraphenyl Platinum disiloxane complex, Shanghai Neutron Star Chemical Technology Co., Ltd.), etc., the dosage is 50-100ppm;

The described aluminum heteroethylene modified nano-silica sol (m-SiO ₂ ) is prepared by the following method: in a three-necked bottle equipped with a reflux condenser, a thermometer, and a stirrer, orthosilicate (TOS) and 1 , Mix 2-bis(trialkoxysilyl)ethane (BTRSE) at a molar ratio of 1-10:0.05-0.2, then add ethanol with a total mass of TOS and BTRSE of 150-300%, stir and mix, and heat Raise the temperature to 40-70°C, add 5-10% AlCl ₃ -2M hydrochloric acid solution dropwise to adjust the pH of the system to 3-4, and then control the amount of deionized water added dropwise so that the molar ratio of H ₂ O:Si-OR in the system = 1.2-1.5:1, then the temperature is controlled at 40-70°C for hydrolysis and polycondensation reaction for 10-24h. After the reaction is finished, dilute the product to a solid content of 3.0-5.0% with ethanol, then add about 0.1-0.3g epoxy silane coupling agent in every 100g product dilution to increase the adhesion of silicon nanoparticles, stir The homogeneously obtained transparent liquid, that is, aluminum-heteroethylene-modified nano-silica sol (m-SiO ₂ ), has an average particle diameter of 20-300nm and a concentration of about 3.0-5.0%.

The orthosilicate is mainly ethyl orthosilicate or methyl orthosilicate.

The 1,2-bis(trialkoxysilyl)ethane (BTRSE) is mainly 1,2-bis(triethoxysilyl)ethane (BTESE), 1,2-bis(trimethyl Oxysilyl)ethane (BTMSE).

The epoxy silane coupling agent is mainly 3-(2,3-glycidoxy)propyltrimethoxysilane, 3-(2,3-glycidoxy)propyltriethoxysilane , 3-(2,3-Glycidoxy)propylmethyldimethoxysilane, 3-(2,3-Glycidoxy)propylmethyldiethoxysilane.

The surface has touch screen glass with anti-fouling and anti-fingerprint properties, water resistance is represented by the static contact angle (θ _{H O} ) of water droplets on the glass surface, and antifouling performance is expressed by the static contact angle (θ _heptane ) of oily substance (heptane) on the glass surface _alkane ) means that the JC 2000C contact angle measuring instrument of Shanghai Zhongchen Digital Co., Ltd. is used to measure at 25±2°C, the measurement result of θ _H2O is 100°-117°, and the θ _heptane is 48°-70.5° (the larger the θ, the It means that the waterproof and antifouling performance of the glass surface is better); the light transmittance of the touch screen glass surface is measured with a UV-265FW ultraviolet-visible spectrophotometer of Japan Shimadzu Corporation, and the light transmittance measurement result is 82-95%; and the treatment The final touch screen glass is evaluated by hand touch method, the surface is smooth, and fingerprints are easy to remove with soft glasses cloth.

The beneficial effects of the present invention are reflected in:

In the present invention, α-olefins and vinyl trialkoxysilanes substituted with long carbon chain perfluoroalkyl groups are subjected to hydrosilylation addition reaction with hydrogen-containing siloxane oligomers with Si-H bond functionality ≥ 2 in the molecule. Firstly, the low surface energy, hydrophobic and oleophobic perfluoroalkyl substituted alkoxysiloxane oligomer R _f Si was synthesized, and then used as a reactive antifouling and anti-fingerprint component, and then impregnated with R _f Si and subjected to hydrogen fluorine Touch screen glass roughened by acid etching and aluminum-heteroethylene modified nano-silica sol, and using the characteristic that the siloxyl group (Si-OR) in the R _f Si molecule can react with Si-OH on the surface of glass and silica sol under high temperature conditions , not only permanently immobilize and chemically bond the hydrophobic and oleophobic perfluoroalkyl-substituted siloxane oligomers on the glass surface, but also make the treated glass both light-transmitting, waterproof, anti-fouling and anti-fingerprint.

detailed description

The present invention will be further described below in conjunction with the examples, but the present invention is not limited to the following examples.

In the present invention, α-olefins substituted with long carbon chain perfluoroalkyl groups, polyfunctional hydrogen-containing siloxane oligomers, and vinyl trialkoxysilanes are subjected to hydrosilylation addition reaction to firstly synthesize reactive hydrophobic and oleophobic Fluoroalkyl substituted alkoxysiloxane oligomers (R _f Si), and then cured R _f Si on the touch screen glass surface roughened by aluminum heteroethylene modified nano-silica sol (m-SiO ₂ ) , so that the glass surface can obtain anti-fouling and anti-fingerprint effects.

(1) Preparation of aluminum heteroethylene modified nano-silica sol (m-SiO ₂ )

In a three-neck flask equipped with a reflux condenser, a thermometer, and a stirrer, orthosilicate (TOS) and 1,2-bis(trialkoxysilyl)ethane (BTRSE) in a molar ratio of 1-10 : 0.05-0.2 mixed, then add TOS and BTRSE two total amount of 150-300% ethanol, stir and mix, heat up to 40-70 ° C, dropwise add 6% AlCl ₃ -2M hydrochloric acid solution to adjust the system pH = 3- 4. Then control the amount of deionized water added dropwise so that the molar ratio of H ₂ O:Si-OR in the system is about 1.2:1, and then carry out the hydrolysis and polycondensation reaction at 40-70°C for 10-24 hours. After the reaction is over, dilute the product with ethanol to a solid content of about 5%, and then add 5-10 drops (about 0.1-0.3g) of 3-(2,3-epoxypropoxy)propyl to every 100g of the diluted solution Trimethoxysilane (KH-560) is used to increase the adhesion of nanoparticles. The transparent liquid obtained after this treatment is aluminum heteroethylene modified nano-silica sol (m-SiO ₂ ). The specific preparation conditions and raw material dosage are detailed See Table 1.

Table _1. Preparation conditions and raw material consumption of m-SiO

^* ——The amount of ethanol is calculated by the mass fraction of the total amount of orthosilicate and 1,2-bis(trialkoxysilyl)ethane;

^** ——The amount of KH-560 refers to the mass of KH-560 added per 100 grams of dilution.

(2) Touch screen glass surface treatment

Example 1

(1) Synthesis of low surface energy hydrophobic and oleophobic components—reactive perfluoroalkyl-substituted alkoxysiloxane oligomers (R _f Si-1)

In a 50mL three-necked bottle equipped with a reflux condenser, a thermometer, and a stirrer, accurately weigh 4.46g (0.01mol) of heptadecafluoro-1-decene (R _f17 V), 1.90g (0.01mol) of ethylene Triethoxysilane (MTES) and 1.34g (0.01mol) tetramethyldisiloxane (D ₂ ^H , containing Si-H 0.02mol) with a Si-H bond functionality of 2 [the molar ratio n (R _f17 V):n(MTES):n(Si-H)=1:1:2], mechanically stirred and mixed, heated to 70°C, then added 50ppm complex platinum catalyst KP22 and reacted at 70°C for 10h , and then under the conditions of absolute pressure of 60mmHg and temperature of 90°C, decompression and decompression for 10 minutes to obtain a light brown transparent liquid, that is, the structure is shown in formula (A), R = -C ₂ H ₅ , R _f = -C ₈ F ₁₇ perfluoroalkyl substituted alkoxysiloxane oligomer—1-heptadecafluorodecyl-2-(triethoxysilylethyl)tetramethyldisiloxane, denoted as R _f Si-1.

(2) Pretreatment and roughening of touch screen glass surface

Take a clean tempered touch screen glass, etch it with 25% hydrofluoric acid for 3 seconds, rinse it with deionized water, dry it, and then impregnate it into the aluminum heteroethylene modified nano-silica sol m-SiO ₂ -1 (see Table 1) Take it out for 5 minutes, bake it at 85°C for 10 minutes, and then put it in a muffle furnace at 300°C for 4 hours. Then, cool to room temperature, clean with acetone and ultrasonic wave with a power of 99w for 3 minutes at 25±2°C, and let it dry naturally to obtain the roughened touch screen glass of aluminum-heteroethylene-modified nano-silica sol, which is recorded as m-SiO ₂ @glass-1.

(3) Anti-fouling and anti-fingerprint treatment on the glass surface of the touch screen

Accurately weigh 0.10g of R _f Si-1, dilute it with 99.90g of acetone to a solid content of about 0.1%, then immerse m-SiO ₂ @glass-1 into the R _f Si-1 dilution for 5s, take out , baked at 80°C for 10 minutes, and then cured at 150°C for 30 minutes, the obtained sample, that is, the touch screen glass with antifouling and antifingerprint properties on the surface, θ _H2O = 100.9°, _θheptane = 48°, light transmittance T = 95%, The surface of the touch screen glass after treatment is smooth, and fingerprints are easy to wipe and remove with glasses cloth.

Example 2

(1) Synthesis of low surface energy hydrophobic and oleophobic components - reactive perfluoroalkyl-substituted alkoxysiloxane oligomers (R _f Si-2)

In a 50mL three-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, accurately weigh 13.38g (0.03mol) of heptadecafluoro-1-decene (R _f17 V), 1.93g (0.01mol) of ethylene Triethoxysilane (MTES) and 24.1g (0.01mol) tetramethylcyclotetrasiloxane (D ₄ ^H , containing Si-H 0.04mol) with Si-H bond functionality of 4 [molar ratio n( R _f17 V): n(MTES):n(Si-H)=3:1:4], mechanically stirred and mixed, heated to 90°C, then added 100ppm complex platinum catalyst KP22 and reacted at 90°C for 6h, Then under the conditions of absolute pressure of 260mmHg and temperature of 90°C, decompression and lower boiling for 30 minutes, to obtain a light brown transparent liquid, that is, the structure is shown in formula (B), R = -C ₂ H ₅ , R _f = -C ₈ Perfluoroalkyl-substituted alkoxysiloxane oligomer of F _17——1 -triethoxysilylethyl-3,5,7-tris(heptadecafluorodecyl)-1,3,5,7 - Tetramethylcyclotetrasiloxane, denoted R _f Si-2.

(2) Pretreatment and roughening of touch screen glass surface

Take clean tempered touch screen glass, etch it with 30% hydrofluoric acid for 2 seconds, rinse it with deionized water, dry it, and then impregnate it into aluminum heteroethylene modified nano-silica sol m-SiO ₂ -2 (see Table 1) Take it out for 3 minutes, bake at 100°C for 5 minutes, and then put it in a muffle furnace at 580°C for 30 minutes to cure. Cool to room temperature, clean with acetone and ultrasonic wave with a power of 99w for 5min at 25±2°C, and then dry it naturally to obtain the roughened touch screen glass of aluminum-heteroethylene modified nano-silica sol, denoted as m-SiO ₂ @glass-2.

(3) Anti-fouling and anti-fingerprint treatment on the glass surface of the touch screen

Accurately weigh 0.10g of R _f Si-2, dilute it with 99.90g of acetone to a solid content of about 0.1%, then immerse m-SiO ₂ @glass-2 into the diluted R _f Si-2 for 3s, take out , baked at 80°C for 10 minutes, and then cured at 150°C for 30 minutes, the obtained sample, that is, the touch screen glass with antifouling and antifingerprint properties on the surface, θ _H2O = 115.0°, _θheptane = 70.5°C, light transmittance T = 94%, The treated glass surface is smooth, and fingerprints are easy to wipe off with glasses cloth.

Example 3

(1) Synthesis of low surface energy hydrophobic and oleophobic components - reactive perfluoroalkyl-substituted alkoxysiloxane oligomers (R _f Si-3)

In a 50mL three-necked bottle equipped with a reflux condenser, a thermometer, and a stirrer, accurately weigh 6.92g (0.02mol) of perfluorohexylethylene (R _f13 V), 2.96g (0.02mol) of vinyltrimethoxy Silane (MTMS) and 24.1g (0.01mol) tetramethylcyclotetrasiloxane (D ₄ ^H , containing Si-H 0.04mol) with Si-H bond functionality of 4 [molar ratio n(R _f13 V): n(MTMS):n(Si-H)=2:2:4], mechanical stirring and mixing, heating to 85°C, then adding 60ppm complex platinum catalyst KP23 and then reacting at 85°C for 12h, then under absolute pressure of 210mmHg, temperature 85 ℃ under the condition of decompression and lower boiling for 15min, a colorless transparent liquid was obtained, that is, the structure as shown in formula (C) and (D), R = -CH ₃ , R _f = -C ₆ F ₁₃ Perfluoroalkyl-substituted alkoxysiloxane oligomer—bis(tridecafluorooctyl)bis(trimethoxysilylethyl)tetramethylcyclotetrasiloxane, denoted as R _f Si-3.

(2) Pretreatment and roughening of touch screen glass surface

Take clean tempered touch screen glass, etch it with 25% hydrofluoric acid for 3 seconds, rinse it with deionized water, dry it, and then impregnate it into nano-silica sol m-SiO ₂ -1 modified by aluminum heteroethylene (see Table 1) Mixed sols composed of aluminum heteroethylene modified nano-silica sol m-SiO ₂ -3 (see Table 1) (mass fractions of m-SiO ₂ -1 and m-SiO ₂ -3 in mixed sols 70% and 30% respectively) for 4 minutes, take it out, bake at 90°C for 15 minutes, and then put it in a muffle furnace at 450°C for 2 hours. Then, cool to room temperature, clean with acetone and 99w ultrasonic wave at 25±2°C for 5 minutes, and dry naturally to obtain the touch screen glass roughened by aluminum-heteroethylene-modified nano-silica sol, denoted as m-SiO ₂ @glass-3.

(3) Anti-fouling and anti-fingerprint treatment on the glass surface of the touch screen

Accurately weigh 0.20g of R _f Si-3, dilute it with 99.80g of acetone to a solid content of about 0.2%, then immerse m-SiO ₂ @glass-3 into the R _f Si-3 dilution for 3s, take out , baked at 90°C for 15 minutes, and then cured at 150°C for 30 minutes. The obtained sample, that is, the touch screen glass with anti-fouling and anti-fingerprint properties on the surface, θ _H2O = 113.7°C, _θheptane = 69.5°C, and the light transmittance is about 91%. The treated glass surface is smooth, and fingerprints are easy to wipe off with glasses cloth.

Example 4

(1) Synthesis of low surface energy hydrophobic and oleophobic components - reactive perfluoroalkyl-substituted alkoxysiloxane oligomers (R _f Si-4)

In a 50mL three-necked bottle equipped with a reflux condenser, a thermometer, and a stirrer, accurately weigh 3.88g (0.02mol) of 2,3,4,5,6-pentafluorostyrene (R _f5 V), 3.80 g (0.02mol) vinyltriethoxysilane (MTES) and 2.68g (0.02mol) tetramethyldisiloxane (D ₂ H, containing Si-H 0.04mol) with Si-H bond functionality of 2 [The molar ratio of the three n(R _f5 V):n(MTES):n(Si-H)=1:1:2] Mix, mechanically stir and mix, heat up to 70°C, then add 80ppm hexachloroplatinum After the acid reaction, react at 70°C for 12 hours, and then decompress and decompress for 12 minutes under the conditions of absolute pressure of 160mmHg and temperature of 85°C to obtain a colorless transparent liquid, that is, the structure is shown in formula (A), R=-C ₂ H ₅ , R _f =-C ₆ F ₅ perfluoroalkyl-substituted alkoxysiloxane oligomer——1-pentafluorophenethyl-2-triethoxysilylethyltetramethyldisiloxane , denoted as R _f Si-4.

(2) Pretreatment and roughening of touch screen glass

Take clean tempered touch screen glass, etch it with hydrofluoric acid with a mass fraction of 25% for 2.5s, rinse it with deionized water, dry it, and then impregnate it into aluminum heteroethylene modified nano-silica sol m-SiO ₂ -4 (see Table 1) for 5 minutes, take it out, bake at 100°C for 8 minutes, and then put it in a muffle furnace at 350°C for 3 hours. Cool to room temperature, clean with acetone and ultrasonic wave with a power of 99w for 3 minutes at 25±2°C, and dry naturally to obtain the touch screen glass roughened by aluminum-heteroethylene-modified nano-silica sol, denoted as m-SiO ₂ @ Glass-4.

(3) Anti-fouling and anti-fingerprint treatment on the glass surface of the touch screen

Accurately weigh 0.15g of R _f Si-4, dilute it with 99.85g of acetone to a solid content of 0.15%, then immerse m-SiO ₂ @glass-4 into the R _f Si-4 dilution for 5s, take it out, Bake at 100°C for 10 minutes, and then cure at 150°C for 25 minutes. The obtained sample is a touch screen glass with antifouling and antifingerprint properties on the surface, θ _H2O = 110.2°, _θheptane = 56.7°C, and the light transmittance is about 82.8%. The smoothness of the glass surface and the easy removal of fingerprints are average.

Example 5

(1) Synthesis of low surface energy hydrophobic and oleophobic components - reactive perfluoroalkyl substituted alkoxysiloxane oligomers (R _f Si-5)

In a 50mL three-necked bottle equipped with a reflux condenser, a thermometer, and a stirrer, accurately weigh 4.8g (0.01mol) of 4-(1H,1H,2H,2H-perfluorooctyloxymethylene)styrene ( R _f13ph V), 1.90g (0.01mol) of vinyltriethoxysilane (MTES) and 1.34g (0.01mol) of tetramethyldisiloxane ( ^D2H , containing Si-H0.02mol)[the molar ratio of the three n(R _f13ph V):n(MTES):n(Si-H)=1:1:2] mixed, mechanically stirred and mixed, heated to 70°C, and then After adding 85ppm complex platinum catalyst KP23, react at 70°C for 10h, then decompress and decompress for 15min under the conditions of absolute pressure of 160mmHg and temperature of 90°C to obtain a colorless transparent liquid, that is, the structure is as shown in formula (A): R=-C ₂ H ₅ , R _f =-C ₆ H ₄ CH ₂ OC ₂ H ₄ C ₆ F ₁₃ perfluoroalkyl-substituted alkoxysiloxane oligomer——1-(perfluorooctyloxy Methylenephenylethyl)-2-triethoxysilylethyltetramethyldisiloxane, denoted as R _f Si-5.

(2) Pretreatment and roughening of touch screen glass

Take a clean tempered touch screen glass, etch it with 30% hydrofluoric acid for 3 seconds, rinse it with deionized water, dry it, and then impregnate it into the aluminum heteroethylene modified nano-silica sol m-SiO ₂ -1 (see Table 1) The mixed sol composed of aluminum heteroethylene modified nano-silica sol m-SiO ₂ -4 (see Table 1) (the mass fractions of m-SiO ₂ -1 and m-SiO ₂ -4 in the mixed sol are equal to 50%) for 3.5 minutes, take it out, bake at 100°C for 10 minutes, and then place it in a muffle furnace at 590°C for 30 minutes to cure. Cool to room temperature, clean with acetone and ultrasonic wave with a power of 99w for 5min at 25±2°C, and then dry it naturally to obtain the roughened touch screen glass of aluminum-heteroethylene modified nano-silica sol, denoted as m-SiO ₂ @glass-5.

(3) Anti-fouling and anti-fingerprint treatment on the glass surface of the touch screen

Accurately weigh 0.3g of R _f Si-5, dilute it with 99.7g of acetone to a solid content of about 0.3%, then immerse m-SiO ₂ @glass-5 into the R _f Si-5 dilution for 4s, Take it out, bake it at 100°C for 20 minutes, and then cure it at 150°C for 30 minutes. The obtained sample is a touch screen glass with anti-fouling and anti-fingerprint properties on the surface, θ _H2O = 116.2°, θ _Heptane = 67.4°, and the light transmittance is about 90%. , The treated glass surface is smooth, and fingerprints are easy to remove with glasses cloth.

Example 6

(1) Synthesis of low surface energy hydrophobic and oleophobic components - reactive perfluoroalkyl substituted alkoxysiloxane oligomers (R _f Si-6)

In a 50mL three-necked bottle equipped with a reflux condenser, a thermometer, and a stirrer, accurately weigh 10.0g (0.01mol) of allyloxy perfluoropolyether (Mn=1000), 1.90g (0.01mol) of ethylene Triethoxysilane (MTES) and 1.34g (0.01mol) of tetramethyldisiloxane (D ² H, containing Si-H 0.02mol) with Si-H bond functionality of 2 [the molar ratio n (Allyloxy perfluoropolyether): n(MTES):n(Si-H)=1:1:2] mix, mechanically stir and mix, heat up to 70°C, then add 100ppm complex platinum catalyst KP22 Afterwards, react at 70°C for 12h, then decompress and deboil for 10min under the conditions of absolute pressure of 210mmHg and temperature of 90°C to obtain a colorless transparent liquid, that is, the structure is shown in formula (A), R=-C ₂ H ₅ , R _f =-CH ₂ O(C ₃ F ₆ O) ₆ CF ₃ perfluoroalkyl-substituted alkoxysiloxane oligomer——1-perfluoropolyetherpropyl-2-triethoxysilane Ethyltetramethyldisiloxane, denoted as R _f Si-6.

(2) Pretreatment and roughening of touch screen glass

Take a clean tempered touch screen glass, etch it with 25% hydrofluoric acid for 3 seconds, rinse it with deionized water, dry it, and then impregnate it into the aluminum heteroethylene modified nano-silica sol m-SiO ₂ -2 (see Table 1) Take it out for 5 minutes, bake it at 100°C for 10 minutes, and then put it in a muffle furnace at 300°C for 2 hours. Cool to room temperature, clean with acetone and ultrasonic wave with a power of 99w for 3 minutes at 25±2°C, and then dry it naturally to obtain the roughened touch screen glass of aluminum-heteroethylene modified nano-silica sol, denoted as m-SiO ₂ @glass-6.

(3) Anti-fouling and anti-fingerprint treatment on the glass surface of the touch screen

Accurately weigh 0.2g of R _f Si-6, dilute it with 99.80g of acetone to a solid content of 0.2%, then immerse m-SiO ₂ @glass-6 into the R _f Si-6 dilution for 5s, take out , baked at 85°C for 10 minutes, and then cured at 150°C for 25 minutes. The obtained sample, that is, the glass with anti-fouling and anti-fingerprint properties on the surface, θ _H2O = 114.6°C, _θheptane = 70.1°C, and the light transmittance is about 90.2%. After the glass surface is smooth, fingerprints are easy to wipe off with glasses cloth.

Claims (10)

1. A method for making the surface of the touch screen glass antifouling and antifingerprint, characterized in that: comprising the following steps: 1) Synthesis of reactive perfluoroalkyl-substituted alkoxysiloxane oligomers Stir and mix vinyltrialkoxysilane, perfluoroalkyl-substituted α-olefin and hydrogen-containing siloxane oligomer with Si-H bond functionality ≥ 2 to obtain mixture A, and heat mixture A to 70 Add a platinum catalyst to the mixture A after -90°C, and then carry out hydrosilylation addition reaction at 70-90°C for 6-12 hours. Remove the low boiler for 10-30min to obtain a transparent liquid, that is, a reactive perfluoroalkyl substituted alkoxysiloxane oligomer, denoted as R _f Si; Si-H of the hydrogen-containing siloxane oligomer Bond: α-olefin substituted by perfluoroalkyl: the molar ratio of vinyltrialkoxysilane is 2-4:1-3:1-2; 2) Roughening of touch screen glass Soak the touch screen glass in hydrofluoric acid with a mass fraction of 25-30% for 2-3s, rinse and dry it, then immerse it in aluminum-heteroethylene-modified nano-silica sol for 3-5 minutes, and bake it at 85-100°C after immersion 5-15min, then placed in a muffle furnace at 300-600°C for 0.5-4h to solidify, cooled to room temperature after solidification, then ultrasonically cleaned and dried in sequence to obtain a roughened touch screen treated with aluminum heteroethylene modified nano-silica sol Glass, recorded as m-SiO ₂ @glass; 3) Anti-fouling and anti-fingerprint treatment on the glass surface of the touch screen Immerse m-SiO ₂ @glass into the R _f Si solution with a solid content of 0.1-0.3% for 3-10s, bake at 80-100°C for 5-20min after dipping, and then cure at 120-150°C for 20-30min, A touch screen glass with anti-fouling and anti-fingerprint properties on the surface is obtained. 2. A method for making the surface of the touch screen glass antifouling and antifingerprint according to claim 1, characterized in that: the reactive perfluoroalkyl substituted alkoxysiloxane oligomer is selected from the group consisting of formula (A)- (D) A mixture of one or more of the structures shown: In the formula, R is selected from -CH ₃ or -C ₂ H ₅ ; R _{f is} selected from perfluoroalkyl groups or organic groups containing perfluoroalkyl groups. 3. A method for making the touch screen glass surface antifouling and antifingerprint according to claim 1, characterized in that: the perfluoroalkyl-substituted α-olefin contains both perfluoroalkyl and α-olefin in the molecular structure. Alkenyl or alkenyl organic compounds containing both perfluoroaryl and α-alkenyl. 4. A method for making the surface of the touch screen glass antifouling and antifingerprint according to claim 1, characterized in that: the hydrogen-containing siloxane oligomer is selected from tetramethyldisiloxane, 1,3, 5,7-tetrahydro-1,3,5,7-tetramethylcyclotetrasiloxane or a mixture of the two in any proportion. 5. A method for making the surface of the touch screen glass antifouling and antifingerprint according to claim 1, characterized in that: the vinyltrialkoxysilane is selected from vinyltrimethoxysilane or vinyltriethoxy silane. 6. A kind of method that makes the surface of touch screen glass antifouling and antifingerprint according to claim 1, it is characterized in that: the preparation method of described aluminum heteroethylene modified nano-silica sol comprises the following steps: orthosilicate, 1,2-bis(trialkoxysilyl)ethane and ethanol with a total mass of 150-300% of the two were stirred and mixed to obtain mixture B, orthosilicate: 1,2-bis(trialkoxysilyl) ) The molar ratio of ethane is 1-10:0.05-0.2, heat the mixture B to 40-70°C, then add AlCl ₃ -2M hydrochloric acid solution to the mixture B to adjust the pH of the system to 3-4, and then add water to the system The molar ratio of H ₂ O:Si-OR is 1.2-1.5:1, then carry out hydrolysis and polycondensation reaction at 40-70°C for 10-24h, and dilute with ethanol to a solid content of 3.0-5.0% after the reaction to obtain a diluted liquid, and then stirred with diluent mass 0.1-0.3% epoxy silane coupling agent to obtain a transparent liquid, that is, aluminum heteroethylene modified nano-silica sol, the average particle size of the nanoparticles in the sol is 20-300nm. 7. A method for making the glass surface of the touch screen anti-fouling and anti-fingerprint according to claim 6, characterized in that: the orthosilicate is selected from ethyl orthosilicate or methyl orthosilicate. 8. A method for making the surface of the touch screen glass antifouling and antifingerprint according to claim 6, characterized in that: said 1,2-bis(trialkoxysilyl)ethane is selected from 1,2-bis (triethoxysilyl)ethane or 1,2-bis(trimethoxysilyl)ethane. 9. A method for making the surface of the touch screen glass antifouling and antifingerprint according to claim 6, characterized in that: the epoxy silane coupling agent is selected from 3-(2,3-glycidyloxy)propane Trimethoxysilane, 3-(2,3-glycidoxy)propyltriethoxysilane, 3-(2,3-glycidoxy)propylmethyldimethoxysilane or 3- (2,3-Glycidoxy)propylmethyldiethoxysilane. 10. A method for making the touch screen glass surface antifouling and antifingerprint according to claim 1, characterized in that: the static contact angle of water on the touchscreen glass surface with antifouling and antifingerprint performance is 100°-117°, The static contact angle of heptane on the glass surface is 48.0°-70.5°; the light transmittance of the glass is 82-95%.