KR101015385B1 - Solution for Thin Film Coating of Organic/Inorganic hybrid complex and Method of Produce for the Same and Method of Coating Using the Same - Google Patents

Abstract

The present invention relates to an organic-inorganic hybrid composite thin film coating solution which improves adhesion to glass even at low heating temperature and low organic content, and a method for preparing the same, and a coating method using the same. According to the present invention, TEOS (Tetraethylorthosilicate) in an ethanol solution is disclosed. ), A method for preparing an organic-inorganic hybrid composite thin film coating solution comprising a solution mixing step of mixing an aqueous solution of nitric acid and an organic pigment, and a first ripening step in which the solution mixed in the solution mixing step is stirred at a predetermined temperature for a predetermined time. do.

Glass substrate, thin film, organic / inorganic hybrid, adhesion

Description

Organic-inorganic hybrid composite thin film coating solution and its manufacturing method and coating method using the same {Solution for Thin Film Coating of Organic / Inorganic hybrid complex and Method of Produce for the Same and Method of Coating Using the Same}

The present invention relates to a coating solution for an organic-inorganic hybrid composite thin film, and more particularly, to an organic-inorganic hybrid composite thin film coating solution having improved adhesion to glass even at low heating temperature and low organic content, and a method for manufacturing the same and coating using the same. It is about a method.

In general, silica-based organic-inorganic hybrid composite thin film using sol-gel technology is mainly applied to the surface of the existing silica glass (soda lime, bon silicic acid, pure silica) to implement various functionalities.

At this time, the quality of the hybrid composite thin film depends on how strong the adhesion is attached to the glass surface.

The hybrid composite thin film as described above is coated on the surface of the glass and then heat-treated to be attached to the glass surface. In the related art, the hybrid composite thin film needs to be heated to 500 ° C. or higher in order to obtain a satisfactory adhesion force, which requires a lot of facilities and energy costs for heating. It was.

Or, even when the coating film is heated at a low temperature, it is difficult to fully exhibit the characteristics of the organic-inorganic hybrid material because a large amount (more than 25wt%) of organic matter must be added.

The present invention is to solve the problems as described above, while maintaining a low organic content content providing an organic-inorganic hybrid composite thin film coating solution exhibiting sufficient adhesion even when heat treatment at a lower temperature than the prior art, and a method for manufacturing the same and a coating method using the same Let's make it a task.

In order to solve the above problems, according to one embodiment of the present invention, TEOS (Tetraethylorthosilicate), a nitric acid solution and an organic pigment are added to the ethanol solution, so that the silanol group on the silica glass surface has a siloxane bond. An organic-inorganic hybrid composite thin film coating solution is provided which is to be replaced.

The TEOS may be mixed to have a volume ratio of 1: 0.6 to 0.9 with respect to the ethanol solution.

Alternatively, the TEOS may be mixed to have a volume ratio of 1: 0.78 with respect to the ethanol solution.

In addition, the aqueous nitric acid solution may be mixed with 15 ~ 22wt% at a concentration of 0.1M.

Alternatively, the aqueous nitric acid solution may be mixed with 18.5 wt% of 0.1M concentrated water.

The organic dye may be used by selectively mixing at least one of Rodamin G, Nigrosine, Coumarine 7, and Methylene blue.

In addition, the organic pigment may be mixed with 0.05 ~ 1.1wt%.

Meanwhile, acetic acid and aqueous hydrochloric acid solution may be further added.

The acetic acid may be mixed at 5.2-11.0 wt%.

Alternatively, the acetic acid may be mixed at 8.5 wt%.

In addition, the hydrochloric acid aqueous solution may be mixed with 3.5 ~ 8.5wt% at a concentration of 1.0M.

Alternatively, the hydrochloric acid aqueous solution may be mixed at 5.0 wt% at a concentration of 1.0 M.

On the other hand, according to another aspect of the present invention, a solution mixing step of mixing TEOS (Tetraethylorthosilicate), an aqueous solution of nitric acid and an organic pigment in the ethanol solution, and the first ripening that the solution mixed in the solution mixing step is stirred at a predetermined temperature for a predetermined time Provided is a method for preparing an organic-inorganic hybrid composite thin film coating solution comprising the step.

In addition, the solution mixing step, the nitric acid solution of 0.1M concentration in the mixed solution produced in the first mixing step and the first mixing step of mixing the TEOS in the volume ratio of 1: 0.6 ~ 0.9 with respect to the ethanol solution 15 ~ It may include a second mixing step of mixing 22wt% and a third mixing step of mixing the organic pigment in 0.05 ~ 1.1wt% in the mixed solution produced in the second mixing step.

In addition, the mixed solution may be stirred during the solution mixing step.

In addition, the first maturation step may be agitation at 400 rpm for 25 degrees Celsius for 24 to 48 hours.

In addition, a mixed catalyst addition step of adding a mixed catalyst for promoting an etherification reaction for separating OH in the form of H 2 O from the silanol group of the glass surface may be further included.

The mixed catalyst addition step, the acetic acid addition step of mixing acetic acid in a mixed solution of TEOS (Tetraethylorthosilicate), nitric acid solution and organic pigment in the ethanol solution of 5.2 ~ 11.0wt% and the solution mixed in the acetic acid addition step for a predetermined time Hydrochloric acid aqueous solution addition step of mixing 1.0 M hydrochloric acid (HCl) solution in 3.5 ~ 8.5wt% to the mixed solution matured in the second maturation stage and the second maturation stage during the stirring step and the hydrochloric acid aqueous solution addition step The mixed solution may include a third aging step of stirring at a predetermined temperature for a predetermined time.

In addition, the second maturation stage and the third maturation stage may be agitation at 400 rpm for 25 degrees Celsius for 24 to 48 hours.

On the other hand, according to another aspect of the present invention, TEOS (Tetraethylorthosilicate), nitrate aqueous solution and organic pigments are added to the ethanol solution, the organic-inorganic made to replace the silanol group on the silica glass surface (silanlol group) The organic-inorganic hybrid composite thin film coating solution comprising a coating step of coating the hybrid composite thin film coating solution on the glass surface, a drying step of drying the glass coated with the coating solution and a heat treatment step of heating the dried glass to 200 to 300 degrees Celsius The coating method used is provided.

According to the organic-inorganic hybrid composite thin film coating solution of the present invention, and a method of manufacturing the same and a coating method using the same, the organic-inorganic hybrid composite thin film can maintain sufficient adhesion even at low heat treatment temperature, thereby reducing the cost required for high temperature heat treatment facilities and energy. Also, since it can maintain sufficient adhesion even in the content of low organic matter has the advantage that it is easy to fully exhibit the characteristics of the organic-inorganic hybrid material.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. In describing the present embodiment, the same designations and the same reference numerals are used for the same components, and further description thereof will be omitted.

In the organic-inorganic hybrid composite thin film coating solution of one embodiment of the present invention, TEOS (Tetraethylorthosilicate) 20, nitric acid solution 30, and organic dye 40 are added to the ethanol solution 10 as shown in FIG. 1. Can be done.

First, TEOS (Tetraethylorthosilicate) 20 is mixed with the ethanol solution 10. At this time, the ethanol (10) and TEOS (20) can be mixed in the volume ratio of 1: 0.6-0.9 range and the preferred mixing ratio is 1: 0.78. That is, 78 ml of TEOS (20) is mixed with 100 ml of ethanol (10).

Then, nitric acid (HNO ₃ ) aqueous solution 30 is added to the ethanol 10 and TEOS 20 mixed solution thus obtained. The aqueous nitric acid solution 30 may be mixed within a range of 15 to 22 wt% at a concentration of 0.1 N, and a preferred mixing ratio is 18.5 wt%.

The aqueous nitric acid solution (30) undergoes hydrolysis and polycondensation reaction of TEOS (20) in the ethanol (10) solution. -Si-O-Si-O-Si-... It can be used as a catalyst to form the backbone of the network.

In addition, the organic dye 40 may be mixed. The organic pigment 40 may be used separately or mixed with Rodamin G (red), Nigrosine (blue), Coumarine 7 (yellow), Methylene blue (blue), etc., depending on the color of the hybrid coating material. The single or mixed amount of the organic dye 40 may range from 0.05 to 1.1 wt%.

In addition, it is preferable that the mixed solution is continuously stirred at about 400 rpm while adding the above additives.

 In addition, OH is separated from the silanol (Si-OH) group on the glass surface in the form of H 2 O in the mixed solution of the ethanol (10) and TEOS (20), the nitric acid solution (30) and the organic dye (40). Mixing catalysts for promoting the esterification reaction can be further mixed.

The mixed catalyst may be composed of acetic acid (50) and aqueous hydrochloric acid (HCl) (60).

The acetic acid 50 may be added to the mixed solution of the ethanol (10) and TEOS (20), the nitric acid solution (30) and the organic dye (40) in the range of 5.2 ~ 11.0wt%, the preferred mixing ratio 8.5 wt%.

In addition, the aqueous hydrochloric acid solution 60 may be added in the range of 3.5 ~ 8.5wt% as a concentration of 1.0M, the preferred mixing ratio is 5.0wt%.

It is preferable to aged the respective solutions before adding the acetic acid 50 above, after adding the acetic acid 50 and after adding the aqueous hydrochloric acid solution 60. As a aging method, the mixed solution may be aged for about 24 to 48 hours at room temperature of about 25 ℃ while stirring at 400rpm.

The adhesion of the coating can be improved through a series of processes of adding and aging each catalyst.

The organic-inorganic hybrid composite thin film coating solution as described above effectively induces esterification of condensation and discharge of OH in the form of water molecules of H 2 O from the Si-OH group on the surface of the glass substrate, thereby producing a silanol group. Siloxane (Si-O) bonds to replace the organic matter to maintain less than 5wt% effective adhesion of less than 5% in the X-cutting test (X-cutting test) even at the heat treatment temperature of less than 250 ℃ Can exert.

Hereinafter, a method of preparing the organic-inorganic hybrid composite thin film coating solution of the above-described form will be described.

As shown in FIG. 1, the method for preparing the organic-inorganic hybrid composite thin film coating solution of this embodiment may include a solution mixing step (S100), a first ripening step (S140), and a mixture catalyst addition step (S200). .

The solution mixing step (S100) is a step in which the TEOS 20, the nitric acid solution 30, and the organic dye 40 are mixed with the ethanol (10) solution, and the first mixing step (S110) and the second mixing step (S120). ) And the third mixing step S130 and the first aging step S140.

The first mixing step S110 is a step in which the TEOS 20 is mixed with the ethanol 10 solution. At this time, the mixing ratio of the TEOS (20) mixed in the ethanol (10) solution is 1: 0.6 ~ 0.9 by volume ratio, preferably having a volume ratio of 1: 0.78.

In addition, the second mixing step (S120) is a step of adding a nitric acid solution 30 to the solution mixed in the first mixing step (S110), the nitric acid solution 30 is 15 ~ 22wt at a concentration of 0.1N It may be added in the range of%, preferably 18.5 wt% is added.

In addition, the third mixing step (S130) is a step of mixing the organic pigment in the solution mixed in the second mixing step (S120). The organic dye 40 may be mixed in the range 0.05 ~ 1.1wt%.

It is preferable that the mixed solution is continuously stirred at about 400 RPM while the first mixing step S110 to the third mixing step S130 are performed.

After the solution mixing step (S100), a first aging step (S140) is performed. The first aging step (S140) is a step of maintaining the solution mixed in the solution mixing step (S100) for 24 to 48 hours, preferably 24 hours while stirring at about 400rpm at a temperature of 25 ℃.

After the first aging step S140, a mixture addition step S200 is performed. The mixture addition step (S200) may include an acetic acid addition step (S210), a second aging step (S220), an aqueous hydrochloric acid solution adding step (S230), and a third aging step (S240).

The acetic acid addition step (S210) is a step of adding acetic acid 50 to the mixed solution passed through the first aging step (S140). At this time, the content of acetic acid (50) is added may be added in the range of 5.2 ~ 11.0wt%, preferably 8.5wt% is added.

After the acetic acid addition step 210, a second aging step S220 is performed. The second aging step (S220) is maintained for 24 to 48 hours preferably 24 hours while stirring the mixed solution to which acetic acid (50) is added at a temperature of 25 ℃ similar to the first aging step (S140) described above It's a step.

After the second aging step S220, an aqueous hydrochloric acid addition step S230 is performed. The aqueous hydrochloric acid addition step (S230) is a step of adding an aqueous hydrochloric acid solution (HCl) to the mixed solution in which the second aging step (S220) is made. The aqueous hydrochloric acid solution 60 may be added in the range of 3.5 ~ 8.5wt% in 1.0M, 5.0wt% is preferably added.

After the hydrochloric acid aqueous solution addition step (S230), a third aging step (S240) is performed. The third ripening step (S240) is 24 to 48 hours, preferably 24 hours while stirring the mixed solution to which the hydrochloric acid aqueous solution 60 is added at a temperature of 25 ℃ similar to the first ripening step (S140) described above It is a step to maintain.

The acetic acid (50) and hydrochloric acid solution (60) added through the above steps are condensed and separated from the OH in the form of H ₂ O in the silanol (Si-OH) group on the glass surface when the solution is applied on a glass substrate. Pulling out is a catalyst for promoting the esterification reaction.

The mixed solution prepared through the above process may be gelated after 30 hours if left at room temperature without refrigeration. Therefore, in order to store the solution, it is preferable to keep refrigerated. The refrigerated storage is preferably stored at -14 ℃.

In addition, when the refrigerated mixed solution is used, it must be heated, and the heating temperature can be heated to about 5 ~ 15 ℃ higher than room temperature. Preferably heating at 30-40 degreeC for 2 hours is preferable.

Hereinafter, a method of coating the surface of the glass specimen using the coating solution prepared by using the organic-inorganic hybrid composite thin film coating solution manufacturing method described above will be described.

The coating method using the organic-inorganic hybrid composite thin film coating solution of this form may include a coating step (S310), a drying step (S320), and a heat treatment step (S330) as shown in FIG.

The application step (S310) is a step of applying the coating solution on the surface of the glass. In the description of the present embodiment, the glass is made of soda-lime glass, which is a material for general window glass, and a coating method is applied to the coating.

The immersion coating can be carried out as follows.

After moving the glass substrate to the surface of the solution at the speed of 40mm / s and stopping for 1 second, the glass substrate was moved at the speed of 16mm / s and soaked in the coating solution and stopped for 10 seconds, and the glass substrate was stopped at the speed of 4mm / s It can be lifted and moved to the surface of the coating solution, stopped for 1 second, and then moved to the original position at a speed of 40 mm / s /.

In addition, the glass substrate after the immersion coating is dried in a range of 30 to 120 minutes in air at 25 ℃ (S320) may be performed. Preferred drying time is 30 minutes.

After the drying step S320, a heat treatment step S330 is performed. The heat treatment step (S330) is a step of heating the dried glass substrate for 5 to 15 minutes in the range of 20 ~ 300 ℃. The preferred heat treatment temperature is 250 ° C. and the preferred drying time is 15 minutes.

The glass substrate coated by the above step is as shown in FIG. 3.

Hereinafter, an example of testing the adhesion of the organic-inorganic hybrid composite thin film formed on the glass substrate subjected to the above steps will be described.

For explanation, a glass substrate coated with two solutions was prepared. Glass substrate 1 is a glass substrate in which a thin film is formed with a coating solution prepared according to the above-described manufacturing method, glass substrate 2 is a coating solution performed only until the solution mixing step (S100) and the first aging step (S140) of the thin film is Formed glass substrate. That is, the coating solution constituting the thin film of the glass substrate 2 is a solution in which acetic acid 50 and hydrochloric acid aqueous solution 60 are not added as compared to the coating solution of the glass substrate 1. In addition, the first aging step was aged for 72 hours at 20 ℃. And, the coating method was the same.

The X-cutting test was performed on the glass substrates prepared as described above. Here, the Xcutting test is a test method of drawing a checkerboard-shaped gold at a 1 mm interval on the surface of the coated glass substrate using a knife, pulling the adhesive tape firmly in a 90 degree direction. In general, if the damage rate is less than 5% in this test, it can be judged as satisfactory adhesion.

The result of the above-described cutting test is as shown in FIG.

As shown in the table of FIG. 4, glass substrate 1 of the thin film coated with the coating solution containing the mixed catalyst consisting of acetic acid and hydrochloric acid solution showed an average damage rate of 4.3%, whereas glass substrate 2 had an average damage rate of 16.3%. It can be seen that.

Therefore, it can be seen that by using the coating solution to which the mixed catalyst is added, satisfactory adhesion strength of the organic-inorganic hybrid composite thin film can be obtained even after heat treatment at a relatively low temperature of 200 to 300 ° C.

Hereinafter, an example of testing a change in the thin film adhesion of the coating solution according to the amount of the organic material will be described.

Similar to the above, for the sake of explanation, a glass substrate coated with two urine solutions was prepared. Glass substrate 3 is a glass substrate in which a thin film is formed with a coating solution prepared according to the above-described manufacturing method, glass substrate 3 is a coating in which all the conditions are in accordance with the above-described manufacturing method, but not added with the organic dye 40. It is a glass substrate on which a thin film is formed with a solution.

5 shows the results of the cutting test on the glass substrates prepared as described above.

As shown in the table of FIG. 5, the average damage rate of the glass substrate 3 and the average damage rate of the glass substrate 4 were all within 5%, showing no significant difference. That is, it can be seen that addition of the organic dye 40 has little effect on the adhesion of the thin film.

Therefore, it can be seen that using the organic-inorganic hybrid composite thin film coating solution according to the present invention, satisfactory adhesion strength of the organic-inorganic hybrid composite thin film can be obtained regardless of the content of the organic dye 40.

 As described above, the preferred embodiments of the present invention have been described, and the fact that the present invention can be embodied in other specific forms in addition to the above-described embodiments without departing from the spirit or scope thereof has ordinary skill in the art. It is obvious to them. Therefore, the above-described embodiments should be regarded as illustrative rather than restrictive, and thus, the present invention is not limited to the above description and may be modified within the scope of the appended claims and their equivalents.

1 is a flow chart showing a method for producing an organic-inorganic hybrid composite thin film coating solution of one embodiment of the present invention;

Figure 2 is a flow chart illustrating a coating method for coating on a glass substrate with a coating solution prepared by the manufacturing method of Figure 1;

3 is a photograph showing a glass substrate on which a thin film is formed by the coating method of FIG. 2;

4 is a chart comparing the results of the cutting test of the glass substrate 1 and the glass substrate 2; And,

5 is a chart comparing the results of the cutting test of the glass substrate 3 and the glass substrate 4.

Description of the Related Art [0002]

10: ethanol 20: TEOS

30: aqueous nitric acid solution 40: organic pigment

50: acetic acid 60: aqueous hydrochloric acid

S100: solution mixing step S110: first mixing step

S120: second mixing step S130: third mixing step

S140: first aging step S200: mixed catalyst addition step

S210: acetic acid addition step S220: second maturation step

S230: adding hydrochloric acid solution S240: third maturation step

S310: coating step S320: drying step

S330: heat treatment step

Claims (16)

delete delete delete delete delete delete delete delete delete TEOS (Tetraethylorthosilicate) is mixed in a volume ratio of 1: 0.6 to 0.9 with respect to the ethanol solution, and a second solution in which 0.1M nitric acid solution is mixed at a concentration of 15 ~ 22wt% in the mixed solution produced in the first mixing step And a third mixing step of mixing the organic dye in the mixed solution generated in the mixing step and the second mixing step at 0.05 to 1.1 wt%, and the solution mixing step of mixing the TEOS, the nitric acid solution and the organic dye in the ethanol solution. ; A first ripening step in which the solution mixed in the solution mixing step is stirred at a predetermined temperature for a predetermined time; Organic-inorganic hybrid composite thin film coating solution manufacturing method comprising a The method of claim 10, The mixed solution of the organic-inorganic hybrid composite thin film coating solution, characterized in that during the solution mixing step is stirred. The method of claim 10, The first maturation step is an organic-inorganic hybrid composite thin film coating solution manufacturing method characterized in that the stirring at 25 ℃ 400rpm for 24 to 48 hours. The method of claim 10, Organic-inorganic hybrid composite further comprises a mixed catalyst addition step of adding a mixed catalyst for promoting the etherification reaction to separate the OH in the form of H ₂ O in the silanol group of the glass surface Thin film coating solution production method. The method of claim 13, The mixed catalyst addition step, Acetic acid addition step of mixing acetic acid in a mixed solution of TEOS (Tetraethylorthosilicate), nitric acid solution and organic pigment in the ethanol solution at 5.2-11.0 wt%; A second maturation step in which the solution mixed in the acetic acid addition step is stirred at a predetermined temperature for a predetermined time; Adding an aqueous hydrochloric acid solution in which 1.0 M hydrochloric acid (HCl) aqueous solution is mixed at 3.5 to 8.5 wt% to the mixed solution matured in the second maturation step; A third ripening step in which the solution mixed in the hydrochloric acid aqueous solution addition step is stirred at a predetermined temperature for a predetermined time; Organic-inorganic hybrid composite thin film coating solution manufacturing method comprising a. The method of claim 14, The second maturity stage and the third maturity stage Method for preparing an organic-inorganic hybrid composite thin film coating solution, characterized in that stirred at 25 degrees Celsius 400rpm for 24 to 48 hours. Tetra ethylorthosilicate (TEOS), an aqueous solution of nitric acid, and an organic pigment are added to the ethanol solution to coat the organic-inorganic hybrid composite thin film coating solution formed on the glass surface to replace the silanol group on the silica glass surface. ; A drying step of drying the glass to which the coating solution is applied; A heat treatment step of heating the dried glass to 200 to 300 degrees Celsius; Coating method using an organic-inorganic hybrid composite thin film coating solution comprising a.

Images