Water-repellent aid, water-repellent agent composition, and water-repellent base material

Abstract

Provided is a water-repellent aid that enhances durability of a water-repellent effect of a water-repellent agent. Specifically, the water-repellent aid is a metal oxide, and the metal of the metal oxide is one or more selected from lithium, sodium, potassium, strontium, silver, niobium, titanium, lanthanum, zirconium, tantalum, gallium, bismuth, vanadium, rhodium, chromium, and tungsten.

Description

Water-repellent enhancers, water-repellent compositions, and water-repellent substrates

[0001] The present invention relates to a water-repellent additive, a water-repellent composition, and a water-repellent substrate.

[0002] Traditionally, textile products, exterior building materials, and interior building materials that have been treated with water-repellent agents have been on the market, making them resistant to water droplets, stains, and dirt.

[0003] Various water-repellent agents have been proposed, including fluorine compounds, silicone resins, silicone oils, and hydrocarbon compounds such as paraffin (for example, Patent Document 1). It has also been proposed to use multiple water-repellent agents (for example, Patent Document 2).

[0004] Japanese Patent Publication No. 2006-328624 Japanese Patent Publication No. 2024-3104

[0005] While water-repellent agents can prevent water from adhering, their water-repellency decreases due to the adhesion of oily dirt, dust, and other particles in the air. For example, the textile products, exterior and interior building materials mentioned above are constantly exposed to dust, dirt, and oily dirt in the air, and tend to lose water-repellency over time. Therefore, there was a challenge in improving the durability of the water-repellent effect of water-repellent agents.

[0006] The problem that this invention aims to solve is to provide a water-repellent enhancer that enhances the durability of the water-repellent effect of a water-repellent agent. Another problem that this invention aims to solve is to provide a water-repellent composition with enhanced durability of water-repellent effect. Another problem that this invention aims to solve is to provide a water-repellent substrate with enhanced durability of water-repellent effect.

[0007] The inventors of the present invention conducted diligent research to solve the above problems and, as a result, discovered that by combining a water-repellent agent with titanium dioxide as a water-repellent enhancer, the water-repellent effect of the water-repellent agent can be made more durable, thus completing the present invention.

[0008] In other words, the present invention relates to the following water-repellent additives, etc. 1. A water-repellent additive that is a metal oxide, wherein the metal of the metal oxide is one or more selected from lithium, sodium, potassium, strontium, silver, niobium, titanium, lanthanum, zirconium, tantalum, gallium, bismuth, vanadium, rhodium, chromium, and tungsten. 2. The water-repellent additive according to 1, wherein the metal oxide is titanium oxide. 3. The water-repellent additive according to 2, wherein the titanium oxide includes rutile-type titanium oxide. 4. The water-repellent additive according to 2 or 3, wherein the titanium oxide is titanium oxide supporting a metal compound. 5. The water-repellent additive according to any one of 2 to 4, wherein the titanium oxide is titanium oxide supporting one or more selected from copper compounds, silver compounds, iron compounds, platinum compounds, and palladium compounds. 6. The water-repellent additive according to any one of 2 to 5, wherein the titanium oxide is titanium oxide supporting a divalent copper compound. 7. 10. A water-repellent additive according to any one of 2 to 6, wherein the titanium dioxide is a titanium dioxide compound containing zirconium and / or niobium. 8. A water-repellent additive according to any one of 2 to 7, wherein the titanium dioxide is a titanium dioxide compound containing zirconium, and the zirconium content ratio (Zr / Ti ratio) to titanium 100 in the titanium dioxide compound is in the range of 0.03 to 0.8. 9. A water-repellent additive according to any one of 2 to 8, wherein the titanium dioxide compound is a titanium dioxide compound containing niobium, and the niobium content ratio (Nb / Ti ratio) to titanium 100 in the titanium dioxide compound is in the range of 0.05 to 0.8. 10. A water-repellent composition containing a water-repellent additive and a water-repellent agent according to any one of 1 to 9. 11. A water-repellent composition according to 10, wherein the water-repellent agent is one or more selected from polymers having a structure derived from (meth)acrylic acid esters having 12 or more carbon atoms, silicone compounds, and fluorine compounds. 12. A water-repellent composition according to 10 or 11, comprising 1.0 to 15,000 parts by mass of the water-repellent additive per 100 parts by mass of the water-repellent agent. A water-repellent substrate which is a substrate to which the water-repellent additive and the water-repellent agent according to any one of 13.1 to 9 are attached.

[0009] According to the present invention, a water-repellent auxiliary agent that enhances the durability of the water-repellent effect of a water-repellent agent can be provided. According to the present invention, a water-repellent agent composition with enhanced durability of the water-repellent effect can be provided. According to the present invention, a water-repellent base material with enhanced durability of the water-repellent effect can be provided.

[0010] Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention. The compounds in the present specification may be derived from fossil resources or may be derived from biological resources. Unless otherwise specified, each component described in the present specification may be used alone, or two or more thereof may be used in combination.

[0011] [Water-repellent auxiliary agent] The water-repellent auxiliary agent of the present invention is a metal oxide of one or more metals selected from lithium, sodium, potassium, strontium, silver, niobium, titanium, lanthanum, zirconium, tantalum, gallium, bismuth, vanadium, rhodium, chromium, and tungsten. The above-mentioned metal oxide is a compound having a photoactive effect, and has a function of preventing adhesion of oily stains or the like or a function of decomposing them. It is presumed that, by this function, the combination of the water-repellent agent and titanium oxide which is a water-repellent auxiliary agent can enhance the durability of the water-repellent effect of the water-repellent agent. Hereinafter, the metal oxide which is the water-repellent auxiliary agent will be described.

[0012] Examples of the metal oxide of the present invention include titanium oxide, zirconium oxide, tantalum oxide, gallium oxide, nickel oxide, tungsten oxide, and sodium tantalum oxide (NaTaO ３ ), rhodium chromium oxide (Ga ２ O ３ ), potassium niobium oxide (K ４ Nb ６ O １７ ), potassium lanthanum titanium oxide (K ２ La ２ Ti ３ O １０ ), strontium titanium oxide (SrTiO ３ ), sodium tantalum oxide (NaTaO ３ ), bismuth vanadium oxide (BiVO ４), silver niobium oxide (AgNbO ３ ), silver lithium titanium oxide (AgLi １／３ Ti ２／３ O ２ ), silver vanadium oxide (Ag ３ VO ４ Examples include:

[0013] The metal oxide of the present invention is preferably titanium oxide (hereinafter sometimes simply referred to as "titanium oxide of the present invention"). While titanium oxide has various crystalline forms, such as rutile titanium oxide, anatase titanium oxide, and brookite titanium oxide, the titanium oxide of the present invention preferably includes rutile titanium oxide.

[0014] When titanium dioxide contains rutile-type titanium dioxide, the content (rutile rate) of such rutile-type titanium dioxide is, for example, 15 mol% or more, 50 mol% or more, 75 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or greater than 95 mol%. The rutile rate is preferably 75 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more. There is no particular upper limit to the rutile rate, but for example it is 100 mol%. The rutile rate of titanium dioxide is confirmed by the method described in the examples.

[0015] The upper limit for the BET specific surface area of ​​titanium dioxide is 200 m². ２ / g or less, 100m ２ / g or less, 90m ２ / g or less, 70m ２ / g or less, 40m ２ / g or less, 30m ２ / g or less or 20m ２ It is less than or equal to / g, and the lower limit is 1m ２ / g or more, 2m ２ / g or more, 3m ２ / g or more or 5m ２ It is 1 / g or more. Examples of combinations of upper and lower limits for the BET specific surface area of ​​titanium dioxide include 1 to 200 m². ２ The range is / g, preferably 3 to 100m ２ The range is / g, more preferably 5 to 90m ２The range is / g. The BET specific surface area of ​​titanium dioxide is confirmed by the method described in the examples.

[0016] The primary particle size of titanium dioxide is, for example, in the range of 0.01 to 0.5 μm, preferably in the range of 0.01 to 0.35 μm, and more preferably in the range of 0.02 to 0.35 μm, from the viewpoint of visible light responsiveness. The primary particle size of titanium dioxide is confirmed by the method described in the examples.

[0017] The titanium dioxide is preferably titanium dioxide supporting a metal compound. Supporting a metal compound in titanium dioxide can improve its photoactivating effect.

[0018] Examples of metals used in metal compounds supported on titanium oxide include transition metals such as copper, iron, tungsten, zirconium, and molybdenum; and non-transition metals such as zinc, aluminum, antimony, and tin.

[0019] The titanium oxide is preferably titanium oxide supporting one or more compounds selected from copper compounds, silver compounds, copper compounds, iron compounds, platinum compounds, and palladium compounds. The form of the above metal compound is not particularly limited and may be any form such as metal oxide, metal hydroxide, metal sulfide, metal nitrate, fatty acid metal salt, etc.

[0020] The metal compound supported on titanium oxide is preferably a copper compound and / or an iron compound, and more preferably a divalent copper compound. Here, the "divalent copper compound" may be, for example, either a divalent copper inorganic compound or a divalent copper organic compound.

[0021] Examples of the aforementioned divalent copper inorganic compounds include inorganic salts of divalent copper such as copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amidosulfate, copper ammonium chloride, copper pyrophosphate, and copper carbonate; halides of divalent copper such as copper chloride, copper fluoride, and copper bromide; and copper oxide, copper sulfide, azurite, malachite, and copper azide.

[0022] Examples of the aforementioned divalent copper organic compounds include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enantate, copper caprylate, copper pelargonate, copper caprate, copper myristicate, copper palmitate, copper margarate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, copper melitate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, and glycol. Copper oxide, copper glycerate, copper gluconate, copper tartrate, copper acetylacetone, copper ethylacetoacetate, copper isovalerate, copper β-resorsylate, copper diacetoacetate, copper formylsuccinate, copper salicylate, copper bis(2-ethylhexanoate), copper sebacate, copper naphthenate, copper oxyne, copper acetylacetone, copper ethylacetoacetate, copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, copper methoxide, copper dimethyldithiocarbamate, etc. can be used.

[0023] The divalent copper compound supported on titanium oxide is preferably a compound represented by the following general formula (1): CuX ２ (1) (In the above general formula (1), X is a halogen atom, CH ３ COO, NO ３ or (SO ４ ) １／２ (X is preferably a halogen atom, and more preferably a chlorine atom.)

[0024] When titanium oxide supports a metal compound, the amount of the metal compound supported is, for example, in the range of 0.01 to 20 parts by mass per 100 parts by mass of titanium oxide, preferably in the range of 0.1 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass, and even more preferably in the range of 0.1 to 3 parts by mass. The amount of the metal compound supported is confirmed by the method described in the examples.

[0025] The metal compound supported on titanium dioxide may be a single compound or two or more compounds may be used in combination.

[0026] The titanium dioxide of the present invention is, for example, a titanium dioxide compound in which titanium dioxide contains zirconium and / or niobium, and preferably a titanium dioxide compound in which titanium dioxide contains both zirconium and niobium. Titanium dioxide containing zirconium and / or niobium has a low cohesive force relative to the specific surface area (BET value) caused by primary particles, and is presumed to contribute to improving the dispersibility of titanium dioxide in the coating composition. It is also presumed that in the titanium dioxide compound, both zirconium and niobium are included in a doped state within the titanium dioxide crystal.

[0027] When the titanium oxide is a titanium oxide compound containing zirconium, the lower limit of the zirconium content ratio (Zr / Ti ratio) to titanium 100 is, for example, 0.02 or more, preferably 0.03 or more, more preferably 0.04 or more, and even more preferably 0.05 or more. Similarly, the upper limit of the zirconium content ratio (Zr / Ti ratio) to titanium 100 in the above titanium oxide compound is, for example, 1.0 or less, preferably 0.8 or less, more preferably 0.5 or less, and even more preferably 0.3 or less. Any combination of these upper and lower limits is acceptable. The zirconium content ratio (Zr / Ti ratio) to titanium 100 in the above titanium oxide compound is preferably in the range of 0.03 to 0.8, more preferably in the range of 0.04 to 0.5, and even more preferably in the range of 0.05 to 0.3.

[0028] When the titanium oxide is a titanium oxide compound containing niobium, the lower limit of the niobium content ratio (Nb / Ti ratio) to titanium 100 is, for example, 0.02 or more, preferably 0.05 or more, more preferably 0.08 or more, and even more preferably 0.1 or more. Similarly, the upper limit of the niobium content ratio (Nb / Ti ratio) to titanium 100 in the above titanium oxide compound is, for example, 1.0 or less, preferably 0.8 or less, more preferably 0.5 or less, and even more preferably 0.3 or less. Any combination of these upper and lower limits is acceptable. The niobium content ratio (Nb / Ti ratio) to titanium 100 in the above titanium oxide compound is preferably in the range of 0.05 to 0.8, more preferably in the range of 0.08 to 0.5, and even more preferably in the range of 0.10 to 0.3.

[0029] The zirconium content ratio (Zr / Ti ratio) relative to titanium 100 in the above titanium oxide compound, and the niobium content ratio (Nb / Ti ratio) relative to titanium 100 in the above titanium oxide compound are both the fluorescence intensity ratios of each element in the titanium oxide compound, and are specifically confirmed by the method described in the examples.

[0030] (Method for producing titanium dioxide) Titanium dioxide can be produced by known methods, and two methods known are the liquid-phase method and the gas-phase method. The liquid-phase method is a method of obtaining titanium dioxide compounds by hydrolysis or neutralization of titanyl sulfate obtained from a solution of raw material ore such as ilmenite ore. The gas-phase method is a method of obtaining titanium dioxide by a gas-phase reaction between titanium tetrachloride, obtained by chlorinating raw material ore such as rutile ore, and oxygen. The titanium dioxide of the present invention is preferably titanium dioxide produced by the liquid-phase method.

[0031] When titanium dioxide is used as a titanium dioxide compound containing zirconium and / or niobium, it is preferable to also react a desired amount of zirconium oxide and / or niobium oxide in the above reaction.

[0032] When supporting a metal compound on titanium dioxide, known methods can be employed. For example, a method in which titanium dioxide is added to a mixture of the metal compound (the support) and a solvent, and the metal compound is adsorbed onto the titanium dioxide in the suspended mixture; or a method in which a mixture of titanium dioxide, the metal compound (the support), a solvent, and an alkaline substance is prepared, and the titanium dioxide and metal compound are reacted.

[0033] The concentration of titanium dioxide in the aforementioned mixture is preferably in the range of 3 to 40% by mass. When the titanium dioxide is titanium dioxide produced by the liquid-phase method, a mixture that is easy to handle can be made even if the concentration of titanium dioxide is increased, for example, the concentration of titanium dioxide can be in the range of more than 25% by mass and 40% by mass or less.

[0034] The amount of the metal compound used as a support in the aforementioned mixture is, for example, in the range of 0.01 to 20 parts by mass, preferably in the range of 0.1 to 15 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass, per 100 parts by mass of titanium oxide. The amount of metal compound supported can be adjusted by adjusting the amount of metal compound used.

[0035] The solvent used for the mixed solution can be water, an organic solvent, or a mixture thereof. If the solvent is a mixture, it is preferably an aqueous solvent mainly composed of water. Here, "aqueous solvent mainly composed of water" refers to a mixture solvent in which water is the most abundant component in the total amount of solvent, and preferably a mixture solvent in which water is 50% by mass or more.

[0036] If the mixed solvent contains an organic solvent, from the viewpoint of reducing environmental impact and improving safety, the content of the organic solvent is preferably 30% by mass or less, and more preferably 5% by mass or less.

[0037] There are no particular limitations on the organic solvents that can be used as solvents, but for example, organic solvents that are miscible with water are preferably used. Suitable organic solvents include monofunctional alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, and 3-methyl-3-pentanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and propylene glycol. Various diols such as chol, 1,2-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2-methyl-1,3-propanediol, 1,2-hexanediol, dipropylene glycol, and diethylene glycol; polyhydric alcohols such as glycerin; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic diols which are adducts of bisphenol A and alkylene oxides with 2 or 3 carbon atoms (average number of added moles 1 or more and 16 or less) of bisphenol A; and lipids such as hydrogenated bisphenol A. Examples of cyclic diols include dimethylformamide, tetrahydrofuran, polyoxypropylene-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane, cyclohexanediol, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, ethyl carbitol, and γ-butyrolactone.

[0038] The organic solvent is preferably 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, methyl ethyl ketone, methanol, ethanol, n-propyl alcohol (NPA), isopropyl alcohol (IPA), propylene glycol, propylene glycol monomethyl ether (1-methoxy-2-propanol) (PGM), or ethylene glycol. The organic solvent used may be a single type or a combination of two or more types.

[0039] When using the alkaline substance in the production of titanium oxide supported with a metal compound, the alkaline substance can be, for example, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, or a basic surfactant, and sodium hydroxide is preferred.

[0040] The alkaline substance is preferably added as an aqueous solution of the alkaline substance because it is easier to control the reaction. The concentration of the alkaline substance in the aqueous solution of the alkaline substance is, for example, in the range of 0.1 to 5 mol / L, preferably in the range of 0.3 to 4 mol / L, and more preferably in the range of 0.5 to 3 mol / L.

[0041] A method for producing titanium oxide supported with a divalent copper compound will be described below as one embodiment. First, water and titanium oxide are mixed by stirring as needed. Then, a divalent copper compound is added to this mixture and stirred. After that, an alkaline substance is added and the prepared mixture is stirred to produce titanium oxide supported with a divalent copper compound.

[0042] The total stirring time in the method for producing titanium oxide supported with the divalent copper compound is, for example, in the range of 5 to 120 minutes, preferably in the range of 10 to 60 minutes. The reaction temperature of the mixture is, for example, in the range of room temperature (25°C) to 70°C.

[0043] Since the support of the divalent copper compound on titanium oxide is good, the pH of the mixed solution after adding the alkaline substance is preferably in the range of 8 to 11, and more preferably in the range of 9.0 to 10.5.

[0044] After the reaction in the aforementioned mixture is complete, the solid components can be separated. Methods for separation include, for example, filtration, sedimentation, centrifugation, and evaporation / drying, but filtration is preferred. The separated solid components may then be washed, crushed, classified, or otherwise processed as needed.

[0045] After obtaining the solid content, the titanium oxide supported with the divalent copper compound is preferably heat-treated to more firmly bond the divalent copper compound to the titanium oxide. The heat treatment temperature is preferably in the range of 150 to 600°C, and more preferably in the range of 250 to 450°C. The heat treatment time is preferably in the range of 1 to 10 hours, and more preferably in the range of 2 to 5 hours.

[0046] [Water-repellent composition] The water-repellent composition of the present invention contains the water-repellent auxiliary agent and the water-repellent agent of the present invention. In the present invention, the "water-repellent agent" is an agent that imparts the function of repelling water to the substrate, and known water-repellent agents can be used.

[0047] The water repellent is preferably one or more selected from polymers having a structure derived from (meth)acrylic acid esters having hydrocarbon groups with 12 or more carbon atoms, silicone compounds, and fluorine compounds.

[0048] The polymer having a structure derived from a (meth)acrylic acid ester having 12 or more hydrocarbon groups, which is a water repellent, is preferably a polymer (A) in which at least a (meth)acrylic acid ester monomer (A) represented by the following general formula (A-1) is a polymerization component. Here, "polymerization component" means a component that makes up the polymer, and does not include solvents or catalysts that do not directly constitute the polymer.

[0049] (In the above general formula (A-1), R １１ R is a hydrogen atom or a methyl group. １２(It is a monovalent hydrocarbon group with 12 to 24 carbon atoms.)

[0050] R １２ The monovalent hydrocarbon group having 12 to 24 carbon atoms may be a straight-chain hydrocarbon group or a branched hydrocarbon group. １２ The monovalent hydrocarbon group having 12 to 24 carbon atoms may be a saturated hydrocarbon group or an unsaturated hydrocarbon group having a carbon-carbon unsaturated bond. １２ The monovalent hydrocarbon group having 12 to 24 carbon atoms may have an alicyclic hydrocarbon structure or an aromatic ring structure.

[0051] R １２ The monovalent hydrocarbon group having 12 to 24 carbon atoms is preferably an alkyl group having 12 to 24 carbon atoms, and more preferably a linear alkyl group having 12 to 24 carbon atoms.

[0052] R １２ The monovalent hydrocarbon group having 12 to 24 carbon atoms preferably has one or more substituents. Examples of such substituents include hydroxyl groups, amino groups, carboxyl groups, epoxy groups, isocyanate groups, and (meth)acryloyloxy groups. The isocyanate group may be a blocked isocyanate group protected with a blocking agent.

[0053] Specific examples of the (meth)acrylic acid ester monomer represented by the general formula (A-1) include stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, behenyl (meth)acrylate, ceryl (meth)acrylate, melicyl (meth)acrylate, and the like.

[0054] (Meth)acrylic acid ester monomer (A) may be used alone, or two or more monomers with different structures may be used in combination.

[0055] The polymerization component of the polymer (A) is preferably R１１ Acrylic acid esters, where R is a hydrogen atom １１ The polymer (A) contains both a methyl group and a methacrylate ester. １１ Acrylic acid esters, where R is a hydrogen atom １１ If it contains both a methyl group and a methacrylate ester, then the mass ratio (R １１ Acrylic acid esters / R where the atom is a hydrogen atom １１ The methyl group methacrylate is, for example, in the range of 30 / 70 to 90 / 10, preferably in the range of 40 / 60 to 85 / 15, and more preferably in the range of 50 / 50 to 80 / 20.

[0056] The lower limit of the content of (meth)acrylic acid ester monomer (A) in the polymerization components of the polymer (A) may be, for example, 30% by mass or more, 40% by mass or more, or 50% by mass or more. The upper limit of the content of (meth)acrylic acid ester monomer (A) in the polymerization components of the polymer (A) may be, for example, 100% by mass or less, 90% by mass or less, 80% by mass or less, or 70% by mass or less.

[0057] The polymerization component of the polymer (A) preferably includes a vinyl chloride monomer (E), which is vinyl chloride and / or vinylidene chloride. When the polymerization component of the polymer (A) includes a vinyl chloride monomer (E), the mass ratio of the (meth)acrylic acid ester monomer represented by the general formula (A-1) to the vinyl chloride monomer ((meth)acrylic acid ester monomer / vinyl chloride monomer represented by the general formula (A-1)) is, for example, in the range of 40 / 60 to 90 / 10, preferably in the range of 50 / 50 to 85 / 15, and more preferably in the range of 60 / 40 to 80 / 20.

[0058] The polymerization component of the polymer (A) may include one or more reactive emulsifier monomers (B) selected from monomers represented by the following general formula (B-1) (B1), monomers represented by the following general formula (B-2) (B2), and monomers obtained by adding a C2-C4 alkylene oxide to a fat or oil having a hydroxyl group and a polymerizable unsaturated group (B3). The reactive emulsifier monomers (B) can impart a surfactant effect to the polymer (A).

[0059] (In the above general formula (B-1), R １３ A is a hydrogen atom or a methyl group, X is an alkylene group having 1 to 6 carbon atoms, and A １ (where m is an alkylene group with 2 to 4 carbon atoms, and m is the number of repeats, for example, an integer in the range of 1 to 80.)

[0060] (In the above general formula (B-2), R １４ A is a hydrocarbon group having 13 to 17 carbon atoms and one or more carbon-carbon unsaturated bonds, ２ (where n is an alkylene group with 2 to 4 carbon atoms, and n is the number of repeats, for example, an integer in the range of 1 to 50.)

[0061] In the monomer (B1) represented by the general formula (B-1) above, if m is an integer of 2 or more, multiple A １ It may be one type alone, or two or more types. A １ If there are two or more types, [A １ The part represented by [O] may be a random addition structure or a block addition structure.

[0062] In the monomer (B2) represented by the general formula (B-2), if n is an integer of 2 or more, multiple A ２ It may be one type alone, or two or more types. A ２ If there are two or more types, [A ２ The part represented by [O] may be a random addition structure or a block addition structure.

[0063] R in the above general formula (B-2) １４ Preferably, one or more groups selected from tridecenyl group, tridecadienyl group, tetradecenyl group, tetradienyl group, pentadecenyl group, pentadecadienyl group, pentadecatriaenyl group, heptadecenyl group, heptadecadienyl group, and heptadecatriaenyl group.

[0064] In monomer (B3) obtained by adding a C2-C4 alkylene oxide to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, the "oil or fat having a hydroxyl group and a polymerizable unsaturated group" can be mono or diglycerides of fatty acids selected from palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, and docosapentaenoic acid; or triglycerides of fatty acids selected from ricinoleic acid, ricinoelaidic acid, and 2-hydroxytetracosenoic acid. The number of moles of alkylene oxide added is, for example, in the range of 20 to 50 moles.

[0065] The reactive emulsifier monomers (B1) to (B3) preferably have an HLB value in the range of 7 to 18, and more preferably in the range of 9 to 15. The HLB value represents the degree of affinity of the reactive emulsifier monomer to water and oil. The HLB value ranges from 0 to 20, with values ​​closer to 0 indicating higher lipophilicity and values ​​closer to 20 indicating higher hydrophilicity. The above HLB values ​​were calculated using the Griffin method.

[0066] The reactive emulsifier monomer (B) may be used alone, or two or more monomers with different structures may be used in combination.

[0067] When the polymerization component of the polymer (A) contains a reactive emulsifier monomer (B), the content of the reactive emulsifier monomer (B) in the polymerization component is, for example, in the range of 0.5 to 20% by mass, preferably in the range of 1 to 15% by mass, and more preferably in the range of 3 to 10% by mass.

[0068] The polymerization component of the polymer (A) may include one or more water-repellent auxiliary monomers (C) selected from monomers represented by the following general formula (C-1) (C1), monomers represented by the following general formula (C-2) (C2), monomers represented by the following general formula (C-3) (C3), and monomers represented by the following general formula (C-4) (C4).

[0069] (In the above general formulas (C-1) to (C-4), R １５ R is a hydrogen atom or a methyl group. １６R is a chain-like hydrocarbon group having 1 to 11 carbon atoms and having one or more substituents selected from a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloyloxy group. １７ R is a hydrogen atom or a methyl group. １８ R is a cyclic hydrocarbon group having 3 to 11 carbon atoms. １９ R is an unsubstituted chain hydrocarbon group having 1 to 4 carbon atoms. ２０ (where L is a hydrogen atom or a methyl group, M is a p+1 valent organic group, p is an organic group having a polymerizable unsaturated group, and p is an integer greater than or equal to 2, for example, an integer in the range of 2 to 6.)

[0070] In the above general formula (C-1), R １６ The chain-like hydrocarbon group having 1 to 11 carbon atoms is preferably an alkyl group having 1 to 11 carbon atoms.

[0071] Specific examples of the monomer (C1) represented by the general formula (C-1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate.

[0072] In the above general formula (C-2), R １８ The cyclic hydrocarbon group having 3 to 11 carbon atoms may be an alicyclic hydrocarbon group having 3 to 11 carbon atoms, or an aromatic hydrocarbon group having 6 to 11 carbon atoms. １８ The cyclic hydrocarbon group having 3 to 11 carbon atoms may be further substituted with substituents such as alkyl groups having 1 to 6 carbon atoms.

[0073] R １８ The cyclic hydrocarbon group having 3 to 11 carbon atoms is preferably an alicyclic hydrocarbon group having 3 to 11 carbon atoms, and more preferably an isobornyl group, a cyclohexyl group, or a dicyclopentanyl group.

[0074] Specific examples of the monomer (C2) represented by the general formula (C-2) include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.

[0075] In the above general formula (C-3), R １９ The unsubstituted chain hydrocarbon group having 1 to 4 carbon atoms is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms.

[0076] Specific examples of monomer (C3) represented by the general formula (C-3) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate.

[0077] In the above general formula (C-4), the organic group having the polymerizable unsaturated group M is preferably a (meth)acryloyloxy group.

[0078] Specific examples of the monomer (C4) represented by the general formula (C-4) include ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.

[0079] The water-repellent auxiliary monomer (C) may be used alone, or two or more monomers with different structures may be used in combination.

[0080] When the polymerization component of the polymer (A) contains a water-repellent auxiliary monomer (C), the content of the water-repellent auxiliary monomer (C) in the polymerization component is, for example, in the range of 1 to 25% by mass, preferably in the range of 3 to 25% by mass, and more preferably in the range of 5 to 20% by mass.

[0081] The polymerization component of the polymer (A) may contain, or be substantially composed of, a (meth)acrylic acid ester monomer (A), any vinyl chloride monomer (E), any reactive emulsifier monomer (B), and any water-repellent auxiliary monomer (C). Here, "substantially composed of" means that the total amount of the (meth)acrylic acid ester monomer (A), any vinyl chloride monomer (E), any reactive emulsifier monomer (B), and any water-repellent auxiliary monomer (C) in the polymerization component is, for example, 80% by mass or more, 85% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass.

[0082] The polymerization components of the polymer (A) may contain other polymerization components other than (meth)acrylic acid ester monomer (A), vinyl chloride monomer (E), reactive emulsifier monomer (B), and water-repellent auxiliary monomer (C), as long as they do not impair the effects of the present invention. Examples of the other polymerization components include (meth)acryloylmorpholine, (meth)acrylic acid, fumarate ester, maleate ester, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ether compounds, vinyl ester compounds, ethylene, styrene, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, and the like.

[0083] The molecular weight of the polymer (A) is not particularly limited; for example, the weight-average molecular weight has a lower limit of 100,000 or more or 500,000 or more, and an upper limit of 5,000,000 or less.

[0084] The polymer (A) can be produced by known methods, and commercially available products may also be used.

[0085] Examples of silicone compounds that act as water repellents include silicone resins that are solid at room temperature (25°C) or silicone oils that are liquid at room temperature (25°C).

[0086] Silicone resin is R ３ SiO １／２ Unit (M units), SiO ４／２ Unit (Q unit), R ２ SiO ２／２ Units (D units) and RSiO３／２ The organopolysiloxane has one or more siloxy units selected from units (T units) (where R is, for example, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, or a phenoxy group). Examples of silicone resins that act as water repellents include MQ-type silicone resin, MDQ-type silicone resin, MT-type silicone resin, MTQ-type silicone resin, MDT-type silicone resin, and MDTQ-type silicone resin.

[0087] Commercially available silicone resins can be used as water repellents, such as KF7312J (trimethylsilyl group-containing polysiloxane / decamethylcyclopentasiloxane mixture), KF7312F (trimethylsilyl group-containing polysiloxane / octamethylcyclotetrasiloxane mixture), KF9021L (trimethylsilyl group-containing polysiloxane / low viscosity methylpolysiloxane mixture), KF7312L (trimethylsilyl group-containing polysiloxane / low viscosity methylpolysiloxane mixture) (all manufactured by Shin-Etsu Chemical Co., Ltd.); MQ-1600 solidResin (trimethylsilyl group-containing polysiloxane), MQ-1640 FlakeResin (trimethylsilyl group-containing polysiloxane, polypropylsilsesquioxane) (all manufactured by Toray Dow Corning Co., Ltd.).

[0088] The silicone oil is, for example, a linear organopolysiloxane. Examples of silicone oils that act as water repellents include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carbinol-modified silicone oil, mercapto-modified silicone oil, carboxyl-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, aralkyl-modified silicone oil, alkylaralkyl-modified silicone oil, higher fatty acid ester-modified silicone oil, and higher aliphatic amide-modified silicone oil. Preferably, it is one or more selected from methyl hydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carbinol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, alkyl-modified silicone oil, and alkylaralkyl-modified silicone oil, and more preferably, it is amino-modified silicone oil.

[0089] Amino-modified silicone oil is an organopolysiloxane having an amino group and / or an imino group. The amino group and / or imino group in amino-modified silicone oil is, for example, -R-NH ２ The organic group represented by -R-NH-R'-NH ２ The amino and imino groups in the amino-modified silicone oil may also be capped with fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, acid halides of fatty acids having 2 to 22 carbon atoms, aliphatic monoisocyanates having 1 to 22 carbon atoms, etc.

[0090] The total functional group equivalent of amino groups and imino groups in the amino-modified silicone oil is, from the viewpoint of water repellency, in the range of, for example, 100 to 20,000 g / mol, preferably in the range of 150 to 12,000 g / mol, and more preferably in the range of 200 to 4,000 g / mol.

[0091] The kinematic viscosity of amino-modified silicone oil at 25°C is, for example, 10 to 100,000 mm². ２ The range is / s, preferably 10 to 30,000 mm ２ The range is / s, more preferably 10 to 5,000 mm ２ The range is / s. Note that the kinematic viscosity at 25°C mentioned above refers to the value measured by the method described in JIS K2283:2000 (Ubbelohde viscometer).

[0092] Commercially available silicone oils can be used, for example, KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., epoxy-modified silicone oil), X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd., carboxyl-modified silicone oil), SF8428 (manufactured by Toray Dow Corning Co., Ltd., carbinol-modified silicone oil), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd., methylhydrogen silicone oil), X-22-715 (manufactured by Shin-Etsu Chemical Co., Ltd., higher fatty acid ester-modified silicone oil), KF-96-3000cp (manufactured by Shin-Etsu Chemical Co., Ltd., dimethyl silicone oil), SF8416 (manufactured by Toray Dow Corning Co., Ltd., alkyl-modified silicone oil), SH Examples include 203 (Toray Dow Corning Co., Ltd., alkyl aralkyl modified silicone oil), SF8410 (Toray Dow Corning Co., Ltd., polyether modified silicone oil), KF8005, KF-868, KF-864, KF-393, KF-8021 (all of the above are amino modified silicone oils, manufactured by Shin-Etsu Chemical Co., Ltd.), TSF-4709, XF42-B1989 (all of the above are amino modified silicone oils, manufactured by Momentive Performance Materials Japan LLC), BY16-872, SF-8417, BY16-853U, BY16-892 (all of the above are amino modified silicone oils, manufactured by Toray Dow Corning Co., Ltd.).

[0093] Fluorine compounds, which are water-repellent agents, are compounds that contain a fluorine atom, such as compounds having a perfluoroalkyl group with 1 to 6 carbon atoms.

[0094] The fluorine compound as a water repellent agent is preferably a copolymer of a (meth)acrylate monomer having a perfluoroalkyl group with 1 to 6 carbon atoms and another polymerizable monomer.

[0095] Specific examples of the (meth)acrylate monomer having a perfluoroalkyl group with 1 to 6 carbon atoms include the following: CF ３ (CF ２ ) ４ CH ２ OCOC(CH ３ )=CH ２ CF ３ (CF ２ ) ２ CH ２ CH ２ OCOC(CH ３ )=CH ２ CF ３ (CF ２ ) ３ CH ２ CH ２ OCOC(CH ３ )=CH ２ CF ３ (CF ２ ) ４ CH ２ CH ２ OCOC(CH ３ )=CH ２ CF ３ (CF ２ ) ５ CH ２ CH ２ OCOC(CH ３ )=CH ２ CF ３ (CF ２ ) ２ CH ２ CH ２ OCOCH=CH ２ CF ３ (CF ２ ) ３ CH ２ CH ２ OCOCH=CH ２ CF ３ (CF ２ ) ４ CH ２ CH ２ OCOCH=CH２ CF ３ (CF ２ ) ５ CH ２ CH ２ OCOCH=CH ２ CF ３ (CF ２ ) ５ (CH ２ ) ２ O(CH ２ ) ２ OCOCH=CH ２ CF ３ CF ２ CH ２ CH(OH)CH ２ OCH ２ CH ２ OCOCH=CH ２ (CF ３ ) ２ CF(CF ２ ) ３ CH ２ CH ２ OCOCH=CH ２ CF ３ (CF ２ ) ５ SO ２ N(C ３ H ７ )CH ２ CH ２ OCOCH=CH ２ CF ３ (CF ２ ) ５ (CH ２ ) ４ OCOCH=CH ２ CF ３ (CF ２ ) ５ SO ２ N(CH ３ )CH ２ CH ２ OCOC(CH ３ )=CH ２ CF ３ (CF ２ ) ５ SO ２ N(C ２ H ５ )CH ２ CH ２ OCOCH=CH ２ CF３ (CF ２ ) ５ CONHCH ２ CH ２ OCOCH=CH ２ (CF ３ ) ２ CF(CF ２ ) ３ CH ２ CH ２ CH ２ OCOCH=CH ２ (CF ３ ) ２ CF(CF ２ ) ３ CH ２ CH(OCOCH ３ )CH ２ OCOC(CH ３ )=CH ２ (CF ３ ) ２ CF(CF ２ ) ３ CH ２ CH(OH)CH ２ OCOCH=CH ２ CF ３ (CF ２ ) ５ CONHCH ２ CH ２ OCOC(CH ３ )=CH ２ CF ３ CF(CF ２ Cl)(CF ２ ) ３ CONHCH ２ CH ２ OCOCH=CH ２ CF ３ CF(CF ２ Cl)(CF ２ ) ３ CONHCH ２ CH ２ OCOC(CH ３ )=CH ２ H(CF ２ ) ６ CH ２ OCOCH=CH ２ CF ２ Cl(CF ２ ) ５ CH２ OCOC (CH ３ ) = CH ２ C ６ F1 ３ CH=CH ２

[0096] Specific examples of polymerizable monomers copolymerized with the (meth)acrylate monomer having a perfluoroalkyl group having 1 to 6 carbon atoms include lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, benzyl acrylate, benzyl methacrylate, glycidyl acrylate, glycidyl methacrylate, azilidinyl acrylate, azilidinyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, alkylenediol acrylate, alkylenediol dimethacrylate, cyclohexyl acrylate, cyclohexyl Examples include (meth)acrylic acid esters such as sil methacrylate; (meth)acrylamides such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, diacetoneacrylamide, diacetone methacrylamide, and methylolated diacetoneacrylamide; alkyl maleate esters such as dibutyl maleate; alkyl phthalate esters, vinyl chloride, vinylidene chloride, ethylene, vinyl acetate, styrene, α-methylstyrene, β-methylstyrene, alkyl vinyl ethers, alkyl vinyl halogenated ethers, alkyl vinyl ketones, maleic anhydride, butadiene, isoprene, and chloroprene.

[0097] When the fluorine compound, which is a water-repellent agent, is a copolymer of a (meth)acrylate monomer having a perfluoroalkyl group with 1 to 6 carbon atoms and another polymerizable monomer, the (meth)acrylate monomer having a perfluoroalkyl group with 1 to 6 carbon atoms constitutes, for example, 40% by mass or more of the polymerization component of the copolymer, and preferably in the range of 50 to 80% by mass.

[0098] The fluorine compound that acts as a water repellent is preferably a (poly)ester of a monovalent or polyhydric alcohol having a perfluoroalkyl group having 1 to 6 carbon atoms and a polyhydric carboxylic acid; a (poly)ester of a monovalent or polyhydric alcohol having a perfluoroalkyl group having 1 to 6 carbon atoms and a polyhydric carboxylic acid having a perfluoroalkyl group having 1 to 6 carbon atoms; or a (poly)ester of a monovalent or polyhydric alcohol having a perfluoroalkyl group having 1 to 6 carbon atoms and a polyhydric carboxylic acid having a perfluoroalkyl group having 1 to 6 carbon atoms.

[0099] The fluorine compound used as a water repellent is preferably a (poly)urethane comprising a monovalent or polyhydric alcohol having a perfluoroalkyl group with 1 to 6 carbon atoms and a monovalent or polyhydric isocyanate. The number-average molecular weight of the (poly)urethane is, for example, 700 or more.

[0100] The fluorine compound that acts as a water repellent is preferably a compound having a perfluoroalkyl group with 1 to 6 carbon atoms and an isocyanate group reactive group (e.g., a hydroxyl group, an amino group, or a carboxyl group). The compound is C ６ F １３ CH ２ CH ２ OH, C ６ F １３ SO ２ N(CH ３ )CH ２ CH ２ OH, C ６ F １３ SO ２ N(CH ２ CH ３ )CH ２ CH ２ OH, C ６ F １３ COOH, C ６ F １３ CONHC ３ H ６ NHCH ３ , C ６ F １３ SO ２ NHCH ３ These are some examples.

[0101] The fluorine compound used as a water repellent is preferably an aliphatic polycarbonate having a perfluoroalkyl group with 1 to 6 carbon atoms.

[0102] The lower limit of the water-repellent additive content in the water-repellent composition of the present invention is, for example, 1.0 part by mass or more, 5.0 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 50 parts by mass or more, or 100 parts by mass or more, per 100 parts by mass of the water-repellent agent. The upper limit of the water-repellent additive content in the water-repellent composition of the present invention is, for example, 30,000 parts by mass or less, 20,000 parts by mass or less, 15,000 parts by mass or less, 10,000 parts by mass or less, 5,000 parts by mass or less, 1,500 parts by mass or less, 1,000 parts by mass or less, or 500 parts by mass or less, per 100 parts by mass of the water-repellent agent. The amount of the water-repellent additive in the water-repellent composition of the present invention is, for example, in the range of 1.0 to 15,000 parts by mass, preferably in the range of 15 to 1,500 parts by mass, more preferably in the range of 15 to 500 parts by mass or 100 to 1,500 parts by mass, per 100 parts by mass of the water-repellent agent.

[0103] The amount of water-repellent additive should be set appropriately depending on the intended use of the water-repellent composition. For example, in applications where high water-repellent durability is required, such as automotive applications and disaster prevention / life-saving clothing (e.g., firefighter uniforms, maritime rescue team uniforms, mountain rescue team uniforms), it is advisable to set a high amount of water-repellent additive. However, for general clothing and interior applications, it is not necessary to set a high amount of water-repellent additive.

[0104] The water-repellent composition of the present invention may contain other components besides water-repellent enhancers and water-repellents, depending on its intended use. Examples of such other components include thickeners, pigments, dyes, penetrating agents, antistatic agents, defoaming agents, flame retardants, antibacterial agents, preservatives, crosslinking agents, adhesion enhancers, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, curing accelerators, and deodorants.

[0105] The form of the water-repellent composition of the present invention is not particularly limited, and may be any of the following: a dispersion in which a water-repellent additive and a water-repellent agent are dispersed in a solvent; a solution in which a water-repellent additive and / or a water-repellent agent are dissolved in a solvent; or a resin composition in which a water-repellent additive and a water-repellent agent are dispersed in a binder resin.

[0106] Examples of the solvent include water, alcohol solvents, ether solvents, ketone solvents, and aromatic solvents. Examples of the binder resin include acrylic resins, urethane resins, phenolic resins, polyester resins, and epoxy resins.

[0107] [Water-repellent substrate] The water-repellent substrate of the present invention is a substrate to which the water-repellent auxiliary agent of the present invention and the water-repellent agent are attached. The water-repellent auxiliary agent of the present invention can enhance the persistence of the water-repellent effect of the water-repellent agent, and the substrate to which the water-repellent auxiliary agent of the present invention and the water-repellent agent are attached has high water-repellent persistence.

[0108] The substrate used to impart water repellency is not particularly limited and includes textiles, leather, paper, metal, wood, rubber, plastic, concrete, cement board, gypsum board, glass, brick, tile, wall material, etc.

[0109] When the base material that imparts water repellency is a fiber, the fiber may be a natural fiber such as cotton, silk, linen, wool, angora, or mohair, or a synthetic fiber such as polyester, nylon, acrylic, urethane, or spandex. Furthermore, the fiber may be in the form of a woven fabric, knitted fabric, nonwoven fabric, or other processed form.

[0110] Conventional known methods such as immersion, spraying, roll coating, bar coating, and brush coating can be applied to the substrate.

[0111] The amount of the water-repellent composition applied to the substrate surface is not particularly limited, but for example, the total amount of the water-repellent additive and water-repellent agent applied is 0.1 to 200 g / m². ２ The range is preferably 1 to 100 g / m². ２ It is within the range.

[0112] In order to impart water repellency to the substrate, the water-repellent aid and water-repellent agent of the present invention may be applied separately, or a water-repellent composition containing both the water-repellent aid and water-repellent agent of the present invention may be applied.

[0113] The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

[0114] (Synthesis Example 1: Preparation of Titanium Dioxide Compound M1) A mixture of ilmenite ore, niobium pentoxide, and zirconium oxide was dissolved with sulfuric acid, water, and iron to obtain a solution mainly composed of titanium sulfate and iron sulfate. Impurities such as iron sulfate were removed, and the mixture was subjected to thermal hydrolysis to obtain a hydrated titanium hydroxide composition. The titanium hydroxide composition was washed and calcined at 900°C, and the resulting solid was pulverized to obtain a titanium oxide compound that is crystalline rutile-type titanium oxide.

[0115] The obtained titanium oxide compound was evaluated for various physical properties using the method described below. The results are shown below: BET specific surface area: 9.0 m² ２ Rutile content per gram: 95.4% Primary particle size: 0.18 μm Zr / Ti ratio: 0.05 Nb / Ti ratio: 0.17

[0116] (Method for measuring the BET specific surface area of ​​titanium oxide compounds) The specific surface area was measured using the "Macsorb HM model-1208" fully automatic BET specific surface area measuring device manufactured by Mountec Co., Ltd. (BET single-point method).

[0117] (Method for measuring the primary particle size of titanium dioxide compounds) The primary particle size of titanium dioxide compounds was measured by directly measuring the size of the primary particles from electron microscope images. Specifically, the short axis diameter and long axis diameter of individual titanium dioxide primary particles were measured under the following conditions, and the average was taken as the particle size of that primary particle. Then, for 100 or more titanium dioxide particles, the volume (weight) of each particle was approximated by a cube of the measured particle size, and the volume-average particle size was taken as the average primary particle size. <Measurement conditions for transmission electron microscope (TEM)> Instrument name: JEM-1400Flash (manufactured by JEOL Ltd.) Acceleration voltage: 120kV Magnification: 20K

[0118] (Method for measuring the rutile content of titanium dioxide compounds) Using the X-ray diffractometer "XRD-6100" manufactured by Shimadzu Corporation, the peak height ratio corresponding to rutile-type crystals was calculated from the peak heights corresponding to the total crystal types of titanium dioxide (rutile-type, brookite-type, anatase-type).

[0119] (Calculation method for Zr / Ti ratio and Nb / Ti ratio) Metal element composition analysis was performed using the bulk fundamental parameter (bulk FP) method with the SEA1200VX X-ray fluorescence analyzer manufactured by Seiko Instruments Inc. Specifically, for the fluorescence intensity (cps: count per second) of each metal element, the intensity ratio of the fluorescence intensity (cps) of zirconium or niobium, with the fluorescence intensity (cps) of titanium set to 100, was calculated as the Zr / Ti ratio or Nb / Ti ratio, respectively.

[0120] The obtained titanium oxide compound was subjected to the following steps (a) to (c) to prepare a copper-supported titanium oxide compound: a) Mixing step (reaction step) 600 parts by mass of the titanium oxide compound, 8 parts by mass of copper(II) chloride dihydrate, and 900 parts by mass of water were mixed in a stainless steel container. The mixture was then stirred with a stirrer (Robomix, manufactured by Tokushu Kika Kogyo Co., Ltd.), and a 1 mol / L sodium hydroxide aqueous solution was added dropwise until the pH of the mixture reached 10. b) Dehydration step The mixture was subjected to vacuum filtration using qualitative filter paper (5C) to separate the solid components, and then washed with deionized water. The washed solids were then dried at 120°C for 12 hours to remove moisture. After drying, a powdered titanium oxide compound was obtained using a mill (Millser, manufactured by Iwatani Sangyo Co., Ltd.). c) Heat treatment step The powdered titanium oxide compound obtained in the dehydration step of b) was heat-treated at 450°C for 3 hours in the presence of oxygen using a precision constant temperature incubator (DH650 manufactured by Yamato Scientific Co., Ltd.) to obtain titanium oxide compound M1, which is a titanium oxide compound on which a divalent copper compound is supported.

[0121] The obtained copper-supported titanium oxide compound was completely dissolved in hydrofluoric acid solution, and the resulting extract was analyzed using an ICP emission spectrometer. As a result, it was found that the amount of copper supported in the copper-supported titanium oxide compound was 0.5 parts by mass per 100 parts by mass of titanium oxide.

[0122] (Example 1: Manufacturing and evaluation of water-repellent textile products) 25 parts by mass of titanium dioxide compound M1, 73.5 parts by mass of water, and 1.5 parts by mass of dispersant (DISPERBIK 181, manufactured by BIC Chemie) were dispersed in a sand grinder (manufactured by AIMEX) to obtain an aqueous slurry. 4 parts by mass of the aqueous slurry, 1 part by mass of acrylic resin (RYUDYE-W FIXER 254PK, manufactured by DIC Corporation) as a binder resin, and 95 parts by mass of water were mixed. Using this mixture, PET de Chine fabric (approximately 75 g / m²) was prepared. ２ ) Apply approximately 100g / m² of paint before drying using a pad dryer (manufactured by Tsujii Dyeing Machinery Co., Ltd.). ２ The fabric was immersed in the following manner. After the impregnation treatment, it was dried in the same machine at 130°C for 2 minutes to obtain a PET de Chine fabric impregnated with a water-repellent additive. A water-repellent treatment solution was prepared by mixing 99.5 parts by mass of water and 0.5 parts by mass of a fluorine-based water-repellent agent (a compound having a C6 perfluoroalkyl group, "NK Guard S-0671" manufactured by Nikka Chemical Co., Ltd., with 32.1% by mass of non-volatile components (active ingredients)). The PET de Chine fabric impregnated with the water-repellent additive was then impregnated with the water-repellent treatment solution in the same manner as above. After the impregnation treatment, it was dried at 130°C for 2 minutes and then at 180°C for 2 minutes to obtain a water-repellent PET de Chine fabric. The obtained water-repellent PET de Chine fabric was evaluated as follows. The results are shown in Table 1.

[0123] (Water-repellent restoration rate) 30 μL of a stain component (A) consisting of 0.01 parts by mass of Oil Red O (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.99 parts by mass of oleic acid, and 99 parts by mass of ethanol was dropped onto the obtained water-repellent PET decine fabric using a micropipette (here, oleic acid is used to simulate human sebum stains). The PET decine fabric with this stain component attached was left under a 1,000 lux fluorescent lamp for two days. (a) The water contact angle of the water-repellent PET decine fabric before stain attachment, (b) the water contact angle of the water-repellent PET decine fabric after stain attachment, and (c) the water contact angle of the water-repellent PET decine fabric after light irradiation were measured using a contact angle meter ("Automatic Contact Angle Meter DM500" manufactured by Kyowa Interface Science Co., Ltd.), and the water-repellent restoration rate was calculated by applying these values ​​to the following formula. The results are shown in Table 1. A higher value indicates a higher duration of the water-repellent effect. Water repellency restoration rate [%] = ((c) - (b)) / ((a) - (b)) × 100 (a) Water contact angle of water-repellent PET de Chine fabric before dirt adhesion (b) Water contact angle of water-repellent PET de Chine fabric after dirt adhesion (c) Water contact angle of water-repellent PET de Chine fabric after light irradiation

[0124] (Example 2: Manufacturing and Evaluation of Water-Repellent Textile Products) 25 parts by mass of titanium dioxide compound M1, 73.5 parts by mass of water, and 1.5 parts by mass of dispersant (DISPERBIK 181, manufactured by BIC Chemie) were dispersed in a sand grinder (manufactured by AIMEX) to obtain an aqueous slurry. 4 parts by mass of the aqueous slurry, 1 part by mass of acrylic resin (RYUDYE-W FIXER 254PK, manufactured by DIC Corporation) as a binder resin, 0.5 parts by mass of fluorine-based water repellent (NK Guard S-0671, manufactured by Nikka Chemical Co., Ltd.) and 94.5 parts by mass of water were mixed. Using this mixture, PET de Chine fabric (approximately 75 g / m²) was prepared. ２ ) Apply approximately 100g / m² of paint before drying using a pad dryer (manufactured by Tsujii Dyeing Machinery Co., Ltd.). ２ The material was immersed in water to achieve the desired result. After the impregnation treatment, it was dried in the same machine at 130°C for 2 minutes and then at 180°C for 2 minutes to obtain a water-repellent PET de Chine fabric. The water repellency of the obtained water-repellent PET de Chine fabric was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0125] In Example 1, the water-repellent additive (titanium dioxide compound) and the water-repellent agent were applied separately to the PET de Chine fabric (in separate baths), whereas in Example 2, the water-repellent additive (titanium dioxide compound) and the water-repellent agent were applied simultaneously to the PET de Chine fabric (in the same bath).

[0126] (Example 3 and Comparative Examples 1-2) For Example 3, the water repellency was evaluated in the same manner as in Example 1, except that the components shown in Table 1 were applied to PET de Chine fabric. For Comparative Examples 1-2, the water repellency was evaluated in the same manner as in Example 2, except that the components shown in Table 1 were applied to PET de Chine fabric. The results are shown in Table 1.

[0127]

[0128] In Table 1, the non-fluorine-based water repellent used was "Neoseed NR-8800" manufactured by Nikka Chemical Co., Ltd., which contains a silicone compound (non-volatile component (active ingredient) 23.3% by mass).

[0129] The results in Table 1 show that the water-repellent enhancer of the present invention can be used to enhance the duration of the water-repellent effect of the water-repellent agent.

Claims

1. A water-repellent additive that is a metal oxide, wherein the metal of the metal oxide is one or more selected from lithium, sodium, potassium, strontium, silver, niobium, titanium, lanthanum, zirconium, tantalum, gallium, bismuth, vanadium, rhodium, chromium, and tungsten.

2. The water-repellent additive according to claim 1, wherein the metal oxide is titanium oxide.

3. The water-repellent additive according to claim 2, wherein the titanium dioxide comprises rutile-type titanium dioxide.

4. The water-repellent additive according to claim 2, wherein the titanium oxide is titanium oxide supporting a metal compound.

5. The water-repellent additive according to claim 2, wherein the titanium oxide is titanium oxide supporting one or more compounds selected from copper compounds, silver compounds, iron compounds, platinum compounds, and palladium compounds.

6. The water-repellent additive according to claim 2, wherein the titanium oxide is titanium oxide supporting a divalent copper compound.

7. The water-repellent agent according to claim 2, wherein the titanium oxide is a titanium oxide compound containing zirconium and / or niobium.

8. The water-repellent additive according to claim 2, wherein the titanium oxide is a titanium oxide compound containing zirconium, and the zirconium content ratio (Zr / Ti ratio) to titanium 100 in the titanium oxide compound is in the range of 0.03 to 0.

8.

9. The water-repellent additive according to claim 2, wherein the titanium oxide compound is a titanium oxide compound containing niobium, and the ratio of niobium content to titanium 100 in the titanium oxide compound (Nb / Ti ratio) is in the range of 0.05 to 0.

8.

10. A water-repellent composition containing a water-repellent aid and a water-repellent agent according to any one of claims 1 to 9.

11. The water-repellent composition according to claim 10, wherein the water-repellent agent is one or more selected from polymers having a structure derived from (meth)acrylic acid esters having hydrocarbon groups with 12 or more carbon atoms, silicone compounds, and fluorine compounds.

12. The water-repellent composition according to claim 10, comprising 1.0 to 15,000 parts by mass of the water-repellent additive with respect to 100 parts by mass of the water-repellent agent.

13. A water-repellent substrate to which a water-repellent aid and a water-repellent agent according to any one of claims 1 to 9 are attached.

Images