JP2023031896A - Liquid composition for forming water and oil repellent black film and production method therefor - Google Patents

Abstract

To provide a liquid composition for forming a film which is black and has water repellency, oil repellency, high strength, and high adhesion.SOLUTION: A liquid composition for forming a water and oil repellent black film is provided, including a titanium oxynitride particle (B) which has a specific surface area diameter of 10 nm-90 nm and with which a fluorine-based functional group component (A) including a perfluoroether structure represented by formula (1) is bound, an autoreactive-type carboxyl group-containing substance or the like (C), and a solvent (D). The liquid composition has a content of the carboxyl group-containing substance or the like (C) of 20 mass%-95 mass% and a sum of the contents of the fluorine-based functional group component (A) and the titanium oxynitride particles (B) of 5 mass%-80 mass% relative to 100 mass% of the whole amount of non-volatile components in the liquid composition. The liquid composition has a mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) in the range of 0.01-0.50.SELECTED DRAWING: Figure 1

Description

The present invention relates to a liquid composition for forming a black film having water repellency and oil repellency, and a method for producing the same. More particularly, the present invention relates to a liquid composition for forming a water- and oil-repellent black film containing titanium oxynitride particles and a method for producing the same.

Heretofore, as a film-forming liquid composition having water repellency and oil repellency, the present applicant disperses hydrophilic calcium carbonate having an average particle size of 5 to 200 nm in an organic solvent to prepare a dispersion liquid. In the first step of adjusting, a carboxylic acid having a nitrogen-containing perfluoroalkyl group represented by the following general formula (28) or a fluorine compound that is a halide thereof is added to the dispersion liquid, and the calcium carbonate and and a second step of synthesizing a composite material in which the fluorine compound is nanocomposited (Patent Document 1 (claim 1, claim 5, claim 6, Paragraph [0006], Paragraph [0017], Paragraph [0056] to Paragraph [0065]).). In this patent document 1, in the second step, a silane coupling agent such as trialkoxysilane represented by the chemical formula [R ₁ Si(OR ₂ ) ₃ ] may be added to the dispersion of the inorganic compound. is indicated. In formula (28), E represents a halogen or hydroxyl group (OH).

On the other hand, there is disclosed a black ink characterized by containing a black pigment made of black titanium oxynitride powder and having an OD value of 4.3 or more at a pigment concentration of 80% (Patent Document 2 (claim 3, See claim 4, claim 6, paragraph [0001]).). This black titanium oxynitride powder is produced by granulating titanium oxide powder using a polymer binder dissolved in water or an organic solvent, and bringing the granulated powder into contact with high-temperature ammonia gas for reduction treatment. 3 to 13% oxygen content, 18 to 25% nitrogen content, 0.3 to 10.0% carbon content, the remainder being Ti, specific surface area of 25 m ² /g or more, blackness (L value) 8.5 above and a specific gravity of 4.2 or less.

JP 2018-39987 A JP 2010-30841 A

In the method for producing fluorine-containing nanocomposite particles disclosed in Patent Document 1, the fluorine compound used there has a perfluoroamine structure, and the perfluoro group is bonded around the nitrogen, so that it has a rigid structure. easy. Therefore, even if the fluorine content in the liquid composition is increased, when the oil adheres to the film formed using the fluorine-containing nanocomposite particles, it may not be possible to improve the oil-shedding property. From the viewpoint of oiliness, the invention of Patent Document 1 still has room for improvement.

In the black ink disclosed in Patent Document 2, the black titanium oxynitride powder contained as the black pigment has high blackness and light shielding properties, and is excellent as a black matrix material. Also, when applied to the surfaces of vehicle interior members to improve their aesthetic appearance, the applied black film lacks a stain-preventing function, and an improvement has been desired.

An object of the present invention is to provide a liquid composition for forming a water- and oil-repellent black film, which forms a black film and has high water repellency, oil repellency, film strength and film adhesion, and a method for producing the same. It is in.

The present inventors found that the perfluoroether structure is more flexible than the perfluoroamine structure, and even if the fluorine content of the fluorine-based compound containing the fluorine-based functional group component of the perfluoroether structure is low, the oil does not form on the film. When it adheres, the oil falls off easily, and the titanium oxynitride particles are bound together with a substance containing a carboxyl group and/or an acetyl group (hereinafter simply referred to as "a substance containing a carboxyl group, etc.") to form a film. A black film is obtained by forming , and the strength and adhesion of the film are improved.

A first aspect of the present invention is titanium oxynitride having a specific surface area diameter of 10 nm to 90 nm to which a fluorine-based functional group component (A) containing a perfluoroether structure represented by the following general formula (1) or formula (2) is bonded. When the liquid composition contains particles (B), a self-reactive carboxyl group-containing substance (C), and a solvent (D), and the total amount of nonvolatile matter in the liquid composition is 100% by mass, the self-reactive carboxyl The content ratio of the group-containing material (C) is 20% by mass to 95% by mass, and the total content ratio of the fluorine-based functional group component (A) and the titanium oxynitride particles (B) is 5 % to 80% by mass, and the mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) is in the range of 0.01 to 0.50. It is a liquid composition for forming a water-repellent and oil-repellent black film.

In formulas (1) and (2) above, p, q and r are the same or different integers of 1 to 6, and the carbon skeleton may be linear or branched. In the above formulas (1) and (2), X is a hydrocarbon group having 2 to 10 carbon atoms and is selected from an ether bond, a CO—NH bond, an O—CO—NH bond and a sulfonamide bond. may contain one or more bonds that Furthermore, in the above formulas (1) and (2), Y is a hydrolyzate of silane or a main component of silica sol-gel.

Further describing this Y, Y is a site that bonds with the titanium oxynitride particles (B). As a specific example, in Formula (3) or Formula (4) described later, Y includes a structure in which the Z portion is hydrolyzed. Y also includes a main component of silica sol-gel obtained by mixing a silane compound of formula (3) or formula (4) and a silicon alkoxide such as tetraethoxysilane or tetramethoxysilane and hydrolyzing and polymerizing the mixture. Furthermore, as Y, the silane compound of formula (3) or (4), a silicon alkoxide such as tetraethoxysilane or tetramethoxysilane, and a silane containing an epoxy group, a vinyl group, or an ether group are mixed, A main component of hydrolytically polymerized silica sol-gel and the like are also included.

A second aspect of the present invention is an invention based on the first aspect, wherein the self-reactive carboxyl group-containing material (C) is an ethylene-acrylic acid copolymer or an ethylene-vinyl acetate copolymer. or a liquid composition for forming a water- and oil-repellent black film, which is an ethylene-vinyl acetate-acrylic acid copolymer.

A third aspect of the present invention is an invention based on the first or second aspect, and when a coating film is formed under conditions where the film thickness is 5.0 μm, the wavelength of the coating film is in the range of 380 nm to 780 nm is a liquid composition for forming a water- and oil-repellent black film having a maximum light transmittance of 25% or less. The reason why the wavelength range is 380 nm to 780 nm here is that the wavelength range visible to the human eye, that is, the visible light range is used for evaluation. This is because the coating film to be evaluated has poor light shielding properties as a decorative coating film, and cannot be concealed by the film.

In a fourth aspect of the present invention, as shown in FIG. 1, an aqueous dispersion of fluorine-containing titanium oxynitride particles, a self-reactive carboxyl group-containing substance, etc., and a solvent are mixed to obtain a water- and oil-repellent black color. A method for producing a film-forming liquid composition.

A fifth aspect of the present invention is an invention based on the fourth aspect, wherein the self-reactive carboxyl group-containing material (C) is an ethylene-acrylic acid copolymer or an ethylene-vinyl acetate copolymer. or a liquid composition for forming a water- and oil-repellent black film, which is an ethylene-vinyl acetate-acrylic acid copolymer.

The sixth aspect of the present invention is an invention based on the fourth aspect, and as shown in FIG. 1, the aqueous dispersion of the fluorine-containing titanium oxynitride particles contains fluorine A method for producing a water-repellent and oil-repellent black film-forming liquid composition prepared by adding and mixing a system compound and adding and mixing a catalyst to the mixed liquid.

The liquid composition for forming a water-repellent and oil-repellent black film according to the first aspect of the present invention (hereinafter sometimes simply referred to as a liquid composition) is a perfluoroether represented by the formula (1) or (2) above. A liquid composition containing titanium oxynitride particles (B) having a specific surface area diameter of 10 nm to 90 nm to which a fluorine-based functional group component (A) containing a structure is bonded, a carboxyl group-containing material (C), and a solvent (D) When the total amount of nonvolatile matter of the product is 100% by mass, the content of the carboxyl group-containing material (C) is 20% by mass to 95% by mass, and the fluorine-based functional group component (A) and the above The total content of the titanium oxynitride particles (B) is 5% by mass to 80% by mass, and the mass ratio (A/B ) is in the range of 0.01 to 0.50. When this liquid composition is formed into a film, it contains the titanium oxynitride particles (B) to which the fluorine-based functional group component (A) is bound. expensive. Also, when a film is formed, the titanium oxynitride particles (B) having a specific surface area diameter of 10 nm to 90 nm are bound together in the film by the carboxyl group-containing substance (C), etc., improving the strength and adhesion of the film. can be made Since the surface of the formed film is not smooth, the fingerprint is less noticeable on the surface of the film after the fingerprint is adhered to the surface of the film.

In the liquid composition of the second aspect of the present invention, the self-reactive carboxyl group-containing substance or the like is an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate-acrylic acid copolymer. Therefore, such a copolymer acts as a binder for the fluorine-containing titanium oxynitride particles, and when the liquid composition is deposited on the substrate surface, the film can be firmly bound to the substrate surface. .

In the liquid composition of the third aspect of the present invention, the maximum light transmittance in the wavelength range of 380 nm to 780 nm is 25% or less when the coating film is formed under the condition that the film thickness is 5.0 μm. The desired blackness is obtained.

In the method for producing a liquid composition according to the fourth aspect of the present invention, as shown in FIG. 1, an aqueous dispersion of fluorine-containing titanium oxynitride particles, a substance containing a carboxyl group, etc., and a solvent are mixed to form a water-repellent composition. A liquid composition for forming an oil-repellent black film is produced. As a result, titanium oxynitride particles whose particle surfaces are water- and oil-repellent are present in the carboxyl group-containing material and the like, and when the liquid composition is formed into a film, the film becomes black and the film is water- and oil-repellent. retained.

In the method for producing a liquid composition according to the fifth aspect of the present invention, a fluorine-based compound is added to and mixed with an aqueous dispersion of titanium oxynitride particles, and a catalyst is added to and mixed with this mixture. is uniformly dispersed in water.

In the method for producing a liquid composition according to the sixth aspect of the present invention, the carboxyl group-containing substance or the like is an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate-acrylic acid copolymer. Therefore, such a copolymer acts as a binder for the fluorine-containing titanium oxynitride particles, and when the liquid composition is deposited on the substrate surface, the film can be firmly bound to the substrate surface.

FIG. 2 is a flowchart for producing the water-repellent and oil-repellent black film-forming liquid composition of the present embodiment. FIG. 2 is an enlarged cross-sectional view of a water- and oil-repellent film formed on a base material of the present embodiment;

Next, a mode for carrying out the present invention will be described with reference to the drawings.

[Method for producing liquid composition for forming water-repellent and oil-repellent black film]
The liquid composition for forming a water-repellent and oil-repellent black film is generally produced by the following method.
As shown in FIG. 1, an aqueous dispersion 11 of titanium oxynitride particles is mixed with a fluorine-based compound 12 containing a fluorine-based functional group component (A), and further mixed with a catalyst 13 to obtain a water dispersion of fluorine-containing titanium oxynitride particles. A dispersion 14 is prepared. By mixing this aqueous dispersion 14, a carboxyl group-containing substance 15, and a solvent 16, a liquid composition 20 for forming a water-repellent and oil-repellent black film is produced. Each step will be described in detail below.

[Preparation of aqueous dispersion of titanium oxynitride particles]
First, titanium oxynitride (TiON) particles are dispersed in an aqueous solvent to prepare an aqueous dispersion of titanium oxynitride particles. The titanium oxynitride particles have a specific surface area diameter of 10 nm to 90 nm, preferably 12 nm to 70 nm. If the specific surface area is less than 10 nm, the titanium oxynitride particles tend to aggregate and become difficult to disperse in the medium. If it exceeds 90 nm, the titanium oxynitride particles fall off from the water- and oil-repellent film when the liquid composition is formed into a film.
The aqueous solvent is exemplified by water or a mixed solvent of water and ethanol. As the water, it is desirable to use ion-exchanged water, pure water, or the like in order to prevent contamination of impurities. Here, the reason why an aqueous solvent is used as the solvent and no organic solvent is used is for safety in handling. In this specification, the specific surface area diameter of the titanium oxynitride particles is calculated from the following formula (A), where S is the specific surface area measured by the BET method and ρ is the density of the titanium oxynitride particles. It is.
Specific surface area diameter = 6/ρS (A)

[Preparation of aqueous dispersion of fluorine-containing titanium oxynitride particles]
Next, a fluorine-based compound containing a fluorine-based functional group component represented by the above formula (1) or (2) is added to the prepared aqueous dispersion of titanium oxynitride particles to obtain titanium oxynitride particles. Synthesize a composite material in which particles and fluorine-based functional group components are nanocomposited. A catalyst is added to further promote the reaction. Thus, an aqueous dispersion of fluorine-containing titanium oxynitride particles is prepared.

Examples of the catalyst include organic acids, inorganic acids and alkalis. Examples of organic acids include formic acid and oxalic acid; examples of inorganic acids include hydrochloric acid, nitric acid and phosphoric acid; examples of alkalis include sodium hydroxide, lithium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, Ammonia is exemplified. Catalysts are not limited to those listed above.

A fluorine-based compound containing a fluorine-based functional group component is represented by the following general formula (3) or formula (4). More specifically, the perfluoroether groups in these formulas (3) and (4) include perfluoroether structures represented by the following formulas (5) to (13).

Further, examples of X in the above formulas (3) and (4) include structures represented by the following formulas (14) to (18). In addition, the following formula (14) is an ether bond, the following formula (15) is an ester bond, the following formula (16) is an amide bond, the following formula (17) is an urethane bond, and the following formula (18) is an example containing a sulfonamide bond. is shown.

In formulas (14) to (18) above, R ² and R ³ are hydrocarbon groups having 0 to 10 carbon atoms, and R ⁴ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of hydrocarbon groups for R ² and R ³ include alkylene groups such as methylene group and ethylene group, and examples of hydrocarbon groups for R ⁴ include alkyl groups such as methyl group and ethyl group, A phenyl group and the like are also included.

In the above formulas (3) and (4), R ¹ includes a methyl group, an ethyl group, and the like.

In formulas (3) and (4) above, Z is not particularly limited as long as it is a hydrolyzable group capable of forming a Si--O--Si bond upon hydrolysis. Specific examples of such hydrolyzable groups include alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups such as phenoxy and naphthoxy; and acyloxy groups such as aralkyloxy group, acetoxy group, propionyloxy group, butyryloxy group, valeryloxy group, pivaloyloxy group, and benzoyloxy group. Among these, it is preferable to apply an ethoxy group.

Here, as specific examples of the fluorine-based compound containing a fluorine-based functional group component having a perfluoroether structure represented by the above formula (3) or formula (4), for example, the following formulas (19) to (27) structures represented. In formulas (19) to (27) below, R is a methyl group or an ethyl group.

As described above, the fluorine-based compound contained in the water-repellent and oil-repellent black film-forming liquid composition of the present embodiment contains a perfluoroalkyl group having a short chain length of 6 or less carbon atoms in the molecule of the oxygen atom and a perfluoroalkylene group. Since it has a perfluoroether group in which multiple groups are bonded and has a high fluorine content in the molecule, it can impart excellent water and oil repellency to the formed film.

[Self-reactive carboxyl group-containing substance, etc.]
The self-reactive carboxyl group-containing material is an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate-acrylic acid copolymer. Commercially available ethylene-vinyl acetate products include Sepoljon VA406N, Sepoljon VA407N (both manufactured by Sumitomo Seika Co., Ltd.), Sumikaflex S-201HQ, S-355HQ, S-401HQ, S-465HQ (both from Sumitomo Seika). Chemical Co.), Aquatex EC-1800, EC-1200 (both manufactured by Japan Coating Resin Co., Ltd.).Ethylene-acrylic acid copolymers include Zaixen A, Zaixen L, and Zaixen N (both Sumitomo Seiko Chemical Co., Ltd.), etc., and ethylene-vinyl acetate-acrylic acid type ones include Sumikaflex S-900HL (manufactured by Sumitomo Chemical Co., Ltd.), etc. Sumika is an ethylene-vinyl acetate-vinyl chloride copolymer. Flex S-830 and Sumikaflex S-950HQ, which is an ethylene-vinyl acetate-vinyl versatate copolymer (both manufactured by Sumitomo Chemical Co., Ltd.), and acrylic TOCRYL BCX-1160R-2. (manufactured by Toyochem).

[Liquid composition for forming a water- and oil-repellent black film]
The liquid composition for forming a water-repellent and oil-repellent black film of the present embodiment is produced by the above production method, and comprises titanium oxynitride particles (B) to which the above-described fluorine-based functional group component (A) is bonded, and a carboxyl group-containing material. Etc. (C) and Solvent (D). This fluorine-based functional group component (A) has a perfluoroether structure represented by the above general formula (1) or formula (2). It is contained in an amount of 1% by mass to 10% by mass in the composition. If the fluorine-based functional group component is less than 1% by mass, the formed film cannot be imparted with oil repellency, and if it exceeds 10% by mass, repelling of the film occurs, resulting in poor film-forming properties. A preferable content ratio of the fluorine-based functional group component is 1.5% by mass to 8% by mass.

The carboxyl group-containing substance (C) is contained in the liquid composition in an amount of 20% by mass to 95% by mass when the total amount of non-volatile matter in the liquid composition is 100% by mass. If the content of carboxyl group-containing substances is less than 20% by mass, the resulting film will be inferior in adhesion and strength to the substrate, and if it exceeds 95% by mass, the film will not be imparted with oil repellency. Furthermore, the total content of the fluorine-based functional group component (A) and the titanium oxynitride particles (B) is 5% by mass or more in the liquid composition when the total amount of nonvolatile matter in the liquid composition is 100% by mass. 80% by mass, preferably 10% to 60% by mass. Furthermore, the mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) is in the range of 0.01 to 0.50, preferably 0.02 to 0.40.

When the total amount of the component (A) and the particles (B) is less than 5% by mass when the total amount of non-volatile matter in the liquid composition is 100% by mass, the water- and oil-repellent performance of the water- and oil-repellent film and the film Blackness is reduced. If the total amount exceeds 80% by mass, the content of (C) such as the carboxyl group-containing material becomes relatively low, and when the liquid composition is formed on the substrate, the water- and oil-repellent film is formed on the substrate. It no longer adheres firmly to the surface. When the mass ratio (A/B) is less than 0.01, the water and oil repellency of the water and oil repellent film is poor, and when it exceeds 0.50, the adhesion of the water and oil repellent film to the substrate surface is reduced. do. The solvent (D) is water or water having an ethanol content of 40% by mass or less. The reason why the content of ethanol is 40% by mass or less is for safety in handling. Further, by using a mixed solvent in which water and ethanol are mixed, the drying speed is improved and the film formability is improved.

Specific examples of the perfluoroether structure include structures represented by formulas (19) to (27) described above.

Since the liquid composition of the present embodiment contains a carboxyl group-containing substance or the like as a main component, when the film is formed on the substrate surface, the water- and oil-repellent film has excellent adhesion to the substrate surface and is difficult to peel off. A strong water- and oil-repellent film can be obtained. In addition, since the liquid composition contains the fluorine-based functional group component of the perfluoroether structure represented by the above general formula (1) or (2), the formed film has the effects of water repellency and oil repellency. Furthermore, since titanium oxynitride particles are included, the formed film is black.

[Method of forming a water-repellent and oil-repellent film on a substrate surface]
In order to form the water- and oil-repellent film of the present embodiment on the substrate surface, the liquid composition for forming a water- and oil-repellent black film is applied onto the substrate, and then dried in the air at room temperature. It is formed by curing the The base material is not particularly limited, but may be stainless steel (SUS), metal plates such as aluminum and iron, glass such as window glass and mirrors, tiles, plastics such as polyvinyl chloride (PVC), or polyethylene terephthalate (PET). , polyester films such as polybutylene terephthalate and polyethylene naphthalate. Examples of methods for applying the liquid composition include screen printing, bar coating, die coating, doctor blade, spin, and brush coating.

As shown in FIG. 2, the water- and oil-repellent black film 2 formed on the surface of the base material 1 consists of a large number of fluorine-containing titanium oxynitride particles 3 whose particle surfaces are covered with a fluorine-based functional group component as a binder. It is composed by binding with 4 such as a carboxyl group-containing material. Since the water-repellent and oil-repellent black film 2 contains the fluorine-containing titanium oxynitride particles 3 to which the fluorine-based functional group component is bonded, the oil-repellent performance of the film is maintained. Further, since the fluorine-containing titanium oxynitride particles 3 having a specific surface area diameter of 10 nm to 90 nm are bonded to each other in the film 2 by the carboxyl group-containing substance 4, the strength and adhesion of the film 2 can be improved. In addition, due to the presence of the fluorine-containing titanium oxynitride particles 3, the film becomes black and the film surface becomes uneven. The film thickness and blackness of the film can be controlled by changing the particle size of the titanium oxynitride particles and the content of the titanium oxynitride particles in the film components.

Next, examples of the present invention will be described in detail together with comparative examples. First, Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3 for preparing an aqueous dispersion of fluorine-containing titanium oxynitride particles will be described, and then the formation of a water- and oil-repellent black film using these Synthesis Examples and Comparative Synthesis Examples. Examples 1 to 5 and Comparative Examples 1 to 5 relating to the production of liquid compositions for use will be described.

[Synthesis Examples 1 to 5 for preparing an aqueous dispersion of fluorine-containing titanium oxynitride particles, Comparative Synthesis Examples 1 to 3]
<Synthesis Example 1>
Water is added to titanium oxynitride particles having a specific surface area diameter of 12 nm obtained by reducing titanium oxide powder with ammonia gas, and mixed with a bead mill device (manufactured by Asada Iron Works, model: Picomil PCM-LR) to a concentration of 30. An aqueous dispersion of titanium oxynitride particles was prepared at a weight percentage. 50 g of the resulting aqueous dispersion of titanium oxynitride particles was placed in a beaker, and 7.50 g of the fluorine-based compound represented by the above formula (19) was added and mixed. Next, 0.02 g of nitric acid was added and mixed at 40° C. for 2 hours to obtain an aqueous dispersion of fluorine-containing titanium oxynitride particles in which the titanium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) was 0.50.

<Synthesis Example 2>
An aqueous dispersion of titanium oxynitride particles having a specific surface area of 25 nm (concentration of 30% by mass) was prepared. 50 g of the resulting aqueous dispersion of titanium oxynitride particles was placed in a beaker, and 0.75 g of the fluorine-based compound represented by the above formula (20) was added and mixed. Next, 0.01 g of nitric acid was added and mixed at 40° C. for 2 hours to obtain an aqueous dispersion of fluorine-containing titanium oxynitride particles in which the titanium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) was 0.05.

<Synthesis Example 3>
An aqueous dispersion (concentration: 30% by mass) of titanium oxynitride particles having a specific surface area of 90 nm was prepared. 50 g of the resulting aqueous dispersion of titanium oxynitride particles was placed in a beaker, and 0.23 g of the fluorine-based compound represented by the above formula (21) was added and mixed. Next, 0.01 g of nitric acid was added and mixed at 40° C. for 2 hours to obtain an aqueous dispersion of fluorine-containing titanium oxynitride particles in which the titanium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) was 0.015.

<Synthesis Example 4>
An aqueous dispersion of titanium oxynitride particles having a specific surface area of 25 nm (concentration of 30% by mass) was prepared. 50 g of the resulting aqueous dispersion of titanium oxynitride particles was placed in a beaker, and 2.25 g of the fluorine-based compound represented by the above formula (22) was added and mixed. Next, 0.01 g of nitric acid was added and mixed at 40° C. for 2 hours to obtain an aqueous dispersion of fluorine-containing titanium oxynitride particles in which the titanium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) was 0.15.

<Synthesis Example 5>
An aqueous dispersion of titanium oxynitride particles having a specific surface area of 25 nm (concentration of 30% by mass) was prepared. 50 g of the resulting aqueous dispersion of titanium oxynitride particles was placed in a beaker, and 1.50 g of the fluorine-based compound represented by the above formula (27) was added and mixed. Next, 0.01 g of nitric acid was added and mixed at 40° C. for 2 hours to obtain an aqueous dispersion of fluorine-containing titanium oxynitride particles in which the titanium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) was 0.10.

<Comparative Synthesis Example 1>
An aqueous dispersion of titanium oxynitride particles having a specific surface area of 25 nm (concentration of 30% by mass) was prepared. 50 g of the resulting aqueous dispersion of titanium oxynitride particles was placed in a beaker, and 0.075 g of the fluorine-based compound represented by the above formula (27) was added and mixed. Next, 0.01 g of nitric acid was added and mixed at 40° C. for 2 hours to obtain an aqueous dispersion of fluorine-containing titanium oxynitride particles in which the titanium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) was 0.005.

<Comparative Synthesis Example 2>
An aqueous dispersion of titanium oxynitride particles having a specific surface area of 25 nm (concentration of 30% by mass) was prepared. 50 g of the resulting aqueous dispersion of titanium oxynitride particles was placed in a beaker, and 9.00 g of the fluorine-based compound represented by the above formula (27) was added and mixed. Next, 0.03 g of nitric acid was added and mixed at 40° C. for 2 hours to obtain an aqueous dispersion of fluorine-containing titanium oxynitride particles in which the titanium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) was 0.60.

<Comparative Synthesis Example 3>
An aqueous dispersion of titanium oxynitride particles having a specific surface area of 120 nm (concentration of 30% by mass) was prepared. 50 g of the resulting aqueous dispersion of titanium oxynitride particles was placed in a beaker, and 2.25 g of the fluorine-based compound represented by the above formula (27) was added and mixed. Next, 0.01 g of nitric acid was added and mixed at 40° C. for 2 hours to obtain an aqueous dispersion of fluorine-containing titanium oxynitride particles in which the titanium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) was 0.15.

Table 1 below shows the contents of the aqueous dispersions of the fluorine-containing titanium oxynitride particles of Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3. In Table 1, R in the formulas of fluorine-containing silanes represented by formulas (19) to (22) and (27) as fluorine-based compounds are all ethyl groups.

[Examples 1 to 5 and Comparative Examples 1 to 5 for producing a liquid composition for forming a water-repellent and oil-repellent black film]
<Example 1>
0.48 g of the aqueous dispersion of the fluorine-containing titanium oxynitride particles obtained in Synthesis Example 1, and 5.00 g of ethylene-vinyl acetate Sumikaflex S-401HQ (manufactured by Sumitomo Chemical Co., Ltd.) as a carboxyl group-containing substance. , and 41.9 g of water as a solvent and 10.5 g of industrial alcohol (AP-7) were mixed to prepare a liquid composition for forming a water- and oil-repellent black film. The contents are shown in Table 2 below.

In Table 2, since Sumikaflex S-401HQ and the like contain non-volatile matter or solid matter and a dispersion medium such as water, they are shown as "Carboxyl Group-Containing Material, etc. Containing a Dispersion Medium". Therefore, the "content ratio in the liquid composition excluding the solvent and the dispersion medium" in Table 2 means the content ratio of the non-volatile matter or solid matter in the liquid composition. Further, the content ratio of "(C)" in Table 2 means the content ratio of carboxyl group-containing substances and the like in the nonvolatile matter excluding the volatile matter. Further, the content ratio of "(A) + (B)" means the content ratio of the fluorine-based functional group component (A) and the titanium oxynitride particles (B) in total and not including the solvent, that is, the content ratio of the non-volatile matter. is. The content ratio (%) of the fluorine-based functional group component (A) in the liquid composition excluding the solvent and the dispersion medium can be expressed as [(A )/[(A)+(B)+(C)]].

<Examples 2 to 5 and Comparative Examples 1 to 5>
As shown in Table 2, in Examples 2 to 5, the aqueous dispersions of the fluorine-containing titanium oxynitride particles obtained in Synthesis Examples 2 to 5 shown in Table 1 were used, respectively, and their respective weighing amounts were determined. In Comparative Examples 1 to 5, the aqueous dispersions of the fluorine-containing titanium oxynitride particles obtained in Synthesis Examples 1 and 3 and Comparative Synthesis Examples 1 to 3 shown in Table 1 were used, and the respective weighing amounts were determined.

Sumikaflex S-950HQ (manufactured by Sumitomo Chemical Co., Ltd.), which is an ethylene-vinyl acetate-vinyl versatate copolymer, was used as the carboxyl group-containing material in Example 2 and Comparative Examples 1 to 5 as the carboxyl group-containing material. were used to determine the respective weights. In Example 3, acrylic TOCRYL BCX-1160R-2 (manufactured by Toyochem Co., Ltd.) was used as the carboxyl group-containing material, and its weighing was determined. In Example 4, Sumikaflex S-830 (manufactured by Sumitomo Chemical Co., Ltd.), which is an ethylene-vinyl acetate-vinyl chloride copolymer, was used as the carboxyl group-containing substance, and the weight was determined. In Example 5, Zaixen N (manufactured by Sumitomo Seika Co., Ltd.), which is an ethylene-acrylic acid copolymer, was used as the carboxyl group-containing material, and the weighing amount was determined.
In this way, liquid compositions for forming water-repellent and oil-repellent black films of Examples 2 to 5 and Comparative Examples 1 to 5 were prepared.

<Comparative test and evaluation>
The 10 kinds of liquid compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were applied to a thickness of 1.1 mm, a length of 100 mm, and a width of 100 mm using a brush (Suematsu Brush Nylon Brush Meister). Ten kinds of coating films were formed by coating each of the glass substrates so that the thickness after drying was 5.0 μm. All the coating films were allowed to stand in an air atmosphere at room temperature for 3 hours, and the coating films were dried to obtain 10 kinds of films on the glass substrates. These films were evaluated for surface water wettability (water repellency), oil repellency, and film appearance, and subjected to Cellotape (registered trademark) peeling test (hereinafter referred to as adhesion test). Also, the light transmittance of the coating film was evaluated. These results are shown in Table 3 below.

(1) Water repellency of film surface (contact angle)
Using Drop Master DM-700 manufactured by Kyowa Interface Science Co., Ltd., ion-exchanged water at 22° C.±1° C. is prepared in a syringe, and a droplet of 2 μL is ejected from the tip of the needle of the syringe. A film on a glass substrate to be evaluated is then brought close to the droplet so that the droplet adheres to the film. The contact angle of this adhering water was measured. The water wettability (water repellency) of the film surface was evaluated using the value obtained by analyzing the contact angle of water one second after the film surface was in a stationary state by the θ/2 method. The water repellency was judged to be "good" when the contact angle of water was 90 degrees or more, and the water repellency was judged to be "bad" when it was less than 90 degrees.

(2) Oil repellency of film surface (contact angle)
Using Kyowa Interface Science Drop Master DM-700, n-hexadecane (hereinafter referred to as oil) at 22 ° C ± 1 ° C is prepared in a syringe, and a droplet of 2 μL is ejected from the tip of the needle of the syringe. do. A film on a glass substrate to be evaluated is then brought close to the droplet so that the droplet adheres to the film. The contact angle of this adhering oil was measured. The oil repellency of the film surface was evaluated using the contact angle of oil obtained by analyzing the contact angle 1 second after the oil touched the film surface in a stationary state by the θ/2 method. An oil contact angle of 50 degrees or more was judged to be "good" in oil repellency, and an oil contact angle of less than 50 degrees was judged to be "poor" in oil repellency.

(3) Appearance of film The film on the glass substrate to be evaluated was visually observed to check whether the film was transparent and whether particles were aggregated in the film. If the film was transparent, it was evaluated as "somewhat good" or "good", and if particles were aggregated in the film, it was evaluated as "poor aggregation".

(4) Film Adhesion Test The film on the glass substrate to be evaluated was cross-cut in a grid pattern with a width of 1 mm, and the cross-cut film was attached to an adhesive tape (manufactured by Nichiban Co., Ltd., trade name “ Cellotape (registered trademark)”) was affixed, and a Cellotape (registered trademark) peeling test (adhesion test) was performed in accordance with the grid tape method of JISK5600-5-6 (cross-cut method). The denominator represents 100 cross-cut squares, and the numerator represents the number of squares remaining on the substrate after the peel test. A case of 100/100 was evaluated as "accepted", and a case where peeling occurred was evaluated as "failed".

(5) Film light transmittance evaluation test For the coating film on the glass substrate to be evaluated, using a spectrophotometer (Hitachi High Technologies, U-4150), the base line with the coating film formed After measuring , the light transmittance in the visible light region with a wavelength of 380 nm to 780 nm was measured to obtain the maximum light transmittance (%).

As is clear from Table 3, in Comparative Example 1, the ratio of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) was as low as 0.005. Although the test passed, the contact angles of water and n-hexadecane were poor, and the water and oil repellency of the film was poor. The maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm was as low as 10%, and a black film was obtained.

In Comparative Example 2, since the ratio of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) was too high at 0.60, the particles in the film aggregated and the appearance of the film was poor. . In addition, the film failed the sellotape (registered trademark) peeling test, and the contact angles of water and n-hexadecane were poor, and the film was inferior in water and oil repellency. The maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm was as low as 21.3%, and a black film was obtained.

In Comparative Example 3, the titanium oxynitride particles had an excessively large specific surface area of 120 nm, so the film had a good appearance, but failed the film peeling test. Moreover, the contact angle of water and n-hexadecane was poor, and the water and oil repellency of the film was also poor. The maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm was as high as 26.2%, and a black film was not obtained. It was considered that this was because the specific surface area of the titanium oxynitride particles was too large, resulting in a low hiding power of the film.

In Comparative Example 4, the total content of the fluorine-based functional group component (A) and the titanium oxynitride particles (B) was too low at 3% by mass when the total non-volatile content of the liquid composition was 100% by mass. Therefore, the peeling test of the film was passed, and the appearance of the film was good, but the contact angle of water and n-hexadecane was poor, and the water and oil repellency of the film was also poor. The maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm was as high as 45.7%, and a black film was not obtained. It is considered that this is because there are few titanium oxynitride particles in the film.

In Comparative Example 5, the total content of the fluorine-based functional group component (A) and the titanium oxynitride particles (B) was too high at 82% by mass when the total non-volatile content of the liquid composition was 100% by mass. Therefore, it was difficult for the water- and oil-repellent film to firmly adhere to the substrate surface. As a result, the contact angles of water and n-hexadecane were poor, particles in the film were aggregated, and the appearance of the film was poor. In the peeling test of the film, the number of squares remaining on the substrate was 30, and some of the squares were peeled off. The maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm was as low as 15.8%, and a black film was obtained.

On the other hand, in Examples 1 to 5, the specific surface area diameter of the titanium oxynitride particles was in the range of 10 nm to 90 nm, and the carboxyl group-containing substances, etc., when the total amount of nonvolatile matter in the liquid composition was 100% by mass. The fluorine-based functional group component (A) and the titanium oxynitride particles (B) when the content of (C) is 20% by mass to 95% by mass and the total amount of nonvolatile matter in the liquid composition is 100% by mass The total content ratio is 5% by mass to 80% by mass, and "(A) / (B)" is in the range of 0.01 to 0.50, satisfying the scope of the invention of the first aspect Therefore, both the contact angle of water and n-hexadecane and the appearance of the film were good, and the adhesion test of the film passed both tests. The maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm was 2.9% to 24.5%, which was 25% or less, and a black film was obtained in each case. In particular, in Example 3, the content of titanium oxynitride particles in the liquid composition was high, so the maximum light transmittance was very low at 2.9%.

The liquid composition for forming a water-repellent and oil-repellent black film of the present invention can be used in interior products such as kitchens and washrooms where good design is required, vehicle interior components such as vehicle instrument panels, air conditioners, car navigation systems, and audio systems. It is used in the field to prevent contamination.

REFERENCE SIGNS LIST 1 base material 2 water- and oil-repellent black film 3 fluorine-containing titanium oxynitride particles 4 carboxyl group-containing material, etc.

Claims (6)

Titanium oxynitride particles (B) having a specific surface area diameter of 10 nm to 90 nm to which a fluorine-based functional group component (A) containing a perfluoroether structure represented by the following general formula (1) or formula (2) is bonded, and a self-reactive type A carboxyl group and / or acetyl group containing material (C) and a solvent (D),
When the total amount of nonvolatile matter in the liquid composition is 100% by mass, the content of the self-reactive carboxyl group- and/or acetyl group-containing material (C) is 20% by mass to 95% by mass, and The total content of the fluorine-based functional group component (A) and the titanium oxynitride particles (B) is 5% by mass to 80% by mass,
Forming a water- and oil-repellent black film, wherein the mass ratio (A/B) of the fluorine-based functional group component (A) to the titanium oxynitride particles (B) is in the range of 0.01 to 0.50. liquid composition.

In formulas (1) and (2) above, p, q and r are the same or different integers of 1 to 6, and the carbon skeleton may be linear or branched. In the above formulas (1) and (2), X is a hydrocarbon group having 2 to 10 carbon atoms and is selected from an ether bond, a CO—NH bond, an O—CO—NH bond and a sulfonamide bond. may contain one or more bonds that Furthermore, in the above formulas (1) and (2), Y is a hydrolyzate of silane or a main component of silica sol-gel. The self-reactive carboxyl group- and/or acetyl group-containing material (C) is an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate-acrylic acid copolymer. 2. The liquid composition for forming a water-repellent and oil-repellent black film according to 1 above. The water and oil repellency according to claim 1 or 2, wherein the maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm is 25% or less when the coating film is formed under the condition that the film thickness is 5.0 µm. A liquid composition for forming a black film. A method for producing a liquid composition for forming a water- and oil-repellent black film by mixing an aqueous dispersion of fluorine-containing titanium oxynitride particles, a self-reactive substance containing a carboxyl group and/or an acetyl group, and a solvent. The self-reactive carboxyl group- and/or acetyl group-containing material (C) is an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate-acrylic acid copolymer. 5. A method for producing the liquid composition for forming a water-repellent and oil-repellent black film according to 4 above. 5. The repellent according to claim 4, wherein the aqueous dispersion of fluorine-containing titanium oxynitride particles is prepared by adding and mixing a fluorine-based compound to an aqueous dispersion of titanium oxynitride particles, and adding and mixing a catalyst to the mixture. A method for producing a liquid composition for forming a water- and oil-repellent black film.

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