TWI461243B - Method for fabricating photocatalyst solution and woven fabrics - Google Patents

Description

Photocatalyst solution and method for producing textile

The present invention relates to a method for producing a photocatalyst solution and a method for producing a textile using the photocatalyst solution, and more particularly to a method for producing a photocatalyst solution having high stability and a textile having antifouling and self-cleaning properties. Production method.

In general, antifouling self-cleaning materials can be divided into two types: hydrophobic type (contact surface greater than 110°) and hydrophilic type (contact angle less than 5°). The hydrophobic self-cleaning principle is based on the low surface energy characteristics of the hydrophobic layer. So that the pollutants are not easy to adhere to the surface of the object, and have the effect of preventing fingerprints and oil stains, and are suitable for indoor use. The hydrophilic self-cleaning method is that the photocatalyst generates free radicals under sunlight (UV) irradiation, and these free radicals will destroy the molecular structure, and the dirt can be easily removed under heavy rain. In order to achieve the antifouling effect of the product itself, it is necessary to measure the use environment and needs, and then choose a self-cleaning material to be used together.

In the case of a hydrophobic self-cleaning material including a fluorine-based resin, the fluorine-based resin can wash the dirt adhering to the surface through rainwater, but has no ability to decompose oil stains adhering to the surface or exhaust gas in the environment. In addition, in the case of a hydrophilic self-cleaning material including a photocatalyst, the photocatalyst can generate radicals under illumination, and react with free radicals by organic radicals, thereby decomposing organic matter. When it is raining or manually washing the hydrophilic self-cleaning material, these decomposed organic substances can be easily removed.

The invention provides a method for producing a photocatalyst solution, which can produce a photocatalyst solution having antifouling and self-cleaning effects.

The present invention provides a method of producing a woven fabric to produce a woven fabric having antifouling and self-cleaning properties.

The present invention provides a method of producing a photocatalyst solution. The oxoxane compound and the photocatalyst are mixed to react the alkoxy group of the siloxane compound and the hydroxyl group of the photocatalyst. A fluorocarbon resin is added so that the epoxy group of the siloxane compound reacts with the hydroxyl group of the fluorocarbon resin.

In one embodiment of the invention, the above oxoxane compound comprises a functionalized alkoxysilane, and the functionalized functional group comprises OH, COOH, NH ₂ , NCO, vinyl or Epoxy group.

In one embodiment of the present invention, the above-mentioned oxoxane compound includes 3-glycidoxypropyltrimethoxysilane, amino trialkoxysilane, epoxytrialtrialkoxysilane Epoxy trialkoxysilane or (3-aminopropyl)triethoxysilane.

In one embodiment of the present invention, the photocatalyst has a chemical formula of TiR _x or TiOR _x , and R represents OH, COOH, CONH ₂ , NCO, a vinyl group or an epoxy group, and x is 1 to 4.

In one embodiment of the invention, the photocatalyst comprises TiO(OH) ₂ or Ti(OH) ₄ .

In an embodiment of the invention, the fluorocarbon resin comprises a resin containing tetrafluoroethylene as a main component.

In one embodiment of the invention, the alkoxy group of the above siloxane compound reacts with the hydroxyl group of the photocatalyst in a sol gel process.

In one embodiment of the invention, the alkoxy group of the above oxirane compound is reacted with the hydroxyl group of the photocatalyst to be stirred at room temperature for 30 minutes.

In one embodiment of the present invention, the fluorocarbon resin is heated at a temperature of 80 degrees Celsius for 3 days after reacting the alkoxy group of the siloxane compound with the hydroxyl group of the fluorocarbon resin.

In one embodiment of the invention, the above-described decane compound, the photocatalyst, and the fluorocarbon resin are mixed in a solvent.

In an embodiment of the invention, the solvent comprises ethyl acetate.

In an embodiment of the invention, the method for fabricating the photocatalyst solution further comprises adding a hydrophobic agent.

In an embodiment of the invention, the hydrophobic agent comprises a fine powder of tetrafluoroethylene.

The invention further proposes a method for producing a textile having antifouling and self-cleaning properties. First, a photocatalyst solution is prepared, which is obtained by the method described in claim 1 of the patent application. Next, the photocatalyst solution is applied to the textile. After that, the drying step is performed.

In an embodiment of the invention, the method for manufacturing a textile having antifouling and self-cleaning properties further includes performing a photodegradation test step.

In an embodiment of the invention, the method for manufacturing a textile having antifouling and self-cleaning properties further includes performing a surface contact angle test step.

In an embodiment of the invention, the method for manufacturing a textile having the antifouling and self-cleaning properties further includes performing a stain resistance test step.

Based on the above, the photocatalyst solution of the present invention is produced by simultaneously reacting a photocatalyst and a fluorocarbon resin with a siloxane compound so as to have a stable chemical bond between the photocatalyst and the fluorocarbon resin, so that the photocatalyst solution of the present invention is simultaneously hydrophobic. Anti-fouling self-cleaning and hydrophilic anti-fouling and self-cleaning effect. Further, the method for producing a textile having the antifouling and self-cleaning properties of the present invention is applied to the woven fabric by using the photocatalyst solution described above, so that the woven fabric can have good antifouling and self-cleaning effects.

The above described features and advantages of the present invention will be more apparent from the following description.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method of producing a textile having antifouling and self-cleaning properties according to an embodiment of the present invention. Referring to FIG. 1, step S120 is performed to mix a oxoxane compound with a photocatalyst to react an alkoxy group of a siloxane compound with a hydroxyl group of a photocatalyst. The reaction of the oxoxane compound with the photocatalyst is, for example, a sol-gel method, the solvent is, for example, ethyl acetate, and the aforementioned reaction is, for example, stirred at room temperature for 30 minutes.

The oxoxane compound is, for example, a functionalized alkoxydecane, and the functionalized functional group comprises OH, COOH, NH ₂ , NCO, a vinyl group or an epoxy group. In the present embodiment, the above-mentioned oxoxane compound includes 3-glycidyltrimethoxydecane, an aminotrialkoxydecane, an epoxytrialkoxydecane or (3-aminopropyl)triethoxylate. Base decane.

The chemical formula of the photocatalyst is TiR _x or TiOR _x , and R represents OH, COOH, CONH ₂ , NCO, vinyl or epoxy, and x is 1 to 4. In the present embodiment, the photocatalyst is, for example, TiO(OH) ₂ or Ti(OH) ₄ .

Next, in step S140, a fluorocarbon resin is added to react the epoxy group of the siloxane compound with the hydroxyl group of the fluorocarbon resin, and the reaction of the siloxane compound with the fluorocarbon resin includes stirring for 30 minutes and then at 80 degrees Celsius. Heat under conditions for 3 days.

The fluorocarbon resin includes a resin containing tetrafluoroethylene as a main component. In the present embodiment, the fluorocarbon resin is a commercially available product, which product model DAIKIN / ZEFFLE ^TM GK570. Further, in other embodiments, the fluorocarbon resin may be DAIKIN / ZEFFLE ^TM GK-Series, for example, GK500, GK510, GK550 or GK580.

It is explained herein that the siloxane compound can be bonded to the photocatalyst and the fluorocarbon resin through chemical bonding. In other words, the photocatalyst can be stably bonded to the fluorocarbon resin through the siloxane compound. Furthermore, since the photocatalyst is bonded to the fluorocarbon resin by means of chemical bonding, the photocatalyst does not have a problem of uneven physical dispersion, and the photocatalyst does not affect the viscosity of the fluorocarbon resin.

So far, the preparation step S220 of the photocatalyst solution of the present embodiment is completed. However, the present invention is not limited thereto, and in other embodiments, the method of producing the photocatalyst solution further includes adding a hydrophobic agent such as a fine powder of tetrafluoroethylene. The hydrophobic agent helps to form a water-repellent structure on the surface of the film formed by the photocatalyst solution after the photocatalyst solution is applied to the surface of the article, and has good hydrophobicity.

Next, in step S240, the photocatalyst solution described above is applied to the textile. Then, step S260 is performed to perform the drying step. So far, the textile having the antifouling and self-cleaning properties of the present embodiment was completed.

In one embodiment, the method of fabricating the above-described textile having antifouling and self-cleaning properties may further comprise performing a photodegradation test step that helps to understand the self-cleaning ability of the textile.

In addition, the above-described method for producing a textile having antifouling and self-cleaning properties may further include performing a surface contact angle test step which helps to understand the degree of adhesion of contaminants to the surface of the textile.

Furthermore, the above-described method for producing a textile having antifouling and self-cleaning properties may further include performing a stain resistance test step which helps to understand the self-cleaning ability of the textile.

In the foregoing embodiments, the oxoxane compound and the photocatalyst are first mixed to react the alkoxy group of the siloxane compound and the hydroxyl group of the photocatalyst. Then, a fluorocarbon resin is further added to react the epoxy group of the siloxane compound with the hydroxyl group of the fluorocarbon resin. However, the invention is not limited thereto.

2 is a schematic flow chart of a method for producing a textile having antifouling and self-cleaning properties according to another embodiment of the present invention. Referring to FIG. 2, the manufacturing method of the present embodiment is similar to the manufacturing method of FIG. 1, except that in the step S220 of preparing a photocatalyst solution, the siloxane compound, the photocatalyst, and the fluorocarbon resin are mixed together and simultaneously. reaction. In detail, the reaction of the alkoxy group of the siloxane compound with the hydroxyl group of the photocatalyst and the reaction of the epoxy group of the siloxane compound with the hydroxy group of the fluorocarbon resin do not interfere with each other, and therefore, it is also possible to simultaneously The three materials were mixed together in a solvent to carry out a reaction to obtain a photocatalyst solution of the present example.

Experimental example

In order to understand the properties of the woven fabric produced by the production method of the present invention, the efficacy will be described below in several experimental examples. Here, a method of producing the textile of Example 1 and Example 2 will be described first.

In the case of the textile of Example 1, the fluorocarbon resin was applied to the textile prior to the drying step. Thereafter, the photocatalyst solution is coated on the textile, wherein the oxoxane compound in the photocatalyst solution is 3-glycidyltrimethoxydecane, the photocatalyst is TiO(OH) ₂ , the fluorocarbon resin is GK570, and the solvent is acetic acid. Ethyl ester. After the drying step, various properties were tested.

In the case of the textile of Example 2, the woven fabric was immersed in a dispersion of polytetrafluoroethylene (PTFE) and then subjected to a drying step. Thereafter, the photocatalyst solution is coated on the textile, wherein the oxoxane compound in the photocatalyst solution is 3-glycidyltrimethoxydecane, the photocatalyst is TiO(OH) ₂ , the fluorocarbon resin is GK570, and the solvent is acetic acid. Ethyl ester. After the drying step, various properties were tested.

FT-IR resin identification

To determine if the photocatalyst solution of Example 1 was successfully synthesized, an FT-IR characterization was performed. 3 is a FT-IR spectrum diagram of a preliminary product of a fluorocarbon resin, a photocatalyst, and a siloxane compound, and a photocatalyst solution. Referring to FIG. 3, a curve a represents a fluorocarbon resin GK570, a curve b represents a preliminary product of the reaction of 3-glycidyltrimethoxydecane with TiO(OH) ₂ , and a curve c represents a photocatalyst solution of Example 1. Curve b has a signal peak of an epoxy group (910 cm ^-1 ) and SiOCH ₃ (700-900 cm ^-1 ). Curve c, and not having an epoxy group peak signal SiOCH _3, whereby there can be estimated with 3 GK570 fluorocarbon resin glycidol trimethoxy Silane react with TiO (OH) _2.

Methylene blue light degradation test

The test method for methylene blue degradation is to put the textile of the example into an aqueous solution of methylene blue, followed by an ultraviolet light irradiation procedure. Since the photocatalyst generates a radical after irradiation, it reacts with methylene blue to reduce the content of methylene blue in the aqueous solution, and the color of the aqueous solution gradually disappears. Thereafter, ultraviolet light absorption spectrum was identified to determine the absorption rate of methylene blue. In the control group, no photocatalyst was placed, and the same ultraviolet light irradiation procedure was carried out simply with an aqueous solution of methylene blue, and the ultraviolet light absorption spectrum was identified. The absorption peak of methylene blue was 609 nm.

Thereafter, the degree of photodegradation was estimated from the difference in intensity of the control group and the methylene blue absorption peak of Example 1, and FIG. 4 is an ultraviolet visible light absorption spectrum of Example 1 and the control group. Please refer to FIG. 4, curve d is the ultraviolet visible light absorption spectrum of the control group, curve e is the ultraviolet visible light absorption spectrum of the example 1, and the light degradation condition can be understood from the absorption change of the absorption peak at 609 nm.

Table 1 shows the results of the methylene blue degradation test, in which Comparative Example 1 was subjected to photodegradation test only with a glass fiber cloth, and Comparative Example 2 was coated with a fluorocarbon resin GK570 on a glass fiber cloth and subjected to photodegradation test.

As can be seen from Table 1, the textiles of Examples 1 and 2 did have a preferred degradation rate of methylene blue. In other words, the textiles of Examples 1 and 2 have a better effect of decomposing methylene blue.

Anti-fouling test

Soy sauce and red ink were dropped onto the textile, and the stain resistance was tested by visually observing the soaking of the soy sauce and the red ink. Table 2 shows the results of the anti-fouling test.

As can be seen from Table 2, both the soy sauce and the red ink are not easily attached to the surface of the textile of the example, and thus the textiles of Examples 1 and 2 have good stain resistance.

Surface contact angle test

The surface contact angle test utilizes a water droplet contact angle measurement method which can be used as a test for the surface self-cleaning ability. Comparative Example 3 is a film of fluorocarbon resin GK570, and Comparative Example 4 is a film of commercially available PTFE.

As can be seen from Table 3, the textiles of Examples 1 and 2 have a large surface contact angle, and thus have a good self-cleaning ability.

Reactive functional group content test

The following is a Ti element analysis of the photocatalyst solution used in the examples by SEM-EDS to understand the content of reactive functional groups.

Nitride decontamination rate test (JIS R 1701-1)

Generally, the final product of the nitride (for example, NO, NO ₂ ) decomposed by the photocatalyst is NO ₃ ^- or NO ₂ ^- and adheres to the surface of the photocatalyst. The NO ₃ ^- or NO ₂ ^{- on the} surface of the photocatalyst can be washed by rain or manual cleaning, and the trace amount of nitric acid or nitrous acid can be combined with calcium in the ground to form salts such as calcium nitrate or calcium nitrite. Will not cause secondary pollution to the environment. Comparative Example 5 was carried out by adding a photocatalyst to a fluorocarbon resin without adding a oxoxane compound to form a physical photocatalyst solution, and applying a physical photocatalyst solution to the woven fabric.

As can be seen from Table 5, the textile of Example 1 has a good nitride decontamination rate.

Weatherability test (ISO 4892-2)

As can be seen from Table 6, the strength retention of the textile of the example is greater than 95%.

Pull Tensile strength and tear strength test

As can be seen from Table 7, the tear strength of the textile of the example is superior to that of the commercial product. In other words, the photocatalytic solution and the textile in the textile of the example are superior to the commercial product.

dial Oil test (JIS L 1096)

In summary, the photocatalyst solution of the present invention is produced by simultaneously reacting a photocatalyst and a fluorocarbon resin with a oxoxane compound to provide a stable chemical bond between the photocatalyst and the fluorocarbon resin, so that the photocatalyst solution of the present invention is simultaneously It has the functions of hydrophobic antifouling and self-cleaning as well as hydrophilic antifouling and self-cleaning. Further, the method for producing a textile having the antifouling and self-cleaning properties of the present invention is applied to the woven fabric by using the photocatalyst solution described above, so that the woven fabric can have good antifouling and self-cleaning effects.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

S120, S140, S220, S240, S260. . . step

a, b, c, d, e. . . curve

1 is a flow chart showing a method of manufacturing a photocatalyst solution according to an embodiment of the present invention.

2 is a schematic flow chart of a method for producing a textile having antifouling and self-cleaning properties according to another embodiment of the present invention.

3 is a FT-IR spectrum diagram of a preliminary product of a fluorocarbon resin, a photocatalyst, and a siloxane compound, and a photocatalyst solution.

Figure 4 is a graph showing the ultraviolet visible light absorption spectrum of the examples and the control group.

S120, S140, S220, S240, S260. . . step

Claims (17)

A method for producing a photocatalyst solution, comprising: mixing a monooxane compound and a photocatalyst to react an alkoxy group of the oxoxane compound and a hydroxyl group of a photocatalyst; and adding a fluorocarbon resin to cause the argon oxygen The epoxy group of the alkane compound reacts with the hydroxyl group of the fluorocarbon resin. The method for producing a photocatalyst solution according to claim 1, wherein the oxoxane compound comprises a functionalized alkoxydecane, and the functionalized functional group comprises OH, COOH, NH ₂ , NCO , vinyl or epoxy. The method for producing a photocatalyst solution according to claim 2, wherein the oxoxane compound comprises 3-glycidyltrimethoxydecane, an aminotrialkoxydecane, and an epoxytrialkoxydecane. Or (3-aminopropyl)triethoxydecane. The method for producing a photocatalyst solution according to claim 1, wherein the photocatalyst has a chemical formula of TiR _x or TiOR _x , and R represents OH, COOH, CONH ₂ , NCO, vinyl or epoxy, and x is 1 ~4. The method for producing a photocatalyst solution according to claim 4, wherein the photocatalyst comprises TiO(OH) ₂ or Ti(OH) ₄ . The method for producing a photocatalyst solution according to claim 1, wherein the fluorocarbon resin comprises a resin containing tetrafluoroethylene as a main component. The method for producing a photocatalyst solution according to claim 1, wherein the alkoxy group of the siloxane compound reacts with the hydroxyl group of the photocatalyst in a sol-gel method. The method for producing a photocatalyst solution according to claim 1, wherein the alkoxy group of the oxirane compound is reacted with the hydroxyl group of the photocatalyst at room temperature for 30 minutes. The method for producing a photocatalyst solution according to claim 1, wherein the fluorocarbon resin is added such that the alkoxy group of the siloxane compound reacts with the hydroxyl group of the fluorocarbon resin, including stirring for 30 minutes, at 80 ° C The condition was heated for 3 days. The method for producing a photocatalyst solution according to claim 1, wherein the siloxane compound, the photocatalyst, and the fluorocarbon resin are mixed in a solvent. The method for producing a photocatalyst solution according to claim 10, wherein the solvent comprises ethyl acetate. The method for producing a photocatalyst solution according to claim 1, further comprising adding a hydrophobic agent. The method for producing a photocatalyst solution according to claim 12, wherein the hydrophobic agent comprises a fine powder of tetrafluoroethylene. A method for producing a textile having antifouling and self-cleaning properties, comprising: preparing a photocatalyst solution prepared by the method described in claim 1; applying the photocatalyst solution to a textile; And performing a drying step. The method for producing a textile having antifouling and self-cleaning properties as described in claim 14 of the patent application, further comprising performing a photodegradation test step. The method for producing a textile having antifouling and self-cleaning properties as described in claim 14 further includes performing a surface contact angle test step. The method for manufacturing a textile having antifouling and self-cleaning properties as described in claim 14 of the patent application further includes performing a stain resistance test step.