KR102234674B1 - A manufacturing method for anti―smudge coating and ladder type polysilsesquioxanes with the fluorine group - Google Patents

Abstract

The present invention relates to ladder-like polysilsesquioxane having a fluorinated functional group, a method for preparing an anti-fouling coating solution using the same, and an anti-fouling coating solution obtained thereby. The method for preparing an anti-fouling coating solution includes the steps of: (a) adding a predetermined amount of trifluoropropyltrimethoxysilane (TETPTMS) to isopropyl alcohol (IPA) solvent, as a first mixed solution, and carrying out agitation for a predetermined time; (b) adding a predetermined amount of K_2CO_3 to distilled water, as a second mixed solution, and carrying out agitation for a predetermined time; (c) introducing the second mixed solution to the first mixed solution, and carrying out agitation so that the two solutions may be mixed homogeneously; (d) aging the mixed solution in step (c) for a predetermined time, and carrying out decantation and washing to obtain resin-like polysilsesquioxane; (e) adding the polysilsesquioxane obtained from step (d) in a fluorinated solvent at a weight ratio of 1-1.5% to perform coating.

Description

A manufacturing method for anti-smudge coating and ladder type polysilsesquioxanes with the fluorine group}

The present invention relates to a method for preparing an antifouling coating solution, and more particularly, to a method for preparing an antifouling coating solution in which a ladder-shaped polysilsesquioxane having a fluorine functional group is synthesized and the synthesized polysilsesquioxane is optimized as a coating solution composition. will be.

With the rapid growth of the smartphone market in recent years, the demand for antifouling coating liquid called anti-fingerprint coating is also on the rise.

In the case of antifouling coating, which is mainly used for touch-type electronic products, it has begun to be applied to various industries as customer satisfaction increases. For example, not only smartphones, but also home appliances, automobiles, and accessories markets have pollution prevention and easy cleaning properties, so they are being applied in a variety of ways. However, in the case of such antifouling coating liquid, the dependence on foreign countries is quite high, and it is composed of a high molecular weight fluorine silane having a molecular weight of 5000 or higher, which increases the cost of the product.

In order to solve this problem, many studies are being conducted, and most of the existing technologies are methods of using expensive fluorine silanes appropriately, direct synthesis of fluorine silanes, and methods of using materials other than fluorine such as non-oxidized graphene. Also being introduced. However, it still does not solve the problem of cost aspect by using a platinum catalyst and an expensive material.

Korean Registered Patent No. 1752182 (registered on March 4, 2013)

The present invention was conceived to solve the above-described problems, by using a monomolecular fluorine silane as a precursor and using a weak base catalyst to synthesize a polymer fluorine silane at room temperature, and synthesized ladder-type polysilsesquioxane and It is an object of the present invention to provide a method for preparing an antifouling coating solution optimized with a coating solution composition.

To this end, the present invention includes the steps of (a) adding TFTPTMS to an IPA solvent in a predetermined range and stirring for a predetermined time as a first mixed solution, and (b) as a second mixed solution, K _{2 in distilled water in a predetermined range.} Adding CO ₃ and stirring for a predetermined time; (c) adding the second mixed solution to the first mixed solution and stirring for a predetermined time so that it is uniformly mixed; and (d) in the (c) step The step of aging the mixed solution for a predetermined period of time, and the step of synthesizing polysilsesquioxane in the form of resin by decantation and washing, and (e) at least 1% by weight of the polysilsesquioxane synthesized in the step (d) in a fluorine solvent. It provides a ladder-type polysilsesquioxane having a fluorine functional group comprising the step of adding and coating in the range of 1.5% or less, and a method for preparing an antifouling coating solution using the same, and an antifouling coating solution.

In addition, the fluorine solvent is C ₆ OH ₅ F ₉ It is characterized by being a fluorine solvent having a molecular structure.

In addition, in step (e), a 1 wt% aqueous hydrochloric acid solution was prepared before the coating, and the material to be coated was added to the prepared hydrochloric acid aqueous solution, followed by ultrasonic cleaning for a predetermined time, and then using IPA or ethanol on the material to be coated. It may further include washing the residual hydrochloric acid.

In addition, in the step (e), the prepared antifouling coating liquid is flowed on the material to be coated by a flow coating method, and then dried at a predetermined temperature for a predetermined period of time to coat.

In addition, the molar concentration of the TFTPTMS added in step (a) is characterized in that the range of 1M ~ 3.5M.

In addition, in step (a), 100 g of the TFPTMS is added to 500 ml of the IPA solvent and stirred for 30 minutes.

In addition, in step (b), _{11 mL and 0.12 g of the distilled water and K 2} CO ₃ are added, respectively, and then the K ₂ CO ₃ It is characterized by stirring for a time when the catalyst is completely dissolved.

In addition, in step (c), the distilled water and TFPTMS are characterized in that the mol ratio is 1:2.

The present invention can provide an easy approach while the cost of raw materials and the cost consumed in the synthesis process are considerably lower than that of the existing technology.

In other words, ladder-shaped polysilsesquioxane can be obtained in the form of resin after synthesis, and the final antifouling coating solution is prepared by mixing the synthesized resin into a coating solution composition, thereby localizing overseas technology and reducing the unit price of the product in Korea. It can be applied inexpensively to various fields of

In addition, it is possible to apply an antifouling coating to plastic products such as PMMA and PC, which are applied not only to general glass products, but also to electronic products and household appliances, so that contamination prevention and super water repellency can be realized, thereby securing product reliability.

1 is a diagram showing a process of synthesizing ladder-type polysilsesquioxane having a fluorine functional group according to a preferred embodiment of the present invention and a process of preparing an antifouling coating solution by appropriately mixing the synthesized polysilsesquioxane as a coating solution composition.
2 is a graph showing Si-NMR results of polysilsesquioxane containing a fluorine functional group according to a preferred embodiment of the present invention.
3 is a graph showing the XRD results of polysilsesquioxane containing a fluorine functional group according to a preferred embodiment of the present invention.
4 is a graph showing the results of GPC analysis of polysilsesquioxane containing a fluorine functional group according to a preferred embodiment of the present invention.
5 is a graph showing the results of FT-IR analysis used as a precursor and polysilsesquioxane containing a fluorine functional group according to a preferred embodiment of the present invention.
6 is a view showing a comparison of contact angles before and after coating of an antifouling coating solution prepared based on polysilsesquioxane containing a fluorine functional group according to a preferred embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1A is a view showing a ladder type polysilsesquioxane synthesis process having a fluorine functional group according to a preferred embodiment of the present invention, and FIG. 1B is a ladder type polysilses having a fluorine functional group synthesized in FIG. 1A It is a diagram showing a process of preparing an antifouling coating solution by appropriately mixing quioxane as a coating solution composition.

First, the process of synthesizing ladder-type polysilsesquioxane having a fluorine functional group according to a preferred embodiment of the present invention includes the steps of (a) preparing a first mixed solution by adding TFPTMS to an IPA solvent in a predetermined range, and (b _{) Preparing a second mixed solution by adding K 2} C03 to distilled water in a predetermined range, and (c) when both the first and second mixed solutions are uniformly mixed, the second mixed solution is mixed with the first Drop-by-drop (dropwise) into the solution and stirring at room temperature for a predetermined time and (d) stirring for 24 hours and then aging for 24 hours are set as 1 set, and 2 sets are repeated for a total of 72 hours to be transparent and resin. It may include the step of synthesizing a ladder-shaped polysilsesquioxane in the form.

In addition, an antifouling coating solution may be prepared by appropriately mixing the synthesized ladder-shaped polysilsesquioxane as a coating solution composition.

First, a slide glass is put in 1 wt% hydrochloric acid aqueous solution, ultrasonically washed, and then residual hydrochloric acid is washed with ethanol or IPA. Thereafter, the prepared antifouling coating solution (0, 0.5%, 1.0%, 1.5%) is poured onto the slide glass substrate in a flow-coating method, and then dried in an oven at 130° C. for 1 hour to coat.

A process for synthesizing a ladder-type polysilsesquioxane having a fluorine functional group according to a preferred embodiment of the present invention will be described with reference to FIG. 1A.

Here, in the present invention, trifluoropropyltrimethoxy silane (TFPTMS) was used as a silane precursor to synthesize a ladder-type polysilsesquioxane having a fluorine functional group, and the synthesis process is as follows.

First, as a first mixed solution, 100 g of TFPTMS as a precursor is added to 500 mL of IPA (isopropyl alcohol) as a solvent, and then stirred for 30 minutes so that it can be uniformly mixed (S110). At this time, the molar concentration of TFPTMS that can be synthesized is preferably in the range of 1M to 3.5M. This, the polysilsesquioxane to be synthesized in the present invention can be largely divided into three structures: a cage type in a box shape, a ladder type in a ladder shape, and a random type having a random structure. Among them, polysilsesquioxane in the form of a ladder can be obtained in the form of a resin after synthesis. In this way, in order to synthesize the ladder-shaped polysilsequioxane, the molar concentration of TFPTMS is preferably in the range of 1M to 3.5M.

Thereafter, as a second mixed solution, _{11 mL and 0.12 g of distilled water and K 2} CO ₃ , respectively, are added to another beaker, and then stirred so that the catalyst can be completely dissolved (S120).

Thereafter, when both solutions are uniformly mixed, the second mixed solution in which distilled water and catalyst are mixed is added dropwise to the beaker of the first mixed solution with a silane precursor. TFPTMS is adjusted to maintain a mol ratio of about 1:2.

Thereafter, the mixture is stirred at room temperature. After stirring for 24 hours (S130), the aging step for 24 hours is set as 1 set, and 2 sets are repeated for a total of 72 hours aging (S140), and decantation and washing in the mixed solution (S150, S160), a transparent and resin-like ladder-type polysilsesquioxane is synthesized (S170). At this time, the decantation and washing process remove residual silane, catalyst, impurities, etc. through the IPA washing process several times to obtain the synthesized material, and finally, a ladder-shaped polysilsesqui having a fluorine functional group through a separatory funnel. Oxane is synthesized. An antifouling coating solution is prepared by appropriately mixing the obtained final material with a coating solution composition.

Then, in order to prepare an antifouling coating solution, C ₆ OH ₅ F ₉ Using a fluorine solvent (KEM7200) having a molecular structure, the ladder-shaped polysilsesquioxane (F-PSSQs) synthesized in the fluorine solvent is added in a weight ratio of 0%, 0.5%, 1%, and 1.5%, respectively. To prepare an antifouling coating solution.

Referring to FIG. 1B, in order to clean the surface of a slide glass before coating, a 1 wt% aqueous hydrochloric acid solution is prepared and filled in a beaker so that the slide glass is immersed. Thereafter, after putting the slide glass in and performing ultrasonic cleaning for 15 minutes (S210), the remaining hydrochloric acid on the slide glass is washed using IPA or ethanol (S220). Then, C ₆ OH ₅ F ₉ Using a fluorine solvent (KEM7200) having a molecular structure, the ladder-shaped polysilsesquioxane (F-PSSQs) synthesized in the fluorine solvent is added in a weight ratio of 0%, 0.5%, 1%, and 1.5%, respectively. Thus, an antifouling coating solution is prepared, and the prepared antifouling coating solution is flow-coated onto the slide glass substrate (S230), and then dried in an oven at 130° C. for 1 hour to coat (S240, S250).

At this time, when the contact angle as a result of the water contact angle is 100° or more, the ladder-shaped polysilsesquioxane (F-PSSQs) synthesized in the fluorine solvent is added in a weight ratio of 1% or 1.5%, preferably When added in the range of 1% or more to 1.5% by weight, a contact angle of 100° can be achieved, so it can be finally selected and used as an antifouling coating solution (see FIG. 6). By directly synthesizing the antifouling coating solution as described above, considering the amount injected in the minimum range in order to reduce the unit cost of the product and to implement it at low cost, the weight ratio of ladder-type polysilsesquioxane (F-PSSQs) synthesized in a fluorine solvent is The range of 1% or more and 1.5% or less is preferable.

2 is a graph showing Si-NMR results of polysilsesquioxane containing a fluorine functional group synthesized according to a preferred embodiment of the present invention.

Referring to FIG. 2, by confirming that the polysilsesquioxane T2 peak and T3 peak clearly appear at 64 ppm and 70 ppm, respectively, it can be seen that the structure of polysilsesquioxane was synthesized in a ladder type. have.

3 is a graph showing the XRD results of polysilsesquioxane containing a fluorine functional group synthesized according to a preferred embodiment of the present invention.

Referring to Figure 3, it shows the analysis through multi-purpose XRD in order to confirm the structure of the ladder-shaped form of the synthesized polysilsesquioxane containing a fluorine functional group. That is, as a result of the measurement, it can be seen that the synthesized polysilsesquioxane was synthesized in a ladder shape by observing each siloxane backbond peak and a ladder-shaped interchain peak ^{around 8 o} and 21 ^{o as a result of the measurement.}

4 is a graph showing the GPC analysis results of polysilsesquioxane containing a fluorine functional group synthesized according to a preferred embodiment of the present invention.

Referring to FIG. 4, the weight average molecular weight and number average molecular weight were measured as 1811 and 1658, respectively, and the PDI value was 1.092557, which was found to have a value approximating 1, so that the synthesized polysilsesquioxane has a fairly constant molecular structure. It can be confirmed that there is.

5 is a graph showing the results of FT-IR analysis of polysilsesquioxane containing a fluorine functional group synthesized according to a preferred embodiment of the present invention. In this case, FIG. 5 is a result of FT-IR analysis of the synthesized polysilsesquioxane containing a fluorine functional group according to the present invention, and the synthesized polysilsesquioxane and Trifluoropropyltrimethoxysilane (TFPTMS) used as a precursor.

Referring to FIG. 5, FT-IR analysis was performed to determine the presence or absence of a fluorine functional group in the ladder-structured polysilsesquioxane after synthesis. Both results showed ^{several strong transmission bands in the range of 1350 ~ 1100cm -1} , and through this, it was confirmed that a fluorine functional group was present even after synthesis. In addition, as a result of precursor analysis, it was confirmed ^{that the CH peak that appeared near 2800 ~ 3000cm -1} was removed through condensation polymerization during the synthesis process and disappeared from the analysis result after synthesis.

6 is a view showing a comparison of contact angles before and after coating of an antifouling coating solution prepared based on polysilsesquioxane containing a fluorine functional group synthesized according to a preferred embodiment of the present invention.

6, the result of measuring the water contact angle for each composition ratio of the polysilsesquioxane contained in the coating solution by coating an antifouling coating solution prepared based on polysilsesquioxane containing a fluorine functional group on the surface of a slide glass. .

At this time, the method of coating the slide glass surface is as follows.

First, in order to prepare an antifouling coating solution, C ₆ OH ₅ F ₉ An antifouling coating solution was prepared by adding ladder-shaped polysilsesquioxane (F-PSSQs) synthesized using a fluorine solvent having a molecular structure in a weight ratio of 0%, 0.5%, 1%, and 1.5%, respectively.

At this time, in order to clean the surface of the slide glass before coating, a 1wt% aqueous hydrochloric acid solution is prepared, and the beaker is filled so that the slide glass is submerged. Thereafter, the slide glass is inserted and ultrasonic cleaning is performed for 15 minutes, and then residual hydrochloric acid on the slide glass is washed with IPA or ethanol. Thereafter, the prepared antifouling coating solution is poured onto the slide glass substrate in a flow-coating method, and then dried in an oven at 130° C. for 1 hour to coat.

Here, looking at the contact angle result, an antifouling coating solution having a contact angle of 100° or more can be finally selected and used.

As described above, the technical ideas described in the embodiments of the present invention may be implemented independently, respectively, and may be implemented in combination with each other. In addition, the present invention has been described through the embodiments described in the drawings and the detailed description of the invention, but this is only illustrative, and various modifications and equivalent other embodiments are provided from those of ordinary skill in the art to which the present invention pertains. It is possible. Therefore, the technical protection scope of the present invention should be determined by the appended claims.

Claims (14)

delete delete delete delete delete (a) As the first mixed solution, Trifluoropropyltrimethoxysilane (TFPTMS) in a predetermined range in IPA solvent
Adding and stirring for a predetermined time,
(b) as a second mixed solution _{, adding K 2} CO ₃ to distilled water in a predetermined range and stirring for a predetermined time; and
(c) adding the second mixed solution to the first mixed solution and stirring for a predetermined time to be uniformly mixed; and
(d) synthesizing a resin-type polysilsesquioxane by aging the mixed solution for a predetermined period of time in step (c), followed by decantation and washing, and
(e) adding and coating the polysilsesquioxane synthesized in step (d) in a weight ratio of 1% or more and 1.5% or less to a fluorine solvent. The method of claim 6,
The fluorine solvent is C ₆ OH ₅ F ₉ An antifouling coating solution manufacturing method, characterized in that it is a fluorine solvent having a molecular structure. The method of claim 6,
In the step (e), a 1wt% aqueous hydrochloric acid solution is prepared before the coating, the material to be coated is added to the aqueous hydrochloric acid solution, and ultrasonic cleaning is performed for a predetermined period of time, and then residual hydrochloric acid on the material to be coated is performed using IPA or ethanol. Antifouling coating solution manufacturing method, characterized in that it further comprises the step of washing. The method of claim 6,
In the step (e), the antifouling coating solution is flow-coated on the material to be coated, and then dried at a predetermined temperature for a predetermined period of time to coat. The method of claim 6,
The antifouling coating solution manufacturing method, characterized in that the molar concentration of the TFTPTMS added in step (a) is in the range of 1M to 3.5M. The method of claim 9,
In the step (a), 100 g of the TFPTMS is added to 500 ml of the IPA solvent and stirred for 30 minutes. The method of claim 6,
In the step (b), _{11 mL and 0.12 g of the distilled water and K 2} CO ₃ are added, respectively, and then the K ₂ CO ₃ A method for producing an antifouling coating solution, characterized in that stirring is performed for a time in which the catalyst is completely dissolved. The method of claim 6,
In the step (c), the distilled water and TFPTMS have a mol ratio of 1:2. Antifouling coating liquid, characterized in that produced by the antifouling coating liquid manufacturing method of claim 6.

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