Water- and oil-repellent black film-forming liquid composition and method for producing the same

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 zirconium oxynitride particle (B) which has a specific surface area diameter of 10 nm-45 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 zirconium 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 zirconium oxynitride particles (B) in the range of 0.01-0.50.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a liquid composition for forming a water- and oil-repellent black film and a method for producing the same, and more particularly to a liquid composition for forming a water- and oil-repellent black film containing zirconium oxynitride particles and a method for producing the same. [Background technology]

[0002] The present applicant has previously proposed a method for producing fluorine-containing nanocomposite particles, which includes the following steps: a first step of dispersing hydrophilic calcium carbonate having an average particle size of 5 to 200 nm in an organic solvent to prepare a dispersion; and a second step of adding a carboxylic acid having a nitrogen-containing perfluoroalkyl group represented by the following general formula (28) or a fluorine compound, which is a halide thereof, to the dispersion to synthesize a nanocomposite material of the calcium carbonate and the fluorine compound (see Patent Document 1 (claims 1, 5, and 6, paragraphs

[0006] ,

[0017] , and

[0056] to

[0065] ). Patent Document 1 also discloses that in the second step, a silane coupling agent, such as trialkoxysilane represented by the chemical formula [R1Si(OR2)3], may be added to the dispersion of the inorganic compound. In formula (28), E represents a halogen or a hydroxyl group (OH).

[0003] [ka]

[0004] Meanwhile, a light-shielding resin composition has been disclosed that can produce a cured film with excellent moisture resistance (see Patent Document 2 (Claim 1, Claim 9, Paragraphs

[0006] and

[0017] )). This light-shielding resin composition contains: a light-shielding pigment that is one or more kinds selected from the group consisting of metal nitride-containing particles containing atom A and metal oxynitride-containing particles containing atom A, wherein the light-shielding pigment contains at least one of a nitride and an oxynitride of a transition metal of Groups 3 to 7 of the transition metals and having an electronegativity of 1.22 to 1.80, and the atom A is at least one kind selected from the group consisting of hafnium and tungsten, and is an atom different from the transition metal; and a resin.

[0005] The light-shielding pigment disclosed in Patent Document 2 contains one or more elements selected from the group consisting of zirconium oxynitride and zirconium nitride. Patent Document 2 describes that this light-shielding pigment contains at least one of a nitride and an oxynitride of a Group 3 to 7 transition metal having an electronegativity within a predetermined range, and an atom A (at least one element selected from the group consisting of hafnium and tungsten), and therefore the moisture resistance of a cured film obtained from the composition is improved. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2018-39987 [Patent Document 2] International Publication No. 2020 / 017184 Summary of the Invention [Problem to be solved by the invention]

[0007] In the method for producing fluorine-containing nanocomposite particles disclosed in Patent Document 1, the fluorine compound used therein has a perfluoroamine structure, and since the perfluoro groups are bonded to the nitrogen at the center, it is prone to have a rigid structure. Therefore, even if the fluorine content in the liquid composition is increased, when oil adheres to a film formed using the fluorine-containing nanocomposite particles, the oil may not slide off well. From the viewpoint of oil repellency, the invention of Patent Document 1 still has room for improvement.

[0008] When a black film is formed using the light-shielding resin composition disclosed in Patent Document 2, the black film has excellent moisture resistance. However, when the light-shielding resin composition is applied to the surface of an interior product that requires design or a vehicle interior member in order to enhance the aesthetics of the product, the applied black film has poor stain-preventing properties, and improvement has been desired.

[0009] 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 that has high water repellency, oil repellency, film strength, and film adhesion, and a method for producing the same. [Means for solving the problem]

[0010] The present inventors have arrived at the present invention by noting that a perfluoroether structure is more likely to have a flexible structure than a perfluoroamine structure, that a fluorine-based compound containing a fluorine-based functional group component of a perfluoroether structure has good oil sliding properties when oil adheres to the film even if the fluorine content is low, and that when a film is formed by binding zirconium oxynitride particles together with a carboxyl group- and / or acetyl group-containing substance (hereinafter simply referred to as a "carboxyl group-containing substance, etc."), a black film is obtained and the strength and adhesion of the film are improved.

[0011] The first aspect of the present invention is a method for manufacturing a semiconductor device comprising the following general steps: Equation (3) and Equation (4)The present invention comprises zirconium oxynitride particles (B) having a specific surface area diameter of 10 nm to 45 nm and having a fluorine-based functional group component (A) containing a perfluoroether structure represented by the formula (I) bonded thereto, a self-reactive carboxyl group- and / or acetyl group-containing substance (C), and a solvent (D), 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; The water- and oil-repellent black film-forming liquid composition is characterized in that, when the total amount of nonvolatile matters in the liquid composition is taken as 100 mass%, the content of the self-reactive carboxyl group- and / or acetyl group-containing material (C) is 20 mass% to 95 mass%, the total content of the fluorine-based functional group component (A) and the zirconium oxynitride particles (B) is 5 mass% to 80 mass%, and the mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) is in the range of 0.01 to 0.50.

[0012] [ka]

[0013] the above Equation (3) and Equation (4) In the formula, p, q, and r are the same or different integers of 1 to 6, and the carbon skeleton may be linear or branched. Equation (3) and Equation (4) wherein X is a hydrocarbon group having 2 to 10 carbon atoms, which may contain one or more bonds selected from an ether bond, a CO—NH bond, an O—CO—NH bond, and a sulfonamide bond; 。

[0016] The present invention Second perspective teeth, First perspective The invention is based on the above, and is a liquid composition for forming a water- and oil-repellent black film, which, when formed into a coating film with a thickness of 5.0 μm, has a maximum light transmittance of 25% or less in the wavelength range of 380 nm to 780 nm. The wavelength range of 380 nm to 780 nm is set so that evaluation is performed in the wavelength range visible to the human eye, i.e., the visible light range, and the maximum light transmittance is set to 25% or less because if the maximum light transmittance exceeds 25%, the coating film being evaluated will have poor light-shielding properties as a decorative coating film and will not be able to provide concealment.

[0017] The present invention Third perspective is the present invention A method for producing a water- and oil-repellent black film-forming liquid composition according to the first and second aspects, As shown in FIG. 1, an aqueous dispersion of fluorine-containing zirconium oxynitride particles, a self-reactive carboxyl group and / or acetyl group-containing substance, and a solvent are mixed to produce a water- and oil-repellent black film-forming liquid composition. The self-reactive carboxyl group and / or acetyl group-containing substance (C) is an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate-acrylic acid copolymer. is.

[0019] The present invention Fourth perspective teeth, Third perspective The present invention is based on the above, and is a method for producing a water- and oil-repellent black film-forming liquid composition, in which the aqueous dispersion of fluorine-containing zirconium oxynitride particles is prepared by adding and mixing a fluorine-based compound to an aqueous dispersion of zirconium oxynitride particles, and then adding and mixing a catalyst to the mixture, as shown in FIG. [Effects of the Invention]

[0020] The water- and oil-repellent black film-forming liquid composition according to the first aspect of the present invention (hereinafter, sometimes simply referred to as the liquid composition) comprises the above-mentioned Formula (3) or Formula (4) The liquid composition comprises zirconium oxynitride particles (B) having a specific surface area diameter of 10 nm to 45 nm and bonded to a fluorine-based functional group component (A) containing a perfluoroether structure represented by the formula: (B), a carboxyl group-containing substance (C), and a solvent (D), wherein, when the total amount of nonvolatile content of the liquid composition is taken as 100 mass%, the content of the carboxyl group-containing substance (C) is 20 mass% to 95 mass%, the combined content of the fluorine-based functional group component (A) and the zirconium oxynitride particles (B) is 5 mass% to 80 mass%, and the mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) is in the range of 0.01 to 0.50. When this liquid composition is used to form a film, the film formed is black and has high water and oil repellency because it contains zirconium oxynitride particles (B) bonded to the fluorine-based functional group component (A). Furthermore, when the film is formed, the zirconium oxynitride particles (B) with a specific surface area diameter of 10 nm to 45 nm are bonded together in the film by the carboxyl group-containing substance (C), etc., thereby improving the strength and adhesion of the film. Since the surface of the formed film is not smooth, fingerprints are less noticeable after being left on the film surface.

[0021] Also, Since the self-reactive carboxyl group-containing substance is an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate-acrylic acid copolymer, these copolymers act as binders for the fluorine-containing zirconium oxynitride particles, and when the liquid composition is formed into a film on the surface of a substrate, the film can be firmly bound to the surface of the substrate.

[0022] The present invention Second perspective When this liquid composition is used to form a coating film with a thickness of 5.0 μm, the maximum light transmittance in the wavelength range of 380 nm to 780 nm is 25% or less, and therefore the desired blackness can be obtained.

[0023] The present invention Third perspective In the method for producing the liquid composition, a water- and oil-repellent black film-forming liquid composition is produced by mixing an aqueous dispersion of fluorine-containing zirconium oxynitride particles, a carboxyl group-containing substance, etc., and a solvent, as shown in Figure 1. As a result, zirconium oxynitride particles having water- and oil-repellent particle surfaces are present in the carboxyl group-containing substance, etc., and when the liquid composition is formed into a film, the film turns black and retains its water- and oil-repellent properties. Furthermore, since the carboxyl group-containing substance is an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate-acrylic acid copolymer, these copolymers act as binders for the fluorine-containing zirconium oxynitride particles, and when the liquid composition is formed into a film on the surface of a substrate, the film can be firmly bound to the surface of the substrate.

[0024] The present invention Fourth perspective In the method for producing the liquid composition, a fluorine-based compound is added and mixed with an aqueous dispersion of zirconium oxynitride particles, and a catalyst is then added and mixed with this mixture, thereby obtaining an aqueous dispersion in which the fluorine-containing zirconium oxynitride particles are uniformly dispersed. [Brief explanation of the drawings]

[0026] [Figure 1] FIG. 1 is a flow diagram showing a production process for a water- and oil-repellent black film-forming liquid composition according to an embodiment of the present invention. [Figure 2] FIG. 2 is an enlarged cross-sectional view of a water- and oil-repellent film formed on a substrate according to the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0027] Next, an embodiment of the present invention will be described with reference to the drawings.

[0028] [Method for producing a water- and oil-repellent black film-forming liquid composition] The water- and oil-repellent black film-forming liquid composition is generally produced by the following method. As shown in Fig. 1, a fluorine-based compound 12 containing a fluorine-based functional group component (A) is mixed with an aqueous dispersion 11 of zirconium oxynitride particles, and a catalyst 13 is further added to prepare an aqueous dispersion 14 of fluorine-containing zirconium oxynitride particles. This aqueous dispersion 14 is mixed with a carboxyl group-containing substance or the like 15 and a solvent 16 to produce a water- and oil-repellent black film-forming liquid composition 20. Each step will be described in detail below.

[0029] [Preparation of aqueous dispersion of zirconium oxynitride particles] First, zirconium oxynitride (ZrON) particles are dispersed in an aqueous solvent to prepare an aqueous dispersion of zirconium oxynitride particles. The zirconium oxynitride particles have a specific surface area diameter of 10 nm to 45 nm, preferably 12 nm to 40 nm. If the specific surface area diameter is less than 10 nm, the zirconium oxynitride particles are likely to aggregate and become difficult to disperse in the medium. If the specific surface area diameter exceeds 45 nm, the zirconium oxynitride particles will fall off from the water- and oil-repellent film when the liquid composition is formed into a film. Examples of aqueous solvents include water and a mixed solvent of water and ethanol. It is desirable to use ion-exchanged water or pure water as the water to prevent the inclusion of impurities. The reason why an aqueous solvent is used as the solvent, and an organic solvent is not used, is to ensure safety in handling. In this specification, the specific surface area diameter of the zirconium 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 zirconium oxynitride particles. Specific surface area diameter = 6 / ρS (A)

[0030] [Preparation of aqueous dispersion of fluorine-containing zirconium 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 zirconium oxynitride particles to synthesize a nanocomposite material of the zirconium oxynitride particles and the fluorine-based functional group component. A catalyst is then added to further promote the reaction. This results in the preparation of an aqueous dispersion of fluorine-containing zirconium oxynitride particles.

[0031] The catalyst may be an organic acid, an inorganic acid, or an alkali. Examples of organic acids include formic acid and oxalic acid, examples of inorganic acids include hydrochloric acid, nitric acid, and phosphoric acid, and examples of alkalis include sodium hydroxide, lithium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia. The catalyst is not limited to the above.

[0032] The fluorine-based compound containing a fluorine-based functional group component is represented by the following general formula (3) or formula (4): More specific examples of the perfluoroether group in formula (3) or formula (4) include perfluoroether structures represented by the following formulas (5) to (13).

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] Furthermore, examples of X in the above formulas (3) and (4) include structures represented by the following formulas (14) to (18): Formula (14) shows an example containing an ether bond, Formula (15) shows an ester bond, Formula (16) shows an amide bond, Formula (17) shows a urethane bond, and Formula (18) shows a sulfonamide bond.

[0037] [ka]

[0038] Here, in the above formulas (14) to (18), R 2 and R 3 is a hydrocarbon group with 0 to 10 carbon atoms, R 4 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. 2 and R 3 Examples of the hydrocarbon group include alkylene groups such as methylene and ethylene groups, and R 4 Examples of the hydrocarbon group include alkyl groups such as methyl and ethyl groups, as well as phenyl groups.

[0039] In addition, in the above formulas (3) and (4), R 1 Examples of the alkyl group include a methyl group and an ethyl group.

[0040] In addition, in the above formulas (3) and (4), Z is not particularly limited as long as it is a hydrolyzable group that can be hydrolyzed to form a Si-O-Si bond. Specific examples of such hydrolyzable groups include alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, aryloxy groups such as phenoxy and naphthoxy groups, aralkyloxy groups such as benzyloxy and phenethyloxy groups, and acyloxy groups such as acetoxy, propionyloxy, butyryloxy, valeryloxy, pivaloyloxy, and benzoyloxy groups. Among these, an ethoxy group is preferred.

[0041] 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 (4) include structures represented by the following formulas (19) to (27), in which R is a methyl group or an ethyl group.

[0042] [ka]

[0043] [ka]

[0044] As described above, the fluorine-based compound contained in the water- and oil-repellent black film-forming liquid composition of the present embodiment has a perfluoroether group in which a plurality of short-chain perfluoroalkyl groups and perfluoroalkylene groups each having 6 or less carbon atoms are bonded to an oxygen atom in the molecule, and the high fluorine content in the molecule can impart excellent water- and oil-repellency to the formed film.

[0045] [Self-reactive carboxyl group-containing substances, etc.] The self-reacting 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 based products include Sepolsion VA406N and Sepolsion VA407N (all manufactured by Sumitomo Seika Chemicals), Sumikaflex S-201HQ, S-355HQ, S-401HQ, and S-465HQ (all manufactured by Sumitomo Chemical), and Aquatex EC-1800 and EC-1200 (all manufactured by Japan Coating Resins). Ethylene-acrylic acid copolymers include Zaixen A, Zaixen L, and Zaixen N (all manufactured by Sumitomo Seika Chemicals). An ethylene-vinyl acetate-acrylic acid based product includes Sumikaflex S-900HL (manufactured by Sumitomo Chemical). Other examples include Sumikaflex S-830, an ethylene-vinyl acetate-vinyl chloride copolymer, and Sumikaflex S-950HQ, an ethylene-vinyl acetate-vinyl versatate copolymer (both manufactured by Sumitomo Chemical). Acrylic based products include TOCRYL An example is BCX-1160R-2 (manufactured by Toyochem Co., Ltd.).

[0046] [Water- and oil-repellent black film-forming liquid composition] The water- and oil-repellent black film-forming liquid composition of this embodiment is produced by the above-described production method and contains zirconium oxynitride particles (B) to which the fluorine-based functional group component (A) is bonded, a carboxyl group-containing material (C), and a solvent (D). The fluorine-based functional group component (A) has a perfluoroether structure represented by the general formula (1) or (2) above, and is contained in the liquid composition in an amount of 1 to 10% by mass, where the total amount of nonvolatile matter in the liquid composition is 100% by mass. If the fluorine-based functional group component is less than 1% by mass, the formed film will not be oil-repellent. If it exceeds 10% by mass, the film will repel water, resulting in poor film-forming properties. The preferred content of the fluorine-based functional group component is 1.5 to 8% by mass.

[0047] Furthermore, the carboxyl group-containing substance (C) is contained in the liquid composition in an amount of 20% by mass to 95% by mass, where the total amount of nonvolatile content of the liquid composition is 100% by mass. If the carboxyl group-containing substance is less than 20% by mass, the formed film will have poor adhesion to the substrate and poor strength, while if it exceeds 95% by mass, the film will not be oil-repellent. Furthermore, the total content of the fluorine-based functional group component (A) and the zirconium oxynitride particles (B) in the liquid composition is 5% by mass to 80% by mass, preferably 10% by mass to 60% by mass, where the total amount of nonvolatile content of the liquid composition is 100% by mass. Furthermore, the mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) is in the range of 0.01 to 0.50, preferably 0.02 to 0.40.

[0048] When the total amount of nonvolatile matter in the liquid composition is taken as 100% by mass, if the total amount of component (A) and particles (B) is less than 5% by mass, the water- and oil-repellent properties and the blackness of the film will be reduced. Furthermore, if the total amount exceeds 80% by mass, the content of the carboxyl group-containing substance (C) will be relatively low, and when the liquid composition is formed into a film on a substrate, the water- and oil-repellent film will not firmly adhere to the substrate surface. Furthermore, if the mass ratio (A / B) is less than 0.01, the water- and oil-repellent film will have poor water- and oil-repellent properties, and if it exceeds 0.50, the adhesion of the water- and oil-repellent film to the substrate surface will be reduced. The solvent (D) is water or water containing 40% or less by mass of ethanol. The ethanol content is 40% or less by mass for safety reasons. Furthermore, using a mixed solvent of water and ethanol increases the drying speed and improves film-forming properties.

[0049] Specific examples of the perfluoroether structure include the structures represented by the above formulas (19) to (27).

[0050] Because the liquid composition of this embodiment contains a carboxyl group-containing substance as a main component, when formed on a substrate surface, the water- and oil-repellent film has excellent adhesion to the substrate surface and is highly durable and resistant to peeling. Furthermore, because the liquid composition contains a fluorine-based functional group component with a perfluoroether structure represented by the general formula (1) or (2), the formed film has water- and oil-repellent properties. Furthermore, because the liquid composition contains zirconium oxynitride particles, the formed film is black.

[0051] [Method for forming a water-repellent and oil-repellent film on a substrate surface] To form the water- and oil-repellent film on a substrate surface, the water- and oil-repellent black film-forming liquid composition of this embodiment is applied to the substrate, followed by drying at room temperature in the atmosphere to harden the liquid composition. Examples of the substrate include, but are not limited to, metal plates such as stainless steel (SUS), aluminum, and iron; glass such as window glass and mirrors; tiles; plastics such as polyvinyl chloride (PVC); and polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of methods for applying the liquid composition include screen printing, bar coating, die coating, doctor blade coating, spin coating, and brush coating.

[0052] As shown in Figure 2, the water- and oil-repellent black film 2 formed on the surface of the substrate 1 is composed of numerous fluorine-containing zirconium oxynitride particles 3, whose particle surfaces are covered with fluorine-based functional group components, bound together by a binder such as a carboxyl group-containing material 4. The water- and oil-repellent black film 2 maintains its oil-repellent properties because it contains fluorine-containing zirconium oxynitride particles 3 bound to fluorine-based functional group components. Furthermore, the fluorine-containing zirconium oxynitride particles 3, each with a specific surface area of ​​10 nm to 45 nm, are bound together within the film 2 by the carboxyl group-containing material 4, improving the strength and adhesion of the film 2. The presence of the fluorine-containing zirconium oxynitride particles 3 also contributes to the blackening of the film and the unevenness of the film surface, which reduces the visibility of fingerprints left on the film 2. The film thickness and blackness can be controlled by varying the particle size of the zirconium oxynitride particles and the proportion of zirconium oxynitride particles in the film components. [Example]

[0053] 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 aqueous dispersions of fluorine-containing zirconium oxynitride particles will be described, followed by Examples 1 to 5 and Comparative Examples 1 to 5 for producing water- and oil-repellent black film-forming liquid compositions using these Synthesis Examples and Comparative Synthesis Examples.

[0054] [Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3 for Preparing an Aqueous Dispersion of Fluorine-Containing Zirconium Oxynitride Particles] <Synthesis Example 1> Zirconium dioxide powder was mixed with metallic magnesium and reduced in nitrogen gas to obtain zirconium oxynitride particles with a specific surface area of ​​12 nm. Water was added to the resulting particles and mixed using a bead mill (Asada Iron Works, model: Picomil PCM-LR) to prepare an aqueous dispersion of zirconium oxynitride particles at a concentration of 30% by mass. 50 g of the resulting aqueous dispersion of zirconium oxynitride particles was placed in a beaker, and 7.50 g of the fluorine-based compound represented by formula (19) was added and mixed. Next, 0.02 g of nitric acid was added, and the mixture was mixed at 40°C for 2 hours to obtain an aqueous dispersion of fluorine-containing zirconium oxynitride particles in which the zirconium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) was 0.50.

[0055] <Synthesis Example 2> An aqueous dispersion (concentration: 30% by mass) of zirconium oxynitride particles with a specific surface area diameter of 20 nm was prepared. 50 g of the obtained aqueous dispersion of zirconium oxynitride particles was placed in a beaker, and 0.90 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 the mixture was mixed at 40°C for 2 hours to obtain an aqueous dispersion of fluorine-containing zirconium oxynitride particles in which the zirconium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) was 0.06.

[0056] <Synthesis Example 3> An aqueous dispersion (concentration: 30% by mass) of zirconium oxynitride particles with a specific surface area diameter of 40 nm was prepared. 50 g of the obtained aqueous dispersion of zirconium 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 the mixture was mixed at 40°C for 2 hours to obtain an aqueous dispersion of fluorine-containing zirconium oxynitride particles in which the zirconium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) was 0.015.

[0057] <Synthesis Example 4> An aqueous dispersion (concentration: 30% by mass) of zirconium oxynitride particles with a specific surface area diameter of 20 nm was prepared. 50 g of the obtained aqueous dispersion of zirconium oxynitride particles was placed in a beaker, and 2.70 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 the mixture was mixed at 40°C for 2 hours to obtain an aqueous dispersion of fluorine-containing zirconium oxynitride particles in which the zirconium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) was 0.18.

[0058] <Synthesis Example 5> An aqueous dispersion (concentration: 30% by mass) of zirconium oxynitride particles with a specific surface area diameter of 20 nm was prepared. 50 g of the obtained aqueous dispersion of zirconium 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 the mixture was mixed at 40°C for 2 hours to obtain an aqueous dispersion of fluorine-containing zirconium oxynitride particles in which the zirconium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) was 0.10.

[0059] <Comparative Synthesis Example 1> An aqueous dispersion (concentration: 30% by mass) of zirconium oxynitride particles with a specific surface area diameter of 20 nm was prepared. 50 g of the obtained aqueous dispersion of zirconium 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 the mixture was mixed at 40°C for 2 hours to obtain an aqueous dispersion of fluorine-containing zirconium oxynitride particles in which the zirconium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) was 0.005.

[0060] <Comparative Synthesis Example 2> An aqueous dispersion (concentration: 30% by mass) of zirconium oxynitride particles with a specific surface area diameter of 20 nm was prepared. 50 g of the obtained aqueous dispersion of zirconium 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 the mixture was mixed at 40°C for 2 hours to obtain an aqueous dispersion of fluorine-containing zirconium oxynitride particles in which the zirconium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) was 0.60.

[0061] <Comparative Synthesis Example 3> An aqueous dispersion (concentration: 30% by mass) of zirconium oxynitride particles with a specific surface area diameter of 80 nm was prepared. 50 g of the obtained aqueous dispersion of zirconium oxynitride particles was placed in a beaker, and 2.70 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 the mixture was mixed at 40°C for 2 hours to obtain an aqueous dispersion of fluorine-containing zirconium oxynitride particles in which the zirconium oxynitride particles were bonded to the fluorine-based compound. The mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) was 0.18.

[0062] Table 1 below shows the contents of the aqueous dispersions of fluorine-containing zirconium oxynitride particles in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3. In Table 1, all of the Rs in the fluorine-containing silanes represented by formulas (19) to (22) and (27) as fluorine-based compounds are ethyl groups.

[0063] [Table 1]

[0064] [Examples 1 to 5 and Comparative Examples 1 to 5 for producing a water- and oil-repellent black film-forming liquid composition] Example 1 0.48 g of the aqueous dispersion of fluorine-containing zirconium oxynitride particles obtained in Synthesis Example 1, 5.00 g of ethylene-vinyl acetate Sumikaflex S-401HQ (manufactured by Sumitomo Chemical Co., Ltd.) as a carboxyl group-containing substance, 41.9 g of water as a solvent, and 10.5 g of industrial alcohol (AP-7) were mixed to prepare a water- and oil-repellent black film-forming liquid composition. The details are shown in Table 2 below.

[0065] In Table 2, Sumikaflex S-401HQ and other compounds contain nonvolatile or solid components and a dispersant such as water, and are therefore listed as "carboxyl group-containing compounds, etc., including dispersant." Therefore, the "content in the liquid composition excluding solvent and dispersant" in Table 2 refers to the content of the nonvolatile or solid components in the liquid composition. The "(C)" content in Table 2 refers to the content of the carboxyl group-containing compounds, etc., in the nonvolatile components excluding the volatile components. The "(A) + (B)" content refers to the combined content of the fluorine-based functional group component (A) and the zirconium oxynitride particles (B), excluding the solvent, i.e., the content of the nonvolatile components. The content (%) of the fluorine-based functional group component (A) in the liquid composition excluding the solvent and dispersant, taking into account the content of the carboxyl group-containing compounds, etc., (C), is expressed as a percentage of [(A) / [(A) + (B) + (C)]].

[0066] [Table 2]

[0067] <Examples 2 to 5 and Comparative Examples 1 to 5> As shown in Table 2, in Examples 2 to 5, the aqueous dispersions of fluorine-containing zirconium oxynitride particles obtained in Synthesis Examples 2 to 5 shown in Table 1 were used, and their respective weights were determined. In Comparative Examples 1 to 5, the aqueous dispersions of fluorine-containing zirconium oxynitride particles obtained in Synthesis Examples 1 and 3 and Comparative Synthesis Examples 1 to 3 shown in Table 1 were used, and their respective weights were determined.

[0068] In Example 2 and Comparative Examples 1 to 5, Sumikaflex S-950HQ (manufactured by Sumitomo Chemical Co., Ltd.), an ethylene-vinyl acetate-vinyl versatate copolymer, was used as the carboxyl group-containing substance, and the weight of each was determined. In Example 3, acrylic TOCRYL BCX-1160R-2 (manufactured by Toyochem Co., Ltd.) was used as the carboxyl group-containing substance, and the weight of each was determined. In Example 4, Sumikaflex S-830 (manufactured by Sumitomo Chemical Co., Ltd.), an ethylene-vinyl acetate-vinyl chloride copolymer, was used as the carboxyl group-containing substance, and the weight of each was determined. In Example 5, Zaixen N (manufactured by Sumitomo Seika Chemical Co., Ltd.), an ethylene-acrylic acid copolymer, was used as the carboxyl group-containing substance, and the weight of each was determined. In this manner, the water- and oil-repellent black film-forming liquid compositions of Examples 2 to 5 and Comparative Examples 1 to 5 were prepared.

[0069] <Comparative testing and evaluation> The ten liquid compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were applied to glass substrates with a thickness of 1.1 mm, a length of 100 mm, and a width of 100 mm using a brush (Nylon Brush Meister, manufactured by Suematsu Brush Co., Ltd.) so that the dry thickness would be 5.0 μm, forming ten types of coating films. All coating films were left to stand in the air at room temperature for three hours, and then dried to obtain ten types of films on the glass substrates. These films were evaluated for water wettability (water repellency), oil repellency, and appearance, and were subjected to a Cellotape (registered trademark) peel test (hereinafter referred to as an adhesion test). The light transmittance of the coating films was also evaluated. The results are shown in Table 3 below.

[0070] (1) Water repellency of the film surface (contact angle) Using a Kyowa Interface Science Dropmaster DM-700, ion-exchanged water at 22°C ± 1°C was prepared in a syringe, and a 2 μL droplet was ejected from the tip of the syringe needle. The film on the glass substrate to be evaluated was then brought close to the droplet, allowing the droplet to adhere to the film. The contact angle of the adhered water was measured. The contact angle measured 1 second after water touched the film surface in a stationary state was analyzed using the θ / 2 method, and this value was used to evaluate the water wettability (water repellency) of the film surface. A water contact angle of 90 degrees or more was considered to be "good" water repellency, and a contact angle of less than 90 degrees was considered to be "poor" water repellency.

[0071] (2) Oil repellency of the film surface (contact angle) Using a Kyowa Interface Science Dropmaster DM-700, n-hexadecane (hereinafter referred to as "oil") at 22°C ± 1°C was prepared in a syringe, and a 2 μL droplet was ejected from the tip of the syringe needle. The film on the glass substrate to be evaluated was then brought close to the droplet, allowing the droplet to adhere to the film. The contact angle of the adhered oil was measured. The contact angle measured 1 second after the oil touched the film surface in a stationary state was analyzed using the θ / 2 method, and this value was used to evaluate the oil contact angle. An oil contact angle of 50 degrees or more was considered to have "good" oil repellency, and an angle of less than 50 degrees was considered to have "poor" oil repellency.

[0072] (3) Appearance of the membrane The film on the glass substrate to be evaluated was visually observed to check whether the film was transparent and whether particles were agglomerated in the film. Films that were transparent were rated as "fairly good" or "good" depending on the degree of transparency, and films that had particles agglomerated in the film were rated as "poor agglomeration."

[0073] (4) Film adhesion test A 1 mm wide cross-cut was made in a grid pattern on the film on the glass substrate to be evaluated, and adhesive tape (manufactured by Nichiban Co., Ltd., product name "Cellotape (registered trademark)") was applied to the grid-cut film. A Cellotape (registered trademark) peel test (adhesion test) was performed in accordance with the grid tape method of JIS K5600-5-6 (cross-cut method). The denominator was the number of 100 cross-cut squares, and the numerator was the number of squares remaining on the substrate after the peel test. A score of 100 / 100 was considered "pass," and any peeled areas were considered "fail."

[0074] (5) Film light transmittance evaluation test For the coating film on the glass substrate to be evaluated, a spectrophotometer (U-4150, manufactured by Hitachi High-Technologies Corporation) was used to measure the baseline of the substrate on which the coating film was formed, and then the light transmittance in the visible light range of wavelengths from 380 nm to 780 nm was measured, and the maximum light transmittance (%) was calculated.

[0075] [Table 3]

[0076] As is clear from Table 3, in Comparative Example 1, the ratio of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) was 0.005, which was too low. Therefore, although the appearance of the film was good and the film passed the peeling test, the contact angles with water and n-hexadecane were poor, and the water- and oil-repellent properties of the film were poor. The maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm was an extremely low 11.6%, and a black film was obtained.

[0077] In Comparative Example 2, the ratio of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) was too high at 0.60, so the particles in the film aggregated and the film had a poor appearance. The film also failed the Cellotape peeling test, had poor contact angles with water and n-hexadecane, and had poor water- and oil-repellent properties. The maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm was low at 24.0%, and a black film was obtained.

[0078] In Comparative Example 3, the specific surface area diameter of the zirconium oxynitride particles was too large at 80 nm, so the appearance of the film was good and the film passed the peeling test, but the contact angles with water and n-hexadecane were poor and the water- and oil-repellent properties of the film were also poor. The maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm was high at 29.8%, and a black film was not obtained. This was thought to be because the specific surface area diameter of the zirconium oxynitride particles was too large, resulting in low hiding power of the film.

[0079] In Comparative Example 4, the combined content of the fluorine-based functional group component (A) and the zirconium oxynitride particles (B) was 3% by mass, which was too low when the total amount of nonvolatile matter in the liquid composition was taken as 100% by mass. Therefore, although the film passed the peeling test and had a good appearance, the contact angles with water and n-hexadecane were 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 high at 50.1%, and a black film was not obtained. This was thought to be due to the small number of zirconium oxynitride particles in the film.

[0080] In Comparative Example 5, the combined content of the fluorine-based functional group component (A) and the zirconium oxynitride particles (B) was 82% by mass, which was too high when the total amount of nonvolatile components in the liquid composition was taken as 100% by mass, making it 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, the particles in the film were aggregated, and the film's appearance was poor. Furthermore, in a film peeling test, only 42 squares remained on the substrate, and some peeled off. The maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm was low at 18.3%, and a black film was obtained.

[0081] In contrast, in Examples 1 to 5, the specific surface area diameter of the zirconium oxynitride particles was in the range of 10 nm to 45 nm, the content of the carboxyl group-containing substance (C) was 20% to 95% by mass when the total nonvolatile content of the liquid composition was 100% by mass, the combined content of the fluorine-based functional group component (A) and the zirconium oxynitride particles (B) was 5% to 80% by mass when the total nonvolatile content of the liquid composition was 100% by mass, and "(A) / (B)" was in the range of 0.01 to 0.50, satisfying the scope of the first aspect of the invention. Therefore, the contact angles with water and n-hexadecane and the appearance of the film were all good, and all film adhesion tests were passed. Furthermore, the maximum light transmittance of the coating film in the wavelength range of 380 nm to 780 nm was 3.4% to 24.2%, which was below 25%, and a black film was obtained in all cases. In particular, in Example 3, the content of zirconium oxynitride particles in the liquid composition was high, and therefore the maximum light transmittance was an extremely low 3.4%. [Industrial Applicability]

[0082] The water- and oil-repellent black film-forming liquid composition of the present invention is used in fields where stains are to be prevented in interior products for kitchens, bathrooms, and the like, where design is required, and in vehicle interior components such as instrument panels, air conditioners, car navigation systems, and audio equipment. [Explanation of symbols]

[0083] 1 Base material 2. Water- and oil-repellent black film 3. Fluorine-containing zirconium oxynitride particles 4. Carboxyl group-containing substances, etc.

Claims

1. The present invention comprises zirconium oxynitride particles (B) having a specific surface area diameter of 10 nm to 45 nm and having bonded thereto a fluorine-based functional group component (A) containing a perfluoroether structure represented by the following general formula (3) and formula (4), a self-reactive carboxyl group- and / or acetyl group-containing substance (C), and a solvent (D), 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; When the total amount of nonvolatile components of the liquid composition is taken as 100% by mass, the content of the self-reactive carboxyl group- and / or acetyl group-containing substance (C) is 20% by mass to 95% by mass, and the total content of the fluorine-based functional group component (A) and the zirconium oxynitride particles (B) is 5% by mass to 80% by mass, a mass ratio (A / B) of the fluorine-based functional group component (A) to the zirconium oxynitride particles (B) in the range of 0.01 to 0.50; 【Chemistry 2】 In the above formulas (3) and (4), p, q, and r are the same or different and are integers of 1 to 6, and the carbon skeleton may be linear or branched. Furthermore, in the above formulas (3) and (4), X is a hydrocarbon group having 2 to 10 carbon atoms and may contain one or more bonds selected from an ether bond, a CO—NH bond, an O—CO—NH bond, and a sulfonamide bond.

2. 2. The water- and oil-repellent black film-forming liquid composition according to claim 1, wherein when a coating film is formed under conditions that result in a film thickness of 5.0 μm, the coating film has a maximum light transmittance of 25% or less in a wavelength range of 380 nm to 780 nm.

3. A method for producing a water- and oil-repellent black film-forming liquid composition according to claim 1 or claim 2, comprising: The water- and oil-repellent black film-forming liquid composition is produced by mixing an aqueous dispersion of fluorine-containing zirconium oxynitride particles, a self-reactive carboxyl group- and / or acetyl group-containing substance, and a solvent, The method for producing a water- and oil-repellent black film-forming liquid composition, wherein the self-reactive carboxyl group- and / or acetyl group-containing substance (C) is an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate-acrylic acid copolymer.

4. 4. The method for producing a water- and oil-repellent black film-forming liquid composition according to claim 3, wherein the aqueous dispersion of fluorine-containing zirconium oxynitride particles is prepared by adding and mixing a fluorine-based compound to an aqueous dispersion of zirconium oxynitride particles, and then adding and mixing a catalyst to the mixture.

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