KR20160024470A - Manufacturing method for titanium dioxide coating solution - Google Patents

Abstract

Provided is a manufacturing method of titanium dioxide coating solution which has improved hardness, transparency, chemical resistance, water resistance, and optical properties by attaching a silane polymer on the surface of a titanium dioxide nanoparticle. According to the present invention, the manufacturing method of titanium dioxide coating solution comprises: a first step for manufacturing a silane polymer by making a reaction between silane and a reactive monomer; and a second step for manufacturing a complex titanium dioxide particle by making a reaction between the silane polymer and a titanium oxide particle.

Description

[0001] The present invention relates to a titanium dioxide coating solution,

The present invention relates to a method for producing a coating liquid, and more particularly, to a method for producing a titanium dioxide coating liquid having excellent coating properties.

Hybrid composite materials are produced by combining organic components and inorganic components in a novel manner, and thus, as disclosed in Japanese Patent No. 351627, Japanese Patent No. 526761 and Japanese Patent No. 1297447, various combinations of electrical conductivity, adsorptivity, transparency, ion conductivity, It is a material that can show characteristics at the same time.

In order for hybrid hybrid materials to exhibit properties different from those of conventional composite materials, organic or inorganic materials must be combined at an atomic or molecular level, while the properties of existing composite materials follow a simple mixing rule, New material properties and synergy effects can be expected. Therefore, organic / inorganic hybrid materials can be defined as the next generation new materials that can overcome the limitation of physical properties of existing composite materials, and various attempts are being made.

In addition, hybrid composite materials are technologies that can control the structure at the molecular level and thereby impart customized functionality and structure to the material. Through this, it is possible to produce hybrid organic / inorganic complex materials or fiber materials having a controlled size, Can be produced.

These materials can be applied to various fields such as electronics, information communication, bio, energy, environment, fuel, medical, space and so on.

Organic and inorganic composite materials can be combined with each other to function and structure, so that organic and inorganic composite materials having various properties can be manufactured.

In particular, since the organic and inorganic complexes are prepared in a solution state, they can be applied to a solution coating process and are actively utilized in various coatings. Recently, it has attracted attention as a new coating material which can overcome drawbacks of inorganic ceramic coating, use of high temperature and formation of cracks, disadvantages of organic polymer coating, low heat resistance and low protection.

Especially, it is possible to manufacture transparent materials due to the nature of molecular composites that are molecularly structured and have no distinction of constituent phases, and thus they are mainly applied to coating of transparent materials such as glass and plastics. Also, since the coating process temperature is relatively low, the functionality of the organic material can be easily introduced into the network structure of the inorganic material, so that the functionalization is easy and the coating material is very useful.

On the other hand, in the case of the plastic material coating, the wear resistance can be increased by using inorganic molecules or nanofill materials (SiO ₂ or Al ₂ O ₃ ) dispersed and introduced into the coating material. In addition to the excellent mechanical strength of the glass, The functionalization of the coating material may add special optical effects or functionality (such as fogging, pollution prevention, anti-static). Therefore, it is the main point of view to apply abrasion resistance and additional value to glass or plastic material based on sol - gel process in organic - inorganic hybrid material coating.

The basic characteristics of the organic-inorganic composite coating can be controlled according to the amount and nature of organic and inorganic molecular structural units. Therefore, the main advantage of the organic hybrid coating is the combination of hardness (amount of inorganic network structure) and flexibility (nature and amount of organic crosslinking). In addition, the chemical functionalization of the organic-inorganic composite material can realize chemically stable (non-dissolved) functionality by the modification of the network structure by covalent bonding of the organic molecules to the inorganic network structure.

An object of the present invention is to provide a titanium dioxide coating composition composition having improved hardness, transparency, chemical resistance, water resistance and optical properties by bonding a silane polymer to the surface of titanium dioxide nanoparticles.

In order to accomplish the above object, the present invention provides a process for producing a silane polymer, comprising: a first step of reacting silane with a reactive monomer to prepare a silane polymer; And a second step of reacting the silane polymer with titanium dioxide particles to prepare composite titanium dioxide particles.

Preferably, the first step is a polymerization using a solvent, and the solvent is selected from the group consisting of methanol, ethanol, isopropanol, propylene glycol methyl ether, ethylene glycol methyl ether, acetone, methyl ethyl ketone, toluene, And ethylene glycol methyl ether.

Preferably, the first step is a polymerization using a catalyst, and the catalyst is selected from the group consisting of titanium (III) trichloride, trichloroacetic acid, nitric acid, hydrochloric acid, inorganic or Lewis acids such as boron trifluoride, triethylamine, triethanolamine , Triethylene pentaamine, and triethylene tetraamine.

Preferably, the first step is a step of carrying out a stirring reaction at 50 to 80 캜.

Preferably, the second step is characterized by further comprising a purified water.

Preferably, the second step further comprises an acid.

Preferably, the titanium dioxide particles have a particle size of 10 nm to 150 nm.

Preferably, the method further comprises a third step of mixing and dispersing the composite titanium dioxide particles of the second step in a solvent.

More preferably, the dispersion in the third step is dispersed using ultrasonic waves, and the ultrasonic waves are dispersed for 30 to 60 minutes using an output of 300 to 1000 watts and 50 to 60 kHz.

Preferably, the solvent in the third step is at least one of methanol, ethanol, isopropanol, propylene glycol methyl ether, ethylene glycol methyl ether, acetone, methyl ethyl ketone, toluene, xylene and triethylene glycol methyl ether .

Preferably, the third step is further carried out by dispersing a dispersant, wherein the dispersant is selected from the group consisting of oleic acid, decanoic acid, dodecanoic acid, sodium oleate, decanoic acid amine, polyethylene glycol, polypropylene glycol, triethylene glycol methyl ether, trimethyl Cetylamine bromide, trioctylphosphine oxide, sodium dodecylsulfonate, 2-methoxy-1-propanol and butyl acetate.

Preferably, the third step further comprises dispersing an additive.

Preferably, the purified water is mixed at a ratio of 0.1 to 1.5 mol per 1 mol of the alkoxy group of the silane.

Preferably, the acid is mixed at a ratio of 0.001 to 0.5 parts by weight based on 1 part by weight of the silane polymer material.

Preferably, the catalyst is mixed at a ratio of 0.01 to 0.5 parts by weight based on 1 part by weight of the monomer.

Preferably, the dispersing agent is mixed at a ratio of 5 to 50 parts by weight based on 1 part by weight of the titanium dioxide.

Preferably, the silane is characterized by the following molecular formula. (Molecular formula: R2-Si (OR) 3, wherein OR is a substance having a linear, branched or cyclic type having 1 to 4 carbon atoms having only one or two or more alkoxy functional groups, R2 is an allyl group, An epoxy group, an aminoalkyl group, a phenyl group, a cycloalkyl group, or a substance having a carbon number of 1 to 10)

Preferably, the reactive monomer is characterized by comprising the following molecular formula. (OCO = CH2) n wherein n is an integer of 1 to 3, R1 is an alkyl group, a phenyl group, a cycloalkyl group, a phenylalkyl group, an epoxy group, an ethylene glycol, an allyl group, A substance having 1 to 15 carbon atoms)

Preferably, the silane polymer is characterized by the following molecular formula. (OR) 3, m is an integer of 1 to 10, OR is a linear, branched or cyclic alkyl group having one or more alkoxy functional groups, R 1 is a substance having 1 to 15 carbon atoms having an alkyl group, a phenyl group, a cycloalkyl group, a phenylalkyl group, an epoxy group, an ethylene glycol, an allyl group, an alkoxy group or an ester group, , R2: a substance having 1 to 10 carbon atoms, which has at least one allyl group, an acrylic group, an epoxy group, an aminoalkyl group, a phenyl group, and a cycloalkyl group,

The titanium dioxide coating liquid preparation method according to the present invention is a titanium dioxide coating composition in which a silane polymer is bonded to the surface of titanium dioxide particles and has excellent storage stability, hardness, transmittance, moisture resistance and adhesion. The protective coating of the coating liquid exhibits excellent abrasion resistance and moisture resistance of high hardness and exhibits excellent adhesion, so that it can be applied to polymethanethylacrylate, polyethylene terephthalate, polycarbonate and the like, and when applied to tin oxide, . ≪ / RTI >

FIG. 1 is a configuration diagram of a first-stage reaction mechanism according to the present invention,
FIG. 2 is a configuration diagram of a second-stage reaction mechanism according to the present invention,
3 is a flow chart of the manufacturing method according to the present invention,
Fig. 4 shows the coating surface shape and surface analysis results of Example 5,
Figure 5 shows the coating surface shape and surface analysis results of Example 6,
Fig. 6 shows the coating surface shape and surface analysis results of Example 7,
FIG. 7 shows the coating surface shape and surface analysis results of Example 8,
8 is a surface roughness AFM image of Example 5,
9 is a surface roughness AFM image of Example 6,
10 is a surface roughness AFM image of Example 7,
11 is a surface roughness AFM image of Example 8. Fig.

Hereinafter, a method for producing a titanium dioxide hybrid coating solution according to the present invention will be described in detail with reference to the accompanying drawings.

The method for preparing a titanium dioxide coating composition according to the present invention comprises a first step of reacting silane with a reactive monomer to prepare a silane polymer and a second step of reacting the silane polymer with titanium dioxide particles to prepare composite titanium dioxide particles .

First, in the process for producing a titanium dioxide coating liquid according to the present invention, a silane polymer is prepared by reacting silane with a reactive monomer as shown in FIG.

Then, as shown in Fig. 2, a composite titanium dioxide particle is prepared by reacting a silane polymer with titanium dioxide particles.

The silane can be represented by the general formula R2-Si (OR) ₃ , wherein OR is a straight-chain, branched or cyclic alkyl group having 1 to 4 carbon atoms, R2 is an allyl group, an acrylic group, an epoxy group, an aminoalkyl group, a phenyl group, or a cycloalkyl group, and has a carbon number of C1-10.

In addition, the reactive monomer may be represented by the general formula _n R1- (OCO = CH _2), wherein R1 is an alkyl group, a phenyl group, a cycloalkyl group, a phenyl group, an epoxy group, a glycol, an allyl group, an alkoxy group, an ester group, either alone or C1-15 material having two or more kinds; n is an integer of 1 to 3, and is a mono, di, triacrylic monomer.

Further, the silane polymer may be represented by _{R1- (OCO = CH 2) m} -R2-Si (OR) 3 wherein m is characterized in that a polymer having 1 to 10 integers.

The titanium dioxide particles have an average particle size of 10 nm to 150 nm, and most preferably 100 nm. If the average particle size is less than 10 nm, the surface area is small and the area to which the silane polymer can bind is not effective because the surface area is small. If the particle size exceeds 150 nm, the silane polymer may be excessively bonded to increase the particle size of the final titanium dioxide particle. Do.

This will be described in more detail with reference to FIG. 3, which will be described in detail below.

First, the catalyst, reactive monomer and silane are added to the solvent. Here, the reactive monomer and silane are as described above. Here, the polymerization can be carried out at a high yield under specific reaction conditions, depending on the type of the reactive monomer and the silane.

The reaction conditions vary depending on the temperature, the solvent, and the conditions of the catalyst. Examples of the solvent include methanol, ethanol, isopropanol, propylene glycol methyl ether, ethylene glycol methyl ether, acetone, methyl ethyl ketone, toluene, xylene, triethylene glycol methyl ether and the like. One or more of them may be used in combination.

The catalyst may be at least one selected from the group consisting of an inorganic acid such as titanium chloride (IV), trihydrochloric acid, nitric acid, hydrochloric acid, boron trifluoride, or a Lewis acid such as triethylamine, triethanolamine, triethylenepentamine, triethylenetetraamine Amines may be used alone or in combination of two or more.

The catalyst may be used in an amount of 0.01 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight, based on 1 part by weight of the reactive monomer.

If the added amount of the catalyst is less than 0.01 part by weight, the reaction time becomes longer. If the added amount exceeds 0.5 part by weight, side reactions other than the desired reaction may occur, which is inappropriate.

After the catalyst, the reactive monomer and the silane are added to the solvent, stirring is carried out at 50 to 80 ° C. If the reaction temperature is lower than 50 ° C, the reaction time becomes longer. If the reaction temperature exceeds 80 ° C, a side reaction other than the intended reaction may occur, which is inappropriate.

Then, as shown in FIG. 1, after the stirring reaction, the silane polymer in the reaction material should be extracted. In this case, alcohol and purified water may be mixed and separated by centrifugation.

Next, titanium dioxide particles, purified water and an acid are added to the silane polymer to cause a hydrolysis and condensation reaction. The reaction is carried out as shown in FIG. 2, resulting in the extraction of composite titanium dioxide particles.

The purified water serves as a catalyst and can be added in a proportion of 0.1 to 1.5 mol per 1 mol of the alkoxy group of the silane, preferably 0.5 to 1 mol.

When the addition amount of the purified water is less than 0.5 mol, the hydrolysis reaction of the silane polymer is not completed. When the addition amount of the silane polymer exceeds 1 mol, the condensation reaction proceeds excessively and the effective bonding of the silane polymer to the surface of the titanium dioxide particles can not be induced. Do.

The acid is added, and the acid acts to accelerate the hydrolysis and condensation reaction between the silane polymer and the titanium dioxide particle surface, and may be used in an amount of 0.001 to 0.5 part by weight based on 1 part by weight of the silane polymer. If the amount of the acid as the hydrolysis catalyst is less than 0.001 part by weight, the hydrolysis does not take place effectively. If the amount exceeds 0.5 part by weight, the hydrolysis rate is higher than the condensation reaction rate and the effective reaction can not be induced.

In the hydrolysis and condensation reaction, the alkoxy group of the silane polymer and the Ti-O-Ti bond on the surface of the titanium dioxide particle are hydrolyzed into a compound having a hydroxy group, and the hydroxyl group-containing silane polymer is reacted with Ti A condensation reaction partially occurs with -OH and bonds to the surface of titanium dioxide.

The hydrolysis and condensation reaction can be carried out at a temperature in the range of 10 to 50 ° C. When the condensation reaction temperature is less than 10 ° C, the condensation reaction rate is excessively retarded. When the condensation reaction temperature exceeds 50 ° C, it is difficult to control the condensation reaction rate, which is inappropriate.

Next, the extracted composite titanium dioxide particles are put into a solvent and dispersed in the solvent. The solvent may be selected from the group consisting of methanol, ethanol, isopropanol, propylene glycol methyl ether, ethylene glycol methyl ether, acetone, methyl ethyl ketone, toluene, xylene, triethylene glycol methyl ether, One or more of them may be mixed and used.

A dispersant may be added to the solvent so that the composite titanium dioxide particles are well dispersed. The dispersant may be selected from the group consisting of oleic acid, decanoic acid, dodecanoic acid, sodium oleate, decanoic acid amine, polyethylene glycol, polypropylene glycol, triethylene glycol methyl ether, trimethylcethylamine bromide, trioctylphosphine oxide, sodium dodecylsulfonate, 1-propanol, butyl acetate BYK 110, 170, 180 (BYK chemie Germany), and the like.

The dispersant may be used in an amount of 5 to 50 parts by weight, and more preferably 10 to 30 parts by weight, based on 1 part by weight of the composite titanium dioxide particles.

When the amount of the dispersant is less than 5 parts by weight, effective dispersion can not be induced. When the amount of the dispersant is more than 50 parts by weight, the amount of the dispersant is too large to show the physical properties of the composite titanium dioxide particles.

Further, ultrasonic waves may be used so that dispersion for the solvent can be performed more easily. The ultrasonic waves may be ultrasonic waves having an output in the range of 300 to 1000 watts, 5 to 60 kHz, preferably 500 to 900 watts, and an output in the range of 10 to 30 kHz for 30 to 60 minutes have.

Here, if the ultrasonic output range is less than 300 watts, effective dispersion does not occur, and if it exceeds 1000 watts, hydrolysis of the silane polymer bonded to the composite titanium dioxide particles is not performed.

In addition, in the present invention, a surfactant and an ultraviolet absorber may be added for the secondary performance of the product.

A surfactant composed of a fluorine-based or copolymer of dimethylsiloxane and polyoxyethylene may be added in order to impart coating property, defoaming property, wettability and surface slip property of the coating film by the product of the present invention.

Further, in order to improve the durability, an ultraviolet absorber may be added in such an amount that the physical properties of the composition of the present invention are not deteriorated.

The titanium dioxide coating composition according to the present invention can be applied to a coating by various methods.

The coating material is applied to a plastic substrate by using roll to roll coating, spin coating, spray coating or bar coating according to the type of the coating material, It is possible to obtain a protective film having a high hardness.

Since the thickness varies depending on each coating method, when the thickness is thin, it is preferable to perform the coating several times so that the thickness of the coating is about 1 to 25 mu m, more preferably about 5 to 15 mu m Thereby forming a coating film.

If the thickness of the coating film is less than 1 탆, it is difficult to exhibit the intrinsic properties of titanium dioxide. If the thickness exceeds 25 탆, the coating film is cracked and peeled, which is inappropriate.

The curing conditions after the coating of the coating composition are somewhat different depending on the compounding ratio and the components, but generally, the desired hardness protective coating can be obtained by curing at 60 to 140 ° C, which is lower than the softening point of the base, for 30 minutes to 4 hours .

Hereinafter, a method for producing a titanium dioxide coating solution according to the present invention will be described in detail with reference to examples.

Example 1 (Reactant A)

A solution of 14.9 g of vinyltrimethoxysilane, 22.6 g of 1,6-hexanediol diacryl, and 19.2 g of phenoxyethyl acrylate in 100 g of propylene glycol methyl ether was placed in a 500 ml round-bottomed flask equipped with a reflux condenser, 0.03 g of chloroacetic acid and 0.1 g of titanium (IV) chloride were added, and the temperature was raised to 60 to react. After cooling the reaction solution to 40, 0.5 g of hydroxyquinone was added to dissolve the solution, and a solid content was obtained as a final reaction product after centrifugation.

Example 2 (Reactant B)

In Example 1, 23.1 g of glycidyltriethoxysilane was used in place of vinyltrimethoxysilane, and the remaining process was carried out in the same manner as in Example 1.

Example 3 (Reactant C)

In Example 1, 23.5 g of methacryloxypropyltrimethoxysilane was used in place of vinyltrimethoxysilane, and the remaining process was carried out in the same manner as in Example 1.

Example 4 (Reactant D)

In Example 1, 13.1 g of aminopropyltriethoxysilane was used instead of vinyltrimethoxysilane, and the remaining process was carried out in the same manner as in Example 1.

Example 5 (coating liquid A)

Sixty grams of TiO2 nanoparticles having an average particle diameter of 100 nm prepared by a conventional method was dissolved in 100 g of ethylene glycol methyl ether, and then the reaction product A, 18 g of purified water and 6 g of glacial acetic acid were added thereto and reacted for 46 hours while maintaining the temperature at 4060.

3 g of trioctylphosphine oxide and 2 g of decanoic acid amine as a dispersant were added to 100 g of propylene glycol methyl ether, and the mixture was ultrasonically dispersed in an ultrasonic wave of 750 watts (watt) at 20 kHz for 30 minutes.

Example 6 (coating liquid B)

Reactant B was used in place of Reactant A in Example 5, and the remaining process was prepared in the same manner as in Example 5.

Example 7 (coating liquid C)

Reactant C was used in place of Reactant A in Example 5, and the remaining process was prepared in the same manner as in Example 5.

Example 8 (coating liquid D)

Reactant D was used in place of Reactant A in Example 5, and the remaining process was prepared in the same manner as in Example 5.

Comparative Example 1

14.9 g of vinyltrimethoxysilane was used instead of the reactant A in Example 5, and the remaining process was carried out in the same manner as in Example 5.

Comparative Example 2

23.1 g of glycidyltriethoxysilane was used instead of the reactant A in Example 5, and the remaining process was carried out in the same manner as in Example 5.

Comparative Example 3

23.5 g of methacryloxypropyltrimethoxysilane was used instead of the reactant A in Example 5, and the remaining process was carried out in the same manner as in Example 5.

Comparative Example 4

13.1 g of aminopropyltriethoxysilane was used instead of the reactant A in Example 5, and the remaining process was carried out in the same manner as in Example 5.

Test Example 1 (Coating Method)

<Example 5><Example8> and <Comparative Example 1> The final coating composition prepared by Comparative Example 4 was coated on a PET (polyethyleneterephthalate) film having a thickness of 0.2 袖 m to a thickness of 10 袖 m, Lt; / RTI &gt;

Test Example 2 (Adhesion test)

The coating film of <Test Example 1> was subjected to a cross-cut tape test of ASTM D 3359-87 to make 100 chambers at intervals of 1 mm in width and length, and then peel test was performed using a cellophane tape of Nichigo Reflective, Japan And the number of chambers attached without being peeled off was counted.

Test Example 3 (Hardness Test)

The coating film of Test Example 1 was measured by a pencil hardness meter according to ASTM D 3363.

Test Example 4 (Measurement of transmittance)

The transmittance of the coating film of Test Example 1 was measured according to ASTM D 1003.

Test Example 5 (Moisture resistance test)

The adhesion of the coating film of Test Example 1 when stored for one month in a constant temperature and humidity condition of 40 and relative humidity of 70% was measured.

Test Example 6 (Storage Safety Test)

<Example 5><Example8> and <Comparative Example 1> The storage stability of the final coating solution composition prepared by Comparative Example 4 for 2 months in a constant temperature and humidity condition of 40 and relative humidity of 70% The viscosity was measured by the change.

Test Example 7 (Particle size and component analysis)

The coating film of Test Example 1 was analyzed by scanning electron microscopy (SEM-EDS) for the size and composition of TiO2 particles on the coated surface. The analysis results showed that the coating surface shapes and analysis images of Examples 5 to 8 were Are shown in Figs. 4 to 8. Fig.

Test Example 8 (Coarse surface roughness measurement)

The roughness of the coating surface was measured from the surface image of the coating film of <Test Example 1> measured by atomic force microscopy (AFM), and as a result, the surface roughness images of Examples 5 to 8 were measured As shown in FIG.

In the present invention, the performance evaluation of the coating composition was tested through the above-described test examples, and the items that can be evaluated by specific values were evaluated using numerical values. In the case of the step, a very insufficient step is indicated by X.

(1) Storage stability

Example 5 6 7 8 Viscosity
(cps, 20 &lt; 0 &gt; C) Before storage 280 221 234 198 After battlefield 278 226 229 206
Comparative Example One 2 3 4 Viscosity
(cps, 20 &lt; 0 &gt; C) Before storage 176 201 184 157 After saving 168 238 152 160

As can be seen from Table 1, in the case of the coating liquid according to the present invention, the variation range of the viscosity before and after storage was small, which can be interpreted as keeping the physical properties of the coating liquid composition constant. On the other hand, when the silane was used instead of the polymer silane (Comparative Examples 1 to 4), the variation of the viscosity was relatively large, indicating that the stability of the coating solution was poor.

(2) Properties of coating film

Example 5 6 7 8 Attachment 4B 3B 3B 3B Transmittance (%) 87 91 88 90 Hardness 3H 2H 4H 2H Moisture resistance ○ ○ △ △ Shape / Particle Size (nm) Amorphous / 200 or less Spherical / 200 or less Amorphous / 200 or less Amorphous / 200 or less Surface roughness (nm) 1.3773 0.7570 1.0737 0.4786
Comparative Example One 2 3 4 Attachment 2B 2B 1B 2B Transmittance (%) 92 86 87 89 Hardness 1H 2H 1H 1H Moisture resistance ○ × △ × Shape / Particle Size (nm) Amorphous / below 500 Amorphous / below 500 Amorphous / below 500 Amorphous / below 500 Surface roughness (nm) 1.3886 1.7682 0.625 1.2406

* Adhesiveness: 5B> 4B> 3B> 2B> 1B> 0B The larger the number, the better the adhesion.

* Hardness: H is harder than B, the larger the number, the greater the hardness

As can be seen from Table 2, when the coating liquid prepared according to the present invention was coated, the surface properties (adhesion, hardness, permeability, moisture resistance, Particle size and surface roughness) were excellent.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And all of the various forms of embodiments that can be practiced without departing from the technical spirit.

Claims (19)

A first step of reacting silane with a reactive monomer to prepare a silane polymer; And
And a second step of reacting the silane polymer with titanium dioxide particles to prepare composite titanium dioxide particles. The method according to claim 1, wherein the first step comprises polymerizing using a solvent, wherein the solvent is selected from the group consisting of methanol, ethanol, isopropanol, propylene glycol methyl ether, ethylene glycol methyl ether, acetone, methyl ethyl ketone, toluene, Triethyleneglycol methyl ether, and triethylene glycol methyl ether. The method of claim 1, wherein the first step is carried out using a catalyst, and the catalyst is selected from the group consisting of titanium (III) trichloride, trichloroacetic acid, nitric acid, hydrochloric acid, inorganic or Lewis acids such as boron trifluoride, triethylamine, Amine, triethylene pentaamine, and triethylenetetraamine. The method for producing a titanium dioxide coating liquid according to claim 1, The method for producing a titanium dioxide coating liquid according to claim 1, wherein the first step comprises stirring at 50 to 80 ° C. [2] The method according to claim 1, wherein the second step comprises reacting further with purified water. [2] The method of claim 1, wherein the second step further comprises an acid. The method for producing a titanium dioxide coating liquid according to claim 1, wherein the titanium dioxide particles have a particle size of 10 nm to 150 nm. The method for producing a titanium dioxide coating liquid according to claim 1, further comprising a third step of mixing and dispersing the composite titanium dioxide particles of the second step in a solvent. The method according to claim 8, wherein the dispersion in the third step is dispersed using ultrasonic waves, and the ultrasonic wave is dispersed for 30 to 60 minutes using an output of 300 to 1000 watts and 50 to 60 kHz. A method for producing a coating liquid. The method according to claim 8, wherein the solvent in the third step is selected from the group consisting of methanol, ethanol, isopropanol, propylene glycol methyl ether, ethylene glycol methyl ether, acetone, methyl ethyl ketone, toluene, xylene and triethylene glycol methyl ether By weight based on the total weight of the titanium dioxide coating solution. [9] The method of claim 8, wherein the third step further comprises a dispersing agent, wherein the dispersing agent is selected from the group consisting of oleic acid, decanoic acid, dodecanoic acid, sodium oleate, decanoic acid amine, polyethylene glycol, polypropylene glycol, triethylene glycol methyl ether, Wherein the titanium dioxide coating solution is at least one selected from the group consisting of trimethylcetylamine bromide, trioctylphosphine oxide, sodium dodecylsulfonate, 2-methoxy-1-propanol and butyl acetate. [Claim 9] The method according to claim 8, wherein the third step further comprises an additive. [6] The method according to claim 5, wherein the purified water is mixed at a ratio of 0.1 to 1.5 mol per 1 mol of the alkoxy group of the silane. [Claim 6] The method according to claim 6, wherein the acid is mixed in a ratio of 0.001 to 0.5 part by weight based on 1 part by weight of the silane polymer material. [4] The method according to claim 3, wherein the catalyst is mixed in a ratio of 0.01 to 0.5 parts by weight based on 1 part by weight of the monomer. [12] The method according to claim 11, wherein the dispersant is mixed at a ratio of 5 to 50 parts by weight based on 1 part by weight of the titanium dioxide. The method for producing a titanium dioxide coating liquid according to claim 1, wherein the silane is formed by the following molecular formula.
(Molecular formula: R2-Si (OR) 3, wherein OR is a substance having a linear, branched or cyclic type having 1 to 4 carbon atoms having only one or two or more alkoxy functional groups, R2 is an allyl group, An epoxy group, an aminoalkyl group, a phenyl group, a cycloalkyl group, or a substance having a carbon number of 1 to 10) The method for producing a titanium dioxide coating liquid according to claim 1, wherein the reactive monomer is composed of the following molecular formula.
(OCO = CH2) n wherein n is an integer of 1 to 3, R1 is an alkyl group, a phenyl group, a cycloalkyl group, a phenylalkyl group, an epoxy group, an ethylene glycol, an allyl group, A substance having 1 to 15 carbon atoms) The method for producing a titanium dioxide coating liquid according to claim 1, wherein the silane polymer has the following molecular formula.
(OR) 3, m is an integer of 1 to 10, OR is a linear, branched or cyclic alkyl group having one or more alkoxy functional groups, R 1 is a substance having 1 to 15 carbon atoms having an alkyl group, a phenyl group, a cycloalkyl group, a phenylalkyl group, an epoxy group, an ethylene glycol, an allyl group, an alkoxy group or an ester group, , R2: a substance having 1 to 10 carbon atoms, which has at least one allyl group, an acrylic group, an epoxy group, an aminoalkyl group, a phenyl group, and a cycloalkyl group,

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