Water repellent composition

Abstract

Provided is a water repellent composition which comprises: a water-repellent resin based on a hydrocarbon having a C5-C40 hydrocarbon group; and hydrophilic particles. The water repellent composition can impart both satisfactory water repellency and satisfactory antislip properties to textile products, and has storage stability.

Description

[Technical Field]

[0001] The present disclosure relates to water repellent compositions. [Background technology]

[0002] It is known that hydrocarbon group-containing polymers can be used as water repellents for imparting water repellency to base materials (particularly textile products). For example, Patent Document 1 discloses that high water repellency and washing durability can be achieved by using a water-repellent fabric made of fibers having, on the fiber surface, hydrophilic particles with an average primary particle diameter of 40 nm to 600 nm and a coating made of a water repellent agent and a binder resin that covers the hydrophilic particles. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-42488 Summary of the Invention [Problem to be solved by the invention]

[0004] When using conventional water-repellent textile products, the seams may slip, which can reduce the reliability of the textile product. Furthermore, when a hydrophobic repellent component is combined with hydrophilic particles, a precipitate may form, resulting in poor storage stability.

[0005] An object of the present disclosure is to provide a water repellent composition that can impart both good water repellency and good slip resistance to textile products and has storage stability. [Means for solving the problem]

[0006] Preferred aspects of the present disclosure are as follows. [Section 1] A water repellent composition comprising a hydrocarbon-based water repellent resin having a hydrocarbon group with 5 to 40 carbon atoms and hydrophilic particles. [Section 2] Item 2. The water repellent composition according to Item 1, wherein the hydrophilic particles are dispersed in water at a concentration of 10 g / L and the resulting aqueous dispersion is adjusted to pH 7, and the turbidity of the aqueous dispersion is 20 ppm or less. [Section 3] Item 3. The water repellent composition according to item 1 or 2, comprising at least one selected from the group consisting of organic acids, surfactants, and organic solvents. [Section 4] Item 4. The water repellent composition according to any one of Items 1 to 3, wherein the hydrophilic particles are dispersed in water at a concentration of 10 g / l and the aqueous dispersion is adjusted to pH 7, and the zeta potential of the aqueous dispersion is +10 mV or more. [Section 5] Item 5. The water repellent composition according to any one of items 1 to 4, wherein the amount of the hydrophilic particles is 2% by weight or more and 12% by weight or less based on the total amount of the hydrocarbon-based water repellent resin and the hydrophilic particles. [Section 6] Item 6. The water repellent composition according to any one of Items 1 to 5, wherein the hydrophilic particles have an average primary particle size of less than 40 nm. [Section 7] Item 7. The water repellent composition according to any one of items 1 to 6, wherein the hydrophilic particles are inorganic particles. [Section 8] Item 8. The water repellent composition according to any one of items 1 to 7, wherein the hydrophilic particles are at least one selected from the group consisting of silica and alumina. [Section 9] Item 9. The water repellent composition according to any one of items 1 to 8, comprising at least one selected from the group consisting of silicones and waxes. [Section 10] The hydrocarbon-based water-repellent resin is represented by the following formula: CH2=C(-R 12 )-C(=O)-Y 11 -(R 11 ) k [In the formula, R 11 is a hydrocarbon group having 5 to 40 carbon atoms, R 12is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 11 represents a direct bond, a divalent to tetravalent hydrocarbon group having 1 carbon atom, and a divalent to tetravalent group consisting of at least one selected from -CH-, -O-, -C(=O)-, -S(=O)-, and -NR'- (R' represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms); k is 1 to 3. Item 10. The water repellent composition according to any one of items 1 to 9, which is a polymer having a repeating unit derived from a monomer represented by the following formula: [Section 11] Item 11. A method for producing a water repellent composition according to any one of items 1 to 10, comprising a step of reacting a hydrocarbon-based water repellent resin raw material in a medium containing the hydrocarbon-based water repellent resin raw material and the hydrophilic particles to obtain the hydrocarbon-based water repellent resin. [Section 12] Item 11. A method for producing a treated product, comprising treating a substrate with the water repellent composition according to any one of items 1 to 10. [Section 13] Item 11. A textile product having the solid component of the water repellent composition according to any one of Items 1 to 10 attached thereto. [Effects of the Invention]

[0007] The water repellent composition of the present disclosure can impart both good water repellency and good slip resistance to a substrate (particularly a textile product), and has storage stability. DETAILED DESCRIPTION OF THE INVENTION

[0008] <Water repellent composition> The water repellent composition of the present disclosure contains a hydrocarbon-based water repellent resin and hydrophilic particles. The water repellent composition may further contain other components (such as silicone, wax, organic acid, surfactant, organic solvent, etc.).

[0009] [Hydrocarbon-based water-repellent resin] The hydrocarbon-based water-repellent resin is a water-repellent resin having a hydrocarbon group with 5 to 40 carbon atoms. Water repellency refers to the property of being able to increase the water repellency of a substrate by adhering to the substrate. The hydrocarbon-based water-repellent resin may have a perfluoroalkyl group with 8 or more carbon atoms, a perfluoroalkyl group with 6 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, or no fluorine atoms. The hydrocarbon-based water-repellent resin is preferably a non-fluorine resin.

[0010] Hydrocarbon-based water-repellent resins are polymers. Here, polymers include not only compounds with large molecular weights (e.g., molecular weights of 2,000 to 10,000,000) but also oligomers (e.g., molecular weights of 200 to less than 2,000). Polymers may be compounds obtained by the reaction of at least two compounds (e.g., monomers) (one type of compound or two types of compounds). The type of polymer is not limited as long as it contains a hydrophobic unit. Methods for modifying the hydrophobic unit in a polymer are not limited, and examples include polymerizing a monomer having a hydrocarbon group and reacting a reactant having a hydrocarbon group and a reactive group with a functional group of the polymer.

[0011] Hydrocarbon-based water-repellent resins generally have a hydrocarbon group having 5 to 40 carbon atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. The hydrocarbon group may be linear or branched, and is preferably linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 11 or more, 12 or more, 14 or more, or 16 or more, and preferably 10 or more. The number of carbon atoms in the hydrocarbon group may be 40 or less, 30 or less, 25 or less, 22 or less, or 20 or less, and preferably 30 or less.

[0012] The hydrocarbon-based water-repellent resin may have 2 or more, 5 or more, 10 or more, 25 or more, 50 or more, 75 or more, 100 or more, 300 or more, or 500 or more hydrocarbon groups per molecule, and preferably has 10 or more hydrocarbon groups. The hydrocarbon-based water-repellent resin may have 1000 or less, 500 or less, 300 or less, 100 or less, 75 or less, or 50 or less hydrocarbon groups per molecule.

[0013] The water contact angle of the hydrocarbon-based water-repellent resin may be 100° or more, 101° or more, 103° or more, 105° or more, 110° or more, 115° or more, or 120° or more. The water contact angle of the hydrocarbon-based water-repellent resin may be 160° or less, or 140° or less. From the viewpoint of water repellency, it is preferable that the water contact angle of the hydrocarbon-based water-repellent resin is within the above range. The "water contact angle of the hydrocarbon-based water-repellent resin" refers to the water contact angle of a spin-coated film obtained by dissolving the hydrocarbon-based water-repellent resin in a good solvent and spin-coating the resultant solution.

[0014] The weight average molecular weight of the hydrocarbon-based water-repellent resin may be 500 or more, 1000 or more, 2500 or more, 5000 or more, 10000 or more, 25000 or more, or 50000 or more, and is preferably 5000 or more. The weight average molecular weight of the hydrocarbon-based water-repellent resin may be 1000000 or less, 500000 or less, 250000 or less, 100000 or less, 500000 or less, 250000 or less, or 10000 or less, and is preferably 100000 or less.

[0015] The amount of the hydrocarbon-based water repellent resin may be 0.01 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, or 30 wt% or more relative to the water repellent composition. The amount of the hydrocarbon-based water repellent resin may be 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, or 3 wt% or less relative to the water repellent composition. For example, the water repellent composition may be stored at a high concentration, and when used as a repellent, it may be diluted to a desired concentration by adding a liquid medium as needed. The water repellent composition of the present disclosure has improved product stability, making it possible to supply high-concentration products that have previously been problematic in terms of stability.

[0016] Examples of hydrocarbon-based water-repellent resins include hydrocarbon-based acrylic polymers, hydrocarbon-based polyurethanes, other hydrocarbon group-containing resins, and combinations thereof.

[0017] [Hydrocarbon-based acrylic polymer] The hydrocarbon-based water-repellent resin may be a hydrocarbon-based acrylic polymer, which refers to a polymer having repeating units derived from an acrylic monomer.

[0018] The hydrocarbon-based acrylic polymer contains a repeating unit derived from a hydrophobic monomer (a1). The hydrocarbon-based acrylic polymer may further contain a repeating unit derived from at least one monomer selected from the group consisting of a repeating unit derived from a chloride monomer (a2), a cyclic hydrocarbon group-containing monomer (a3), and a crosslinkable monomer (a4). The hydrocarbon-based acrylic polymer may further contain a repeating unit derived from another monomer (a5).

[0019] (Hydrophobic Monomer (a1)) The hydrophobic monomer (a1) has one ethylenically unsaturated double bond and a hydrocarbon group having 5 to 40 carbon atoms.

[0020] The hydrophobic monomer (a1) may have at least one hydrocarbon group having 5 to 40 carbon atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. The hydrocarbon group may be linear or branched, and is preferably linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 11 or more, 12 or more, 14 or more, or 16 or more, and preferably 10 or more. The number of carbon atoms in the hydrocarbon group may be 40 or less, 30 or less, 25 or less, 22 or less, or 20 or less, and preferably 30 or less.

[0021] The hydrophobic monomer (a1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 -(R 11 ) k [In the formula, R 11 is a hydrocarbon group having 5 to 40 carbon atoms, R 12 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 11 represents a direct bond, a divalent to tetravalent hydrocarbon group having 1 carbon atom, and a divalent to tetravalent group consisting of at least one selected from -CH-, -O-, -C(=O)-, -S(=O)-, and -NR'- (R' represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms); k is 1 to 3. The monomer may be represented by the formula:

[0022] R 11is preferably a branched or linear (preferably long-chain linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The -CH3 group has a lower surface free energy than -CH2- and is more likely to exhibit liquid repellency. For this reason, a structure with many branches and many -CH3 groups is preferred. On the other hand, long-chain alkyl groups of a certain length exhibit high liquid repellency due to their crystallinity. Therefore, R may be a branched hydrocarbon group (for example, a branched alkyl group), particularly a t-butyl group or an isopropyl group, a group with a multi-branched structure, or a long-chain hydrocarbon group (or a long-chain linear hydrocarbon group), for example, an alkyl group. 11 The number of carbon atoms in R may be 5 or more, 6 or more, 8 or more, 10 or more, 11 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and is preferably 10 or more. 11 may have 40 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 12 or less carbon atoms, and preferably 30 or less.

[0023] k is 1, 2, or 3. Y 11 In the case where Y has a tetravalent hydrocarbon group having one carbon atom, k=3. 11 In the case where Y has a trivalent hydrocarbon group having one carbon atom, k=2. 11 does not have a trivalent or tetravalent hydrocarbon group having one carbon atom (for example, Y 11 has (for example, 1 to 6) divalent hydrocarbon groups (-CH2-) having one carbon atom, then k=1.

[0024] R 12 R may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Alternatively, R may be a -CF group. 12 Examples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, a -CF3 group, and a cyano group. 12 is preferably a hydrogen atom, a methyl group, or a chlorine atom. 12 More preferably, R is a methyl group. 12 When R is a methyl group, higher liquid repellency is obtained.12 may be a hydrogen atom, particularly from the viewpoint of reactivity.

[0025] Y 11 is preferably a divalent group. Examples of the divalent to tetravalent hydrocarbon group having 1 carbon atom include -CH2-, -CH= having a branched structure, and -C≡ having a branched structure.

[0026] Y 11 -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-X'-, -Y'-X'-Y'- , -Y'-X'-Y'-C(=O)-, -Y'-X'-C(=O)-Y'-, -Y'-X'-Y'-C(=O)-Y'-, or -Y'-X'-Y'-X'- [In the formula, each Y' independently represents a direct bond, -O-, -NR'- (R' represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), or -S(=O)2-, X' is -(CH2) m -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l - (each l is independently an integer of 0 to 5, and -C6H4- is a phenylene group). Y 11 is preferably not only a divalent hydrocarbon group.

[0027] Y 11 Specific examples are -O-, -NH-, -OC(=O)-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m-C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2-, -NH-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, or -NH-(CH2) m -NH-C6H4- [where m is an integer from 1 to 5, particularly 2 or 4].

[0028] Y 11 is, -O-, -NH-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m-OC(=O)-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -NH-C(=O)-NH- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] It is preferable that Y 11 is -O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, or -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, especially -O-(CH2) m It is more preferably -NH-C(=O)-.

[0029] The hydrophobic monomer (a1) preferably does not have a reactive group or a hydrophilic group. Examples of reactive groups include epoxy groups, chloromethyl groups, bromomethyl groups, iodomethyl groups, isocyanate groups, and blocked isocyanate groups. Examples of hydrophilic groups include hydroxyl groups, polyalkylene oxide groups, amino groups, carboxylic acid groups, sulfonic acid groups, phosphate groups, alkali metal or alkaline earth metal salts of carboxylic acid, sulfonic acid, and phosphate, ammonium salts with chlorine, bromine, or iodine ions as counter anions, and other ionic groups. Here, the reactive group and the hydrophilic group may overlap with each other.

[0030] The hydrophobic monomer (a1) may have a water solubility at 25° C. of 10 g / L or less, 5 g / L or less, 3 g / L or less, 1 g / L or less, 0.5 g / L or less, or 0.1 g / L or less, preferably 3 g / L or less. The homopolymer of the hydrophobic monomer (a1) may have a water solubility at 25° C. of 10 g / L or less, 5 g / L or less, 3 g / L or less, 1 g / L or less, 0.5 g / L or less, or 0.1 g / L or less, preferably 3 g / L or less.

[0031] The water contact angle of the homopolymer of hydrophobic monomer (a1) may be 75° or more, 80° or more, 85° or more, 90° or more, 95° or more to 100° or more, 101° or more, 103° or more, 105° or more, 110° or more, 115° or more, or 120° or more, preferably 90° or more or 100° or more. The water contact angle of the homopolymer of hydrophobic monomer (a1) may be 160° or less, 150° or less, 140° or less, 130° or less, 125° or less, or 110° or less. A water contact angle within the above range is preferred from the viewpoint of the liquid repellency, particularly water repellency, of the copolymer. The water contact angle of the homopolymer may be a value obtained by spin-coating a chloroform solution of the homopolymer having a solids concentration of 1.0% on a silicon wafer substrate, dropping 2 μL of water on the coating, and measuring the contact angle 1 second after the drop has landed.

[0032] Specific examples of the hydrophobic monomer (a1) are as follows: The compound of the following chemical formula is an acrylic compound having a hydrogen atom at the α-position, but may also be a methacrylic compound having a methyl group at the α-position or an α-chloroacrylic compound having a chlorine atom at the α-position. CH2=CHC(=O)OC 18 H 37 CH2=CHC(=O)OC n H 2n+1 CH2=CHC(=O)OC2H4OC(=O)NHC 18 H 37 CH2=CHC(=O)OC2H4NHC(=O)OC 18 H 37 CH2=CHC(=O)OC m H 2m NHC(=O)C n H 2n+1 CH2=CHC(=O)OC2H4OC(=O)NHC n H 2n+1 CH2=CHC(=O)OC2H4NHC(=O)OC n H 2n+1 CH2=CHC(=O)OC2H4NHC(=O)NHCn H 2n+1 CH2=CHC(=O)OC4H8OC(=O)NHC n H 2n+1 CH2=CHC(=O)NHC m H 2m OC(=O)NHC n H 2n+1 TIFF0007824536000001.tif2966 TIFF0007824536000002.tif3069CH2=CHC(=O)OC m H 2m NHSO2C n H 2n+1 CH2=CHC(=O)OC m H 2m SO2NHC n H 2n+1 [In the above formula, n is a number from 3 to 40, and m is a number from 1 to 5.] TIFF0007824536000003.tif3142

[0033] Preferred specific examples of the hydrophobic monomer (a1) include stearyl (meth)acrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, behenyl α-chloroacrylate, stearamidoethyl (meth)acrylate, 2-stearamidoethyl acrylate, CH═CHC(═O)OCHNHSOC 18 H 37 These may be used alone or in combination of two or more.

[0034] From the viewpoint of the liquid repellency of the water repellent composition, the hydrophobic monomer (a1) preferably contains a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group. A combination of a hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group with a hydrophobic monomer (a1) not having an amide group, a urea group, or a urethane group is also possible. Examples of the hydrophobic monomer (a1) having an amide group, a urea group, or a urethane group include a hydrophobic monomer (a1) having a CH═C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-R 11 , CH2=C(-R 12 )-C(=O)-O-(CH2) m -OC(=O)-NH-R 11 , CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-OR 11 , and CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R 11 The hydrophobic monomer (a1) is CH2=C(-R 12 )-C(=O)-O-(CH2) m -NH-C(=O)-R 11 Here, m may be an integer of 1 to 5, particularly 2 or 4.

[0035] (Chloride monomer (a2)) The hydrocarbon-based acrylic polymer may contain repeating units derived from at least one chloride monomer (a2) selected from the group consisting of vinyl chloride and vinylidene chloride. The chloride monomer (a2) is preferably vinyl chloride.

[0036] (Cyclic hydrocarbon group-containing monomer (a3)) The hydrocarbon-based acrylic polymer may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (a3). The cyclic hydrocarbon group-containing monomer (a3) ​​is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0037] The cyclic hydrocarbon group-containing monomer (a3) ​​preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may, for example, have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0038] The cyclic hydrocarbon group may be aliphatic or aromatic, preferably aliphatic. The cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a linear or branched chain hydrocarbon group).

[0039] The cyclic hydrocarbon group may have 4 or more, 6 or more, or 8 or more carbon atoms, and may have 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less carbon atoms.

[0040] Specific examples of cyclic hydrocarbon groups include cyclohexyl, t-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, bornyl, isobornyl, norbornyl, dicyclopentanyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-t-butylphenyl, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene, adamantylene, phenylene, naphthylene, etc.), and groups that are substitution products thereof.

[0041] Specific examples of the cyclic hydrocarbon group-containing monomer (a3) ​​include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0042] (Crosslinkable monomer (a4)) The hydrocarbon-based acrylic polymer may have a repeating unit derived from a crosslinkable monomer (a4). The crosslinkable monomer (a4) is a monomer capable of imparting crosslinkability to the copolymer and may have at least two groups selected from the group consisting of reactive groups and olefinic carbon-carbon double bonds. The crosslinkable monomer (a4) may be a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group.

[0043] The crosslinkable monomer (a4) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may, for example, have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0044] Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a carbonyl group, an isocyanate group (blocked isocyanate group), and the like.

[0045] Specific examples of the crosslinkable monomer (a4) include diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxyethyl (meth)acrylamide, glycidyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and compounds in which these acrylates are substituted with acrylamide. These may be used alone or in combination of two or more. These may be used alone or in combination of two or more.

[0046] (Other monomers (a5) ) The hydrocarbon-based acrylic polymer may contain a repeating unit derived from a monomer (a5) other than the monomers (a1) to (a4).

[0047] Specific examples of the other monomer (a5) include, for example, ethylene, halogenated olefin, vinyl acetate, acrylonitrile, alkoxypolyalkylene glycol (meth)acrylate, and vinyl alkyl ether. The other monomer is not limited to these examples. These may be used alone or in combination of two or more.

[0048] (Polymer composition) The amount of repeating units derived from the hydrophobic monomer (a1) may be 15% by weight or more, 20% by weight or more, 25% by weight or more, 35% by weight or more, 45% by weight or more, 55% by weight or more, or 65% by weight or more, based on the hydrocarbon-based acrylic polymer. The amount of repeating units derived from the hydrophobic monomer (a1) may be 98% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less, based on the hydrocarbon-based acrylic polymer.

[0049] The proportion of the hydrophobic monomer (a1) having an amide group, urea group, or urethane group in the repeating units derived from the hydrophobic monomer (a1) may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, or 75% by weight or more. The proportion of the hydrophobic monomer (a1) having an amide group, urea group, or urethane group in the repeating units derived from the hydrophobic monomer (a1) may be 100% by weight or less, 90% by weight or less, 80% by weight or less, or 70% by weight or less.

[0050] The amount of the repeating units derived from the chloride monomer (a2) may be 3% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, or 35% by weight or more, based on the hydrocarbon-based acrylic polymer. The amount of the repeating units derived from the chloride monomer (a2) may be 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less, preferably 60% by weight or less, based on the hydrocarbon-based acrylic polymer.

[0051] The amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, based on the hydrocarbon-based acrylic polymer. The amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or 5% by weight or less, based on the hydrocarbon-based acrylic polymer.

[0052] The amount of the repeating units derived from the crosslinkable monomer (a4) may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, based on the hydrocarbon-based acrylic polymer. The amount of the repeating units derived from the crosslinkable monomer (a4) may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or 5% by weight or less, based on the hydrocarbon-based acrylic polymer.

[0053] The amount of repeating units derived from the other monomer (a5) may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, based on the hydrocarbon-based acrylic polymer. The amount of repeating units derived from the other monomer (a5) may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less, based on the hydrocarbon-based acrylic polymer.

[0054] The amount of the repeating units derived from the chloride monomer (a2) may be 5 parts by weight or more, 10 parts by weight or more, 25 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, based on 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1). The amount of the repeating units derived from the chloride monomer (a2) may be 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, or 25 parts by weight or less, based on 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1).

[0055] The amount of the repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, based on 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1). The amount of the repeating units derived from the cyclic hydrocarbon group-containing monomer (a3) ​​may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, based on 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1).

[0056] The amount of the repeating units derived from the crosslinkable monomer (a4) may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1). The amount of the repeating units derived from the crosslinkable monomer (a4) may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1).

[0057] The amount of the repeating units derived from the other monomer (a5) may be 2.5 parts by weight or more, 5 parts by weight or more, 12.5 parts by weight or more, 25 parts by weight or more, 35 parts by weight or more, or 45 parts by weight or more, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1). The amount of the repeating units derived from the other monomer (a5) may be 75 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 100 parts by weight of the repeating units derived from the hydrophobic monomer (a1).

[0058] The total of the repeating units derived from the hydrophobic monomer (a1) and the repeating units derived from the chloride monomer (a2) may be 50% by weight or more, 60% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more, based on the hydrocarbon-based acrylic polymer.

[0059] (Amount of hydrocarbon-based acrylic polymer) The amount of the hydrocarbon-based acrylic polymer may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more, relative to the water repellent composition. The amount of the hydrocarbon-based acrylic polymer may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less, relative to the water repellent composition.

[0060] [Hydrocarbon-based polyurethane] The hydrocarbon-based water-repellent resin may be a hydrocarbon-based polyurethane, which may be a polyurethane having a hydrocarbon group having 5 to 40 carbon atoms.

[0061] A hydrocarbon-based polyurethane having a hydrocarbon group having 5 to 40 carbon atoms can be produced by reacting an isocyanate group-containing compound (for example, a monoisocyanate or polyisocyanate, specifically a diisocyanate) with a hydroxyl group-containing compound having a hydrocarbon group having 5 to 40 carbon atoms. The reaction can be carried out, for example, at 80°C for 1 hour or more.

[0062] The isocyanate group-containing compound is not particularly limited, and examples thereof include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, araliphatic polyisocyanate compounds, and modified products of these isocyanate compounds. These compounds may also be used in combination of two or more. The isocyanate group-containing compound is preferably an aliphatic polyisocyanate compound, an aromatic polyisocyanate compound, or a modified product of these isocyanate compounds. The isocyanate group-containing compound is not particularly limited, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and modified polyisocyanates such as dimers and trimers thereof. Commercially available products such as "DESMODUR N-100" (manufactured by Bayer, product name), "Duranate THA-100" (manufactured by Asahi Kasei Corporation, product name), and "Duranate 24A-100" (manufactured by Asahi Kasei Corporation, product name) can be used.

[0063] Examples of aliphatic polyisocyanate compounds that can be used include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate. These may be used alone or in combination of two or more.

[0064] Examples of alicyclic polyisocyanate compounds that can be used include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, etc. These may be used alone or in combination of two or more.

[0065] Examples of aromatic polyisocyanate compounds that can be used include dialkyldiphenylmethane diisocyanate, tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (monomeric MDI), polymethylene polyphenyl polyisocyanate (polymeric MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate. These may be used alone or in combination of two or more.

[0066] Examples of aromatic aliphatic polyisocyanate compounds that can be used include xylylene diisocyanate, tetraalkyldiphenylmethane diisocyanate, α,α,α,α-tetramethylxylylene diisocyanate, etc. These may be used alone or in combination of two or more.

[0067] Examples of modified polyisocyanate compounds that can be used include isocyanurate modified compounds, biuret modified compounds, adduct modified compounds, carbodiimide modified compounds, bifunctional modified compounds, etc. These may be used alone or in combination of two or more.

[0068] Examples of hydroxyl group-containing compounds having a hydrocarbon group with 5 to 40 carbon atoms include hydroxyl group-containing compounds (monohydric alcohol derivatives or monocarboxylic acid derivatives) such as hydrocarbon group-containing monoalcohols and hydrocarbon group-containing monocarboxylic acids; and hydroxyl group-containing compounds (polyhydric alcohol derivatives or polycarboxylic acid derivatives) in which a hydrocarbon group with 5 to 40 carbon atoms has been introduced into a polyhydric alcohol or polycarboxylic acid such as sorbitan, citrate, and pentaerythritol. The hydroxyl group-containing compounds having a hydrocarbon group with 5 to 40 carbon atoms have at least one hydroxyl group (for example, one, two, or three).

[0069] Preferred examples of the hydroxyl group-containing compound having a hydrocarbon group having 5 to 40 carbon atoms include polyhydric alcohol derivatives or polycarboxylic acid derivatives of sorbitan (1a), citrate (1b), and pentaerythritol (1c) represented by the following formulae: TIFF0007824536000004.tif11192 [wherein each R is independently -H, -R 1 , -C(O)R 1 , -(CH2CH2O) n (CH(CH3)CH2O) m R 2 , or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R 1 and each n is independently 0 to 20; Each m is independently 0 to 20, m+n is greater than 0, Each R 1 are independently a hydrocarbon group having 5 to 40 carbon atoms, optionally containing at least one unsaturated bond, Each R 2 are independently —H or a hydrocarbon group having 5 to 40 carbon atoms and optionally containing at least one unsaturated bond; Each R 3 are independently -H, -R 1 , -C(O)R 1 , -(CH2CH2O) n' (CH(CH3)CH2O) m' R 2 , or -(CH2CH2O) n' (CH(CH3)CH2O) m' C(O)R 1 and Each R 4 are independently -H, a hydrocarbon group having 5 to 40 carbon atoms optionally containing at least one unsaturated bond, or a combination thereof; -(CH2CH2O) n' (CH(CH3)CH2O) m' R 2 ; or -(CH2CH2O) n' (CH(CH3)CH2O)m' C(O)R 1 ; and each n' is independently 0 to 20; each m' is independently 0 to 20; m'+n' is greater than 0, Each R 19 -H, -C(O)R 1 , or -CH2C[CH2OR]3. It is a compound represented by the formula:

[0070] When the compound has formula (Ia), at least one of R or R 2 is -H, When the compound has formula (Ib), at least one R 2 , R 3 or R 4 is -H, When the compound has formula (Ic), at least one R 19 or provided that R is —H.

[0071] Specific examples of the hydroxyl group-containing compound having a hydrocarbon group having 5 to 40 carbon atoms include sorbitan monocarboxylate, sorbitan dicarboxylate, sorbitan tricarboxylate, monoalkyl citrate, dialkyl citrate, trialkyl citrate, pentaerythritol monocarboxylate, pentaerythritol dicarboxylate, and pentaerythritol tricarboxylate. The carboxylate is preferably stearate or behenate. The hydrocarbon group is preferably alkyl, and preferred examples of alkyl include stearyl and behenyl.

[0072] The hydrocarbon-based polyurethane may be a dendritic polymer compound (dendrimer) having a radial and regularly branched structure from the center. The polyurethane obtained by the above reaction can be a dendritic polymer compound (dendrimer).

[0073] For hydrocarbon-based polyurethanes, reference can be made to the descriptions in WO2014 / 160906, WO2016 / 049278, etc.

[0074] (amount of hydrocarbon-based polyurethane) The amount of hydrocarbon-based polyurethane may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more, based on the water repellent composition. The amount of hydrocarbon-based polyurethane may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less, based on the water repellent composition.

[0075] [Other hydrocarbon-based water-repellent resins] The hydrocarbon-based water-repellent resin is not limited to a hydrocarbon-based acrylic polymer or a hydrocarbon-based polyurethane. Other hydrocarbon-based water-repellent resins can be used instead of or in addition to a hydrocarbon-based acrylic polymer or a hydrocarbon-based polyurethane. Examples of other hydrocarbon-based water-repellent resins include dendrimer-based resins having hydrocarbon groups at their terminals. Examples of dendrimer-based resins include the RUCO-DRY series manufactured by Rudolph (e.g., RUCO-DRY DHE, RUCO-DRY ECO, RUCO-DRY ECO PLUS).

[0076] [Hydrophilic particles] The water repellent composition of the present disclosure contains hydrophilic particles. Here, hydrophilicity refers to the property of particles easily dispersing in an aqueous solvent without agglomeration. For example, when 1.0 wt % of particle powder and an optional dispersant are added to an aqueous solvent, the mixture is stirred at 700 rpm for 10 minutes using a homomixer, and then allowed to stand for 1 hour, and no precipitation or aggregation of the particles is visually observed, the water repellent composition is deemed to have hydrophilicity. Furthermore, the particles contained in commercially available aqueous particle dispersions in which particles are dispersed in an aqueous solvent are also deemed to have hydrophilicity.

[0077] The hydrophilic particles may have hydrophilic groups on their surfaces. Examples of the hydrophilic groups include cationic groups, anionic groups, amino groups, and hydroxyl groups. The surfaces of the hydrophilic particles may be subjected to a hydrophilization treatment, but are generally not subjected to a hydrophobic treatment.

[0078] The hydrophilic particles are not particularly limited as long as they are hydrophilic. Examples include inorganic particles (e.g., inorganic oxide particles) such as alumina, silica, and titania, and organic particles such as latex, acrylic, and nylon. Among these, inorganic particles are preferred due to their ease of handling, and at least one selected from the group consisting of silica and alumina is particularly preferred. Examples of commercially available products include silicon oxide particles such as "Snowtex ST-OYL," "Snowtex ST-AK-L," and "Snowtex ST-AK-YL" (all manufactured by Nissan Chemical Industries Co., Ltd.), titanium oxide particles such as "TA300" and "TA300D" (both manufactured by Fuji Titanium Industry Co., Ltd.), and aluminum oxide particles such as "TM-5D" (manufactured by Taimei Chemical Industry Co., Ltd.). These may be used alone or in combination.

[0079] (Average primary particle size) The average primary particle diameter of the hydrophilic particles may be 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, or 30 nm or more. The average primary particle diameter of the hydrophilic particles may be 600 nm or less, 400 nm or less, 200 nm or less, 100 nm or less, 40 nm or less, 37.5 nm or less, 35 nm or less, 32.5 nm or less, 30 nm or less, 27.5 nm or less, 25 nm or less, or 22.5 nm or less, preferably 40 nm or less. By being within the above range, water repellency, slip resistance, and storage stability can be excellently combined. The average primary particle diameter can be measured using a microscope (scanning electron microscope or transmission electron microscope). Specifically, an arbitrary position on the fabric is observed from above using a microscope at an arbitrary magnification. Next, if the particle shape is spherical, the diameter is considered to be the particle diameter (particle size). If the particle shape is non-spherical, the average of the longest and shortest diameters is considered to be the particle size (particle size). The particle size of all particles present in the field of view is measured, and then the field of view is moved and the particle size is measured again. This process is repeated until particle sizes are measured at 10 or more points, and the average value is taken as the average primary particle size.

[0080] (Turbidity) The turbidity of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 may be 0.1 ppm or more, 1 ppm or more, 5 ppm or more, or 10 ppm or more. The turbidity of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 may be 200 ppm or less, 100 ppm or less, 50 ppm or less, 20 ppm or less, 10 ppm or less, 5 ppm or less, or 2.5 ppm or less, preferably 20 ppm or less. By being in the above range, water repellency, slip resistance, and storage stability can be excellently combined. The turbidity can be calculated based on a calibration curve (0 to 1000 ppm range) prepared using an integrating sphere turbidimeter PT200 manufactured by Nitto Seiko Analytech Co., Ltd., based on JIS K0101, Drinking Water Testing Method, using the turbidity of a standard sample, kaolin (pigment), based on the calibration curve.

[0081] (zeta potential)

[0082] The zeta potential of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 may be -20 mV or higher, -10 mV or higher, 0 mV or higher, +5 mV or higher, +10 mV or higher, or +20 mV or higher, preferably 0 mV or higher or +10 mV or higher. The zeta potential of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 may be +200 mV or lower, +150 mV or lower, +100 mV or lower, +50 mV or lower, +30 mV or lower, +100 mV or lower, +10 mV or lower, or +5 mV or lower, preferably +100 mV or lower. Having a turbidity within the above range ensures good water repellency, slip resistance, and storage stability. The zeta potential can be measured, for example, using a commercially available zeta potential measuring device.

[0083] (amount of hydrophilic particles) The amount of hydrophilic particles may be 0.01 wt% or more, 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, 1 wt% or more, 2 wt% or more, 3 wt% or more, or 5 wt% or more, preferably 0.5 wt% or more, and particularly preferably 2 wt% or more, based on the total amount of the hydrocarbon-based water-repellent resin and the hydrophilic particles. The amount of hydrophilic particles may be 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, 3 wt% or less, or 2 wt% or less, preferably 12 wt% or less, based on the total amount of the hydrocarbon-based water-repellent resin and the hydrophilic particles. When the amount of hydrophilic particles is within the above range, water repellency, slip resistance, and storage stability can be excellently achieved. When the amount of hydrophilic particles is 2 wt% or more based on the total amount of the hydrocarbon-based water-repellent resin and the hydrophilic particles, slip resistance can be particularly excellent.

[0084] [silicone] The water repellent composition of the present disclosure preferably contains silicone in addition to the hydrocarbon-based water repellent resin, which can provide a good combination of water repellency, slip resistance, and storage stability.

[0085] Silicones have the formula: (R53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )2-O-] b -Si(R 53 )3(S1) [In the formula, R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an alkoxy group having 1 to 40 carbon atoms; R 53 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a saturated hydrocarbon group having 1 to 40 carbon atoms; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200. The polymer may be represented by the formula:

[0086] R 51 and R 53 In the above, the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 40 carbon atoms may be unsubstituted or substituted. R 51 and R 53 Specific examples of R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; a phenyl group, a tolyl group, a naphthyl group, or a group in which some or all of the hydrogen atoms bonded to these groups have been substituted with a halogen atom, an amino group, a cyano group, or the like. 51 and R 53 is preferably a methyl group or an ethyl group. R 51 and R 53 In the above formula, the alkoxy group having 1 to 40 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 40 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0087] The silicone may have at least one long chain hydrocarbon group. For example, R 51 At least one of R 53 At least one of or R 51 and R 53 may be a long chain hydrocarbon group, and 51 At least one (for example, one) of the above may be a long-chain hydrocarbon group. Here, the long-chain hydrocarbon group may be a saturated hydrocarbon group having 6 or more, 10 or more, 15 or more, or 20 or more carbon atoms, preferably 10 or more or 23 or more carbon atoms. Here, the hydrocarbon group may be linear or branched, and is preferably an alkyl group. Specific examples of hydrocarbon groups include a hexyl group (6 carbon atoms), an octyl group (8 carbon atoms), a lauryl group (12 carbon atoms), a myristyl group (14 carbon atoms), a stearyl group (18 carbon atoms), a behenyl group (22 carbon atoms), a tricosyl group (23 carbon atoms), a lignoceryl group (tetracosyl group, 24 carbon atoms), a cellotyl group (hexacosyl group, 26 carbon atoms), a monthyl group (octacosyl group, 28 carbon atoms), a melissyl group (triacontane group, 30 carbon atoms), and a dotriacontane group (32 carbon atoms).

[0088] The long-chain hydrocarbon group R is preferred because it is easy to produce industrially and is readily available. 51 and R 53 Other than R 51 and R 53 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0089] a is an integer of equal to or greater than 0. In terms of ease of industrial production and availability, a may be equal to or less than 40, equal to or less than 30, or equal to or less than 20, and is preferably equal to or less than 30.

[0090] The sum of a and b is 5 to 200. From the viewpoints of ease of industrial production, availability, and handling, the sum of a and b is preferably 10 to 100, and more preferably 40 to 60. a may be 0 to 150, for example, 1 to 100. The lower limit of b may be 1, 2, or 3, and the upper limit of b may be 150, 10, or 5.

[0091] When a or b is 2 or more, multiple R 51 and R 52 may be the same or different.

[0092] R 51 and R 53 group (for example, when represented by the following formula (S2), R 51 and R 52 Group and R 53 It is preferred that 50 mol % or more of the total of the alkyl groups) are methyl groups.

[0093] The order of the repeating units bound by a or b is not limited to the order shown in the chemical formula, and can be any order. That is, the silicone may be a random polymer or a block polymer.

[0094] For example, silicones may have the formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )(R 52 )-O-] b -Si(R 53 )3(S2) [In the formula, R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group; R 52 each independently represents a long chain hydrocarbon group; R 53 each independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group; a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200. The polymer may be represented by the formula: In formula (S2), R 51 and R 53may have an alkyl group having 3 to 40 carbon atoms or an unsaturated hydrocarbon group having 6 to 40 carbon atoms (for example, a hydrocarbon group having an aromatic ring), but it is preferable that it does not have these groups.

[0095] Examples of silicones are: TIFF0007824536000005.tif2371 [wherein a represents an integer of 0 to 150; b represents an integer from 1 to 150; (a+b) is 5 to 200, and n is an integer of 1 to 36 (preferably n is a long-chain hydrocarbon group).

[0096] Silicone can be synthesized by a conventionally known method, for example, by subjecting silicone having a SiH group to a hydrosilylation reaction with an α-olefin.

[0097] Examples of silicones containing SiH groups include methylhydrogensilicones with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicones are preferred due to their ease of industrial production and availability. Hydrogensilicones (e.g., methylhydrogensilicones) are polydiorganosiloxanes in which a portion of the side chain is substituted with hydrogen, and the hydrogen atoms are directly bonded to silicon atoms. When using hydrogensilicones, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. Metal salts of organic acids are preferred as catalysts, and fatty acids are preferred as organic acids. From the perspective of safety, zinc stearate or the like can be used. The catalyst is preferably used in an amount of 10 to 40% relative to the methylhydrogensilicone, as this enhances its effectiveness. Two or more of amino-modified, epoxy-modified, carboxy-modified, and methylhydrogensilicones may be mixed. All of these silicones have reactive groups, and it is preferable that they have film-forming properties. The term "film-forming ability" refers to the ability of the silicone to form a solid film, rather than an oil or gel film, after being attached to the surface of a fiber in an emulsion state.

[0098] α-olefins are compounds from which long-chain hydrocarbon groups in silicones are derived. Specific examples of α-olefins include 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacontene, and 1-dotriacontene. The hydrosilylation reaction may be carried out by reacting the above-mentioned silicone having an SiH group with an α-olefin in stages or all at once, if necessary in the presence of a catalyst.

[0099] The amounts of the SiH group-containing silicone and the α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight or number average molecular weight of the SiH group-containing silicone.

[0100] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, with platinum compounds being preferred, such as platinum(IV) chloride.

[0101] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10 to 200° C., preferably 50 to 150° C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150° C. The hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction proceeds without a solvent, but a solvent may also be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0102] (reactive silicone) The silicone may include a reactive silicone. Examples of reactive silicones include polysiloxanes having reactive groups in the side chain, one end, both ends, or the side chain and both ends. However, from the viewpoint of achieving excellent slip resistance and water repellency at the same time, polysiloxanes having reactive groups in the side chain and / or both ends may also be used. The reactive silicone is not particularly limited as long as it has a reactive group in the molecule, and examples include amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, and hydrogen-modified silicone. The reactive silicone may be one in which one or more substituents in the above formula (S1) or formula (S2) have been replaced with a reactive group.

[0103] Examples of amino-modified silicones include those having a structure in which an amino group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has 2 or more carbon atoms. The divalent aromatic group preferably has 6 or more carbon atoms. The amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group. Examples of organic groups having an amino group bonded thereto include the following: 2-aminoethyl group, N-methyl-2-aminoethyl group, N,N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N,N-diethyl-2-aminoethyl group, N,N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl-3-aminopropyl group, N,N-dimethyl-3-aminopropyl group, N-ethyl-3-aminopropyl group, N,N-diethyl-3-aminopropyl group, and N,N-methylethyl-3-aminopropyl group. These functional groups may be located on the side chains of the polysiloxane or at the terminals.

[0104] Epoxy-modified silicones include those having a structure in which an epoxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Typically, the bond between the organic group and the epoxy group is in the form of a glycidyl ether. Examples of such functional groups include 3-glycidoxypropyl and 2-glycidoxyethyl groups. These functional groups may be present on the side chain or at the terminal of the polysiloxane.

[0105] Examples of carboxy-modified silicones include those having a structure in which a carboxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. The alkylene group preferably has two or more carbon atoms. The divalent aromatic group preferably has six or more carbon atoms. Examples of such functional groups include a 3-carboxypropyl group and a 2-carboxyethyl group. These functional groups may be present on the side chain of the polysiloxane or at the terminal.

[0106] (amount of silicone) The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin. The amount of silicone may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin.

[0107] [wax] The water repellent composition of the present disclosure preferably contains a wax in addition to the hydrocarbon-based water repellent resin. By containing a wax, water repellency, slip resistance, and storage stability can be satisfactorily achieved. The water repellent composition of the present disclosure may contain both a silicone and a wax, or may contain only one of a silicone and a wax.

[0108] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, animal and vegetable wax, and mineral wax. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane), and normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane). The number of carbon atoms in the compound constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, or 300 to 1000. These may be used alone or in combination of two or more.

[0109] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0110] (amount of wax) The amount of wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin. The amount of wax may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin.

[0111] [Liquid medium] The water repellent composition contains a liquid medium. The liquid medium is water, an organic solvent, or a mixture of water and an organic solvent. A mixture of water and an organic solvent is preferred. By including an organic solvent, the water repellent composition can have a good combination of water repellency, slip resistance, and storage stability.

[0112] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., polyhydric alcohols such as alcohols, glycol-based solvents, ethers of polyhydric alcohols (e.g., monoethers), etc.). These may be used alone or in combination.

[0113] (amount of liquid medium) The amount of the liquid medium may be 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 97% by weight or more, based on the water repellent composition. The amount of the liquid medium may be 99.9% by weight or less, 99% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less, based on the water repellent composition.

[0114] The amount of the organic solvent may be 0.5% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, 5% by weight or more, 7.5% by weight or more, 10% by weight or more, 12.5% ​​by weight or more, 15% by weight or more, or 20% by weight or more, based on the water repellent composition. The amount of the organic solvent may be 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less, based on the water repellent composition.

[0115] The amount of the organic solvent may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 40% by weight or more, based on the liquid medium. The amount of the organic solvent may be 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, 12.5% ​​by weight or less, 7.5% by weight or less, or 5.0% by weight or less, based on the liquid medium.

[0116] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin. The amount of the organic solvent may be 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin.

[0117] The amount of the organic solvent may be 0.5 parts by weight or more, 1 part by weight or more, 1.5 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, or 40 parts by weight or more, relative to 100 parts by weight of water. The amount of the organic solvent may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 25 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of water.

[0118] [Organic acid] The water repellent composition may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one organic acid may be used, or two or more organic acids may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0119] (amount of organic acid) The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin. The amount of organic acid may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin. The amount of organic acid may be adjusted so that the pH of the water repellent composition is 3 to 10, for example, 5 to 9, particularly 6 to 8. The water repellent composition may be acidic (pH 7 or less, for example, 6 or less).

[0120] [Dispersant] The water repellent composition may contain a dispersant to enhance the dispersibility of the hydrophilic particles. The dispersant may be a polymer dispersant, preferably a hydrophilic polymer dispersant. Examples of dispersants that can be used include polyvinylpyrrolidone, polyvinyl alcohol, polyglycerin, and polyacrylates. These may be used alone or in combination.

[0121] (amount of dispersant) The amount of the dispersant may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrophilic particles. The amount of the dispersant may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the hydrophilic particles.

[0122] [Surfactants] The water repellent composition preferably contains a surfactant. In the water repellent composition, the surfactant may contain a nonionic surfactant. By containing a surfactant, water repellency, slip resistance, and storage stability can be satisfactorily achieved. Furthermore, the surfactant may contain one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

[0123] (nonionic surfactant) Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.

[0124] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0125] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0126] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0127] An example of an alkanolamide is formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamine. An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0128] The polyhydric alcohol may be a dihydric to pentahydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (having, for example, 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0129] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100. The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

[0130] The nonionic surfactant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct moiety and the polyalkylene glycol moiety is polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic surfactant preferably has a structure that does not contain an aromatic group in view of environmental issues (biodegradability, environmental hormones, etc.).

[0131] The nonionic surfactants are those having the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, R 2 are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number greater than or equal to 2, q is a number of 0 or 1 or more. The compound may be a compound represented by the formula:

[0132] R 1 R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. 1 Preferred specific examples include a lauryl group, a tridecyl group, and an oleyl group. R 2 Examples of the alkyl group include a propylene group and a butylene group. In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among these, an oxypropylene chain is preferred.

[0133] Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) Thiol, Sorbitan Mono Fatty Acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amines and the like.

[0134] The proportion of the polyoxyethylene block can be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic surfactant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. An example of a compound having an HLB of less than 15 is a sorbitan fatty acid ester. An example of a compound having an HLB of 15 or more is a polyoxyethylene alkyl ether. The weight ratio of the compound having an HLB of less than 15 to the compound having an HLB of 15 or more may be 90:10 to 20:80, for example 85:15 to 55:45. The nonionic surfactant may be used alone or in combination of two or more kinds.

[0135] (cationic surfactant) The cationic surfactant is preferably a compound having no amide group.

[0136] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene adduct ammonium salt. Specific examples of the cationic surfactant include, but are not limited to, amine salt surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, and quaternary ammonium salt surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.

[0137] Preferred examples of the cationic surfactant are: R 21 -N + (-R 22 )(-R 23 )(-R 24 ) X - [In the formula, R 21 , R 22 , R 23 and R 24 is a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. is a compound of R 21 , R 22 , R 23 and -R 24 Specific examples of X include alkyl groups (for example, methyl, butyl, stearyl, and palmityl groups). Specific examples of X include halogens (for example, chlorine) and acids (for example, hydrochloric acid and acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0138] Preferably, the cationic surfactant is an ammonium salt. The cationic surfactant has the formula: R 1 p - N + R 2 q X - [In the formula, R 1 is C12 or higher (e.g., C12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH3 and C2H5 are particularly preferred), X is a halogen atom (for example), a C1-C4 fatty acid base, p is 1 or 2, q is 2 or 3, and p+q=4. R 1 may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0139] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0140] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid surfactants, phosphoric acid mono- or diester surfactants, and sulfosuccinate esters.

[0141] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0142] The surfactant may be a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant, each of which may be one type or a combination of two or more types.

[0143] (amount of surfactant) The amount of the surfactant may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrophilic particles. The amount of the surfactant may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the hydrophilic particles. The amount of the cationic surfactant may be 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, based on the total amount of surfactants. The weight ratio of the nonionic surfactant to the cationic surfactant is preferably 95:5 to 20:80, more preferably 85:15 to 40:60. The amount of the cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight, relative to 100 parts by weight of the water-repellent resin. The total amount of the surfactants may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, relative to 100 parts by weight of the water-repellent resin.

[0144] [Hardening agent] The water repellent composition may contain a curing agent (an active hydrogen reactive compound or an active hydrogen-containing compound). After the hydrocarbon-based water repellent resin is obtained by polymerization, the curing agent may be added to the water repellent composition.

[0145] The curing agent (crosslinking agent) in the water repellent composition can satisfactorily cure the hydrocarbon-based water repellent resin. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of the hydrocarbon-based water repellent resin. Examples of the active hydrogen-reactive compound include polyisocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0146] The curing agent may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.

[0147] Examples of aliphatic polyisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate, Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0148] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0149] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0150] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0151] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0152] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent.The use of a blocked polyisocyanate compound is preferable for reasons such as its relative stability in an aqueous solution and its usability in the same aqueous solution as the water repellent composition.

[0153] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination.

[0154] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include chloromethyl polystyrene. The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid and (poly)methacrylic acid.

[0155] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of the hydrazide compound include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0156] (Amount of hardener) The amount of the curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin. The amount of the curing agent may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin.

[0157] [Other ingredients] The water repellent composition may contain other components in addition to the above components. After producing the hydrocarbon-based water repellent resin, other components may be added. Examples of other components include water and / or oil repellents, antislip agents, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above ingredients, other ingredients may include texture adjusters, fabric softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, anti-wrinkle agents after washing, shape retention agents, drape retention agents, ironing improvers, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty Chemicals' Chinopal CBS-X), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, and stain removers. Fiber surface modifiers include enzymes such as cellulase, amylase, protease, lipase, and keratinase, and agents that can impart silk texture and functionality such as foam inhibitors and moisture absorption and release properties include silk protein powder, surface-modified products, and emulsified dispersions thereof.Specific examples include K-50, K-30, K-10, A-705, S-702, L-710, and FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos), and stain inhibitors such as nonionic polymeric compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, such as FR627 manufactured by GOO Chemical Industry and SRC-1 manufactured by Clariant Japan.These may be used alone or in combination.

[0158] (antistatic agent) Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, and nonionic antistatic agents such as aminoalcohols and their derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. Ion-conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ion-conductive groups may also be used. These may be used alone or in combination.

[0159] (preservatives) Preservatives are mainly used to enhance antiseptic and bactericidal properties and maintain antiseptic properties during long-term storage. Examples of preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The content of the preservative is preferably 0.0001 to 1 wt % relative to the total weight of the water repellent composition. When the content of the preservative is equal to or greater than the lower limit of the above range, the effect of adding the preservative can be sufficiently obtained, and when it is equal to or less than the upper limit, the storage stability of the water repellent composition is good.

[0160] (ultraviolet absorber) An ultraviolet absorber is a chemical agent that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0161] (Antibacterial agent) Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors caused by microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0162] (Deodorant) Examples of deodorizing agents include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (e.g., zinc complex of trisodium methylglycinediacetate described in WO 2012 / 090580).

[0163] (fragrance) The fragrance is not particularly limited, and lists of usable fragrance raw materials can be found in various documents, such as "Perfume and Flavor Chemicals," Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994); "Synthetic Fragrances: Chemistry and Product Knowledge," by Genichi Indo, The Chemical Daily (1996); "Perfume and Flavor Materials of Natural Origin," by Steffen Arctander, Allured Pub. Co. (1994); "Encyclopedia of Fragrances," edited by the Japan Fragrance Manufacturers Association, Asakura Shoten (1989); "Perfumery Material Performance V.3.3," by Boelens Aroma Chemical Information Service (1996); and "Flower Oils and Floral Compounds in Perfumery," by Danute Lajaujis Anonis, Allured Pub. Co. (1993), each of which is incorporated herein by reference.

[0164] (amount of other ingredients) The amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin. The amount of the other components may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the hydrocarbon-based water-repellent resin.

[0165] <Production of Water Repellent Composition> The method for producing the water repellent composition may include a step of reacting (polymerizing) a hydrocarbon-based water repellent resin raw material in a medium (e.g., a liquid medium) containing the hydrocarbon-based water repellent resin raw material and the hydrophilic particles to obtain the hydrocarbon-based water repellent resin. Alternatively, the method for producing the water repellent composition may include a step of adding a powder of hydrophilic particles to a solution or dispersion of a water repellent resin, or a step of mixing a solution or dispersion of a water repellent resin with a dispersion of hydrophilic particles.

[0166] In order for the water repellent composition to exhibit high water repellency, it is preferable to subject the water repellent composition to ultrasound (ultrasonic treatment). It is preferable to perform the ultrasonic treatment immediately before applying it to the object to be treated. For example, the water repellent composition is applied to the object to be treated 1 minute to 1 hour after the ultrasonic treatment. The ultrasonic treatment can be performed by subjecting the water repellent composition to ultrasound. There are no particular restrictions on the ultrasonic generator, but an output of 500 W or more, for example, 500 to 2000 W, is preferred in terms of efficient mixing. The ultrasonic treatment time may be 0.5 to 60 minutes. For example, a uniform water repellent composition can be obtained by treating with a 500 W ultrasonic generator for 10 minutes.

[0167] Without being bound by theory, it is believed that the agglomerated particles formed by aggregation of primary particles are separated into primary particles by ultrasonic treatment (ultrasonic cleaning), and the primary particles have an appropriate particle size, resulting in high water repellency.

[0168] In general, the solution or dispersion of the water-repellent resin is a solution or dispersion of a polymer having a hydrocarbon group.

[0169] Polymers having hydrocarbon groups can be produced by any of the usual polymerization methods, and the polymerization reaction conditions can be selected arbitrarily, such as solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0170] In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of the monomers.

[0171] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, relative to 100 parts by weight of the total of the monomers.

[0172] Emulsion polymerization involves emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, purging with nitrogen, and then polymerizing the mixture at 50-80°C for 1-20 hours with stirring. Polymerization initiators include water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01-10 parts by weight per 100 parts by weight of monomer.

[0173] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to polymerize the monomer by microparticulating it in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0174] The water-soluble organic solvent may be any of the organic solvents described above. Examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0175] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomers.

[0176] The water repellent composition may be in the form of a solution, an emulsion (especially an aqueous dispersion), or an aerosol.

[0177] <Uses of water repellent composition> Examples of applications of the water repellent composition according to the present disclosure include an external treatment agent (surface treatment agent) or an internal treatment agent, a repellent (a water repellent, an oil repellent, or a water and oil repellent, etc., particularly a water repellent), an antifouling agent, a stain release agent, a stripping agent, a release agent (an external release agent or an internal release agent), and the like.

[0178] <Manufacturing method of treated products> A method of making a treatment product in the present disclosure includes treating a substrate with a water repellent composition.

[0179] [Processed products] Substrates that can be treated with the water repellent composition of the present disclosure include textiles, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Various examples of textiles can be mentioned. Examples include natural fibers of animal and plant origin, such as cotton, linen, wool, and silk; synthetic fibers, such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers, such as rayon and acetate; inorganic fibers, such as glass fiber, carbon fiber, and asbestos fiber; and mixtures of these fibers. As an example of a substrate that can be treated with the water repellent composition, a woven or knitted fabric will be described in detail.

[0180] (woven and knitted fabrics) ·Method of manufacturing knitted fabrics The woven or knitted fabric can be obtained by weaving or knitting the mixed and intertwined yarn to obtain a grey fabric, and then post-processing and water-repellent finishing the grey fabric. The weaving and knitting can be carried out using a known loom or knitting machine, and the preparation step prior to the weaving and knitting can also be carried out using known equipment.

[0181] In post-processing, the grey fabric is first scoured and relaxed. Scouring and relaxation can be carried out at a temperature of 80 to 130°C using a continuous or batch method. Usually, it is preferable to carry out the process at a temperature of 100°C or less using a batch method, and it is particularly preferable to carry out the process using a high-pressure jet dyeing machine equipped with a jet nozzle.

[0182] After scouring and relaxing, the woven or knitted fabric is preset. Presetting is usually done by dry heat treatment at 170-200°C for 30-120 seconds using a pin tenter. After presetting, the fabric is dyed according to the usual method, and then a final setting is carried out if necessary.

[0183] After the post-processing, the woven or knitted fabric may be subjected to a water-repellent treatment. In the water-repellent treatment, first, an aqueous solution containing a water repellent (which may be the water repellent composition of the present disclosure) is prepared. Next, the aqueous solution is applied to the woven or knitted fabric after the post-processing using a padding method, a spray method, a kiss roll coater method, a slit coater method, or the like, and then dry heat treated at 105 to 190°C for 30 to 150 seconds. The aqueous solution may also contain a crosslinking agent, a softener, an antistatic agent, etc., as necessary. After the water-repellent treatment, the woven or knitted fabric may be calendered to further improve the water-repellent performance.

[0184] The woven and knitted fabrics are suitably used for clothing applications, particularly for uniforms, ladies' wear, and sportswear.

[0185] Laminated fabric The woven or knitted fabric of the present disclosure may be provided as a laminated fabric having a moisture-permeable waterproof layer on one side thereof. The moisture-permeable waterproof layer may be laminated directly onto the woven or knitted fabric, or may be laminated onto the woven or knitted fabric via an adhesive layer. When the laminated fabric of the present disclosure is used for clothing or the like, it is positioned so that the woven or knitted fabric side is exposed to rainwater or the like.

[0186] Breathable waterproof layer The moisture-permeable waterproof layer is a layer that covers one side of the woven or knitted fabric and is formed from a resin that has waterproof and moisture-permeable properties.

[0187] The moisture-permeable waterproof layer may be formed by applying a resin (the resin that constitutes the moisture-permeable waterproof layer) directly to the woven or knitted fabric, or may be laminated on one side of the woven or knitted fabric via an adhesive layer, which will be described later. In the present disclosure, a mixed fiber interlaced yarn having minute protrusions due to loops or slack is used in the woven or knitted fabric. Therefore, the protrusions are firmly entangled with the adhesive layer or the moisture-permeable waterproof layer, thereby creating an anchoring effect, making it even more difficult for the woven or knitted fabric and the moisture-permeable waterproof layer to peel off. If a normal woven or knitted fabric (a woven or knitted fabric in which the above-mentioned protrusions are not sufficiently maintained on the surface) is used, the anchoring effect may not be fully exerted, and in such cases, the woven or knitted fabric and the moisture-permeable waterproof layer tend to peel off easily.

[0188] The resin constituting the moisture-permeable waterproof layer is not particularly limited, but is preferably composed primarily of polyurethane resin, and preferably contains polyurethane resin at a ratio of 80% by weight or more. Polyurethane resins are generally suitable for forming resin layers that are moisture-permeable and waterproof. In particular, microporous types are preferred in terms of moisture permeability, but if the product is expected to be exposed to rain for long periods of time or to be used repeatedly through washing, etc., non-porous moisture-permeable urethane may be used instead of the microporous type.

[0189] As the polyurethane resin, a conventionally known resin obtained by reacting a polyisocyanate component with a polyol component can be used.

[0190] The moisture-permeable waterproof layer may have a microporous structure or a non-porous structure. When the moisture-permeable waterproof layer has a microporous structure, the layer may contain an inorganic fine powder to ensure the desired moisture permeability.

[0191] Examples of inorganic fine powders include fine powders made of silicon dioxide, aluminum dioxide, titanium dioxide, etc. The average primary particle size of the inorganic fine powder is preferably about 7 to 40 nm. The content of the inorganic fine powder is preferably 3 to 50 wt %, and more preferably 5 to 50 wt %, of the total amount of the moisture-permeable waterproof layer.

[0192] The thickness of the moisture-permeable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. A thickness within this range provides an excellent balance between waterproofness and moisture permeability, and is also advantageous in terms of texture and tear strength.

[0193] ·Adhesive layer The laminated fabric preferably includes an adhesive layer. That is, the woven / knitted fabric and the moisture-permeable waterproof layer are preferably laminated via an adhesive layer. The reason for this is described below. In the present disclosure, as described above, the woven / knitted fabric has minute protrusions on the surface caused by loops or slack. Therefore, the protrusions are firmly entangled with the adhesive layer, which produces an anchor effect, making it even more difficult for the woven / knitted fabric and the moisture-permeable waterproof layer to peel off.

[0194] Furthermore, when a moisture-permeable waterproof layer is directly laminated to the above-mentioned woven or knitted fabric, for example, by a coating method, the protrusions on the surface of the woven or knitted fabric may penetrate the moisture-permeable waterproof layer, resulting in the formation of pinholes and reduced water resistance and strength. There is also a concern that the coating may not be uniform, resulting in uneven thickness of the moisture-permeable waterproof layer. If attempts are made to smooth the surface of the woven or knitted fabric by, for example, calendaring to prevent this, the protrusions or air-retaining layer may be reduced, resulting in reduced water repellency. Therefore, in the present disclosure, it is preferable to laminate the woven or knitted fabric and the moisture-permeable waterproof layer via an adhesive layer.

[0195] The type of adhesive that constitutes the adhesive layer is not particularly limited, but it is preferable that it is one that has excellent compatibility with the moisture-permeable waterproof layer. For example, if a resin containing polyurethane resin as the main component is selected as the resin that constitutes the moisture-permeable waterproof layer, it is preferable to use an adhesive layer made of a polyurethane-based adhesive. The polyurethane-based adhesive may be any of ether-based, ester-based, polycarbonate-based, etc., but from the viewpoint of imparting excellent moisture permeability, an ether-based adhesive is preferable.

[0196] The adhesive layer may be formed over the entire surface of one side of the woven or knitted fabric, or may be formed in a pattern from the viewpoint of moisture permeability, texture, etc. The pattern shape is not particularly limited, but examples include dots, lines, a grid, a checkerboard pattern, a tortoiseshell pattern, etc., and it is preferable that any of these patterns be uniformly arranged over the entire surface.

[0197] The thickness of the adhesive layer is preferably about 10 to 100 μm, more preferably 20 to 80 μm. If the thickness is less than 10 μm, it is difficult to obtain a durable laminated fabric even if the adhesive occupies a large area, and if it exceeds 100 μm, not only will the manufacturing cost increase but further adhesiveness will also tend to be difficult to expect, both of which are undesirable.

[0198] Lining fabric In the laminated fabric of the present disclosure, a lining fiber fabric may be laminated on the moisture-permeable waterproof layer (on the side of the moisture-permeable waterproof layer opposite to the side on which the woven or knitted fabric of the present disclosure is laminated). The lining fiber fabric can protect the moisture-permeable waterproof layer, thereby providing even better waterproofness (water pressure resistance) and strength. Furthermore, by laminating the lining fiber fabric, the overall elongation of the laminated fabric can be suppressed, which can prevent the protruding parts of the mixed fiber composite yarn from being pulled by elongation of the woven or knitted fabric due to tension during the finishing process after lamination or when worn, and thus can maintain the above-mentioned water repellency at a higher level. Furthermore, laminating the lining fiber fabric can further improve water repellency.

[0199] Examples of lining fiber fabrics include various woven and knitted fabrics. Knitted fabrics are particularly suitable because, compared to woven fabrics, the constituent yarns tend to protrude from the surface, resulting in an uneven surface, and the knitted fabric exhibits a stronger anchoring effect, making it less likely to peel from the moisture-permeable waterproof layer. Tricot knitted fabrics are particularly preferred because they have less stretchability than knitted fabrics with other structures, preventing excessively large stitch gaps and enabling more effective water repellency. Tricot knitted fabrics are also preferred because they can be knitted to produce long gray fabrics with fewer seams, allowing them to be evenly layered on the moisture-permeable waterproof layer.

[0200] The material of the fibers constituting the lining fiber fabric is not particularly limited and can be selected as appropriate, but nylon fiber is preferred. This is because acid dyes are generally used in nylon fibers, which makes it less likely for the disperse dye to migrate and sublimate into the moisture-permeable waterproof layer, a problem that occurs with polyester fibers, etc., which use disperse dyes. The form (long fiber, short fiber, or spun yarn) or fineness of the fibers constituting the lining fiber fabric are not particularly limited and can be selected as appropriate as long as the effects of the present disclosure are not impaired.

[0201] · Properties of laminated fabric The laminated fabric has excellent waterproofness. Suitable examples of waterproofness possessed by the laminated fabric of the present disclosure include a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) of, for example, 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more. The upper limit of the water level is not particularly limited, but examples include 50,000 mm or 25,000 mm.

[0202] The laminated fabric has excellent moisture permeability. A preferred example of the moisture permeability of the laminated fabric of the present disclosure is a moisture permeability of, for example, 10,000 g / m 2 as measured in accordance with JIS L 1099:2012 B-1 method (potassium acetate method). 2 24 hours or more, preferably 15,000 g / m 2 24 hours or more, more preferably 20,000 g / m 2 The upper limit of the moisture permeability is not particularly limited, but for example, 40,000 g / m 2 24h or 35,000g / m 2 ·24h·mm are examples.

[0203] In the laminated fabric, delamination between the woven / knitted fabric and the moisture-permeable waterproof layer is suppressed. In the laminated fabric of the present disclosure, a suitable example of the peel strength between the woven / knitted fabric and the moisture-permeable waterproof layer is, for example, 5 N / 2.54 cm or more, preferably 5 to 50 N / 2.54 cm, more preferably 6 to 30 N / 2.54 cm, and particularly preferably 9 to 25 N / 2.54 cm, as measured according to the method of JIS L 1089. To achieve the peel strength within the above range, for example, a woven / knitted fabric that has not been subjected to calendering may be used, or an adhesive layer may be provided.

[0204] ·Laminated fabric manufacturing method The method for producing the laminated fabric is not particularly limited, but examples thereof include the first and second production methods described below. First manufacturing method: The first manufacturing method includes a step of forming the moisture-permeable waterproof layer by applying a resin that constitutes the moisture-permeable waterproof layer to the surface of a woven or knitted fabric. Second manufacturing method: This method includes the steps of forming an adhesive layer on the woven or knitted fabric or the moisture-permeable waterproof layer, and bonding the woven or knitted fabric and the moisture-permeable waterproof layer together via the adhesive layer.

[0205] It is preferable that the woven / knitted fabric used in the laminated fabric (i.e., the woven / knitted fabric of the present disclosure described above) maintain as many protrusions on the fabric surface as possible. For example, if the woven / knitted fabric is subjected to a calendering process to facilitate coating or other processes, the fine protrusions of the mixed / entangled yarns are crushed to form a flat surface, which may prevent a specific water droplet rolling angle from being achieved. Furthermore, if the calendering process is performed, the air retention layer described above may not be sufficiently maintained, and the desired water repellency may not be achieved. Therefore, it is preferable to carefully consider the calendering conditions. For example, when calendering a woven / knitted fabric, normal conditions (e.g., a temperature of 130°C or higher and a linear pressure of 200 to 20,000 N / cm) may be used so as not to excessively reduce the protrusions of the mixed / entangled yarns. Calendering may also be performed without heating.

[0206] In the first manufacturing method, the resin that constitutes the moisture-permeable waterproof layer can be applied to the surface of the woven or knitted fabric by, for example, a coating method. A knife coater or a comma coater can be used in the coating method. From the viewpoint of providing excellent moisture permeability, it is preferable to obtain the moisture-permeable waterproof layer by a wet method.

[0207] In the second manufacturing method, an example of a method for forming an adhesive layer on a woven or knitted fabric or a moisture-permeable waterproof layer is a lamination method. In the lamination method, a method using a resin solution or a hot melt method can be used to form the adhesive layer. First, a moisture-permeable waterproof layer-forming resin composition (e.g., a resin composition containing a resin and an organic solvent) is applied to the surface of a release material (such as release paper, release cloth, or release film) with a clearance, and a moisture-permeable waterproof layer is formed while adjusting the thickness, followed by heat treatment to completely react and obtain a film. The release material can be removed as appropriate after lamination or aging.

[0208] An adhesive layer is then formed on the woven or knitted fabric or the moisture-permeable waterproof layer. For example, if a resin solution is used, a two-component curing polyurethane resin solution with a viscosity in the range of 500 to 5,000 mPa·s may be applied to the entire surface or in a pattern. The resulting solution is then dried to form an adhesive layer. The woven or knitted fabric and the moisture-permeable waterproof layer are then bonded together via the adhesive layer, and the two are then pressure-bonded or thermocompression-bonded to complete the second manufacturing method.

[0209] On the other hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practice, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, first, the hot melt resin is melted while taking into consideration the melting point of the resin and its viscosity when melted. The molten resin is then applied to the woven or knitted fabric or the moisture-permeable waterproof layer and allowed to mature while cooling at room temperature to form an adhesive layer. The woven or knitted fabric and the moisture-permeable waterproof layer are then bonded together via the adhesive layer and pressure-bonded, thereby completing the second manufacturing method.

[0210] It is preferable to adopt the second manufacturing method as the manufacturing method. This is because, when a moisture-permeable waterproof layer is laminated using a coating method, there is a concern that pinholes will occur in the moisture-permeable waterproof layer due to fine protrusions on the surface of the woven or knitted fabric, which will tend to reduce water pressure resistance. Furthermore, when a woven or knitted fabric is subjected to a calendering process in an attempt to form a uniform moisture-permeable waterproof layer, there is a concern that the protrusions or air retaining layer will be reduced and the desired water repellency will not be achieved. Furthermore, since careful examination of the calendering conditions is required separately, the process itself may become complicated.

[0211] Thereafter, a lining fiber fabric can be laminated on the moisture-permeable waterproof layer using any known appropriate method.

[0212] ·Applications of laminated fabric The laminated fabric has excellent water repellency and breathable waterproof properties, and the breathable waterproof layer does not peel off even in harsh environments, making it suitable for use in fields such as uniforms, sportswear, and outdoor products used outdoors.

[0213] [Processing method] The water repellent composition of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by conventionally known methods. The water repellent composition of the present disclosure may be dispersed and diluted in an organic solvent or water, if necessary, and applied to the surface of the substrate by known methods such as dip coating, spray coating, foam coating, etc., followed by drying. After drying, a textile product is obtained to which the solid components of the water repellent composition are attached. If necessary, the composition may be applied together with an appropriate crosslinking agent and cured. Furthermore, the water repellent composition of the present disclosure can also be used in combination with various additives such as water and / or oil repellents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and antifoaming agents. Examples of various additives may be the same as those described above under "Other Components" for the water repellent composition. The concentration of the hydrocarbon-based water-repellent resin in the treatment agent to be brought into contact with the substrate may be changed as appropriate depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0214] [Textile products] There are various examples of textile products that can be used as the substrate, such as cloth products and paper products.

[0215] Examples of textile products include natural fibers of animal or plant origin such as cotton, linen, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, clothing fabrics, and carpets, but the treatment may also be applied to fibers, yarns, and intermediate textile products (for example, slivers or rovings) in a state before they are made into textiles.

[0216] Examples of paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating mediums, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc.

[0217] The water repellent composition can be applied to a textile by any of the known methods for treating textiles (e.g., fabric) with a liquid. The textile may be immersed in the water repellent composition, or the solution may be applied or sprayed onto the textile. The treated textile is preferably dried and cured by heating to develop water and oil repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0218] Alternatively, the polymer may be applied to the textile by a cleaning process, such as in a laundry application or a dry cleaning process.

[0219] The textiles to be treated may be fabrics, including woven fabrics, knitted fabrics, and nonwoven fabrics, clothing fabrics, carpets, etc., but may also be fibers or yarns or intermediate textile products (e.g., slivers or rovings, etc.). The water repellent compositions of the present disclosure are particularly effective in making textiles (e.g., synthetic fibers) water repellent.

[0220] The fibers constituting the textile product may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers or inorganic fibers. The fibers may be used alone or in combination of two or more types.

[0221] Examples of natural fibers include cotton, flax, cellulose fibers such as pulp, chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as ground wood pulp (GP), pressure-raised ground wood pulp (PGW), and thermomechanical pulp (TMP), chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N wood), bleached softwood kraft pulp (NBKP; N wood, NB wood), unbleached hardwood kraft pulp (LUKP; L wood), and bleached hardwood kraft pulp (LBKP; L wood), recycled paper pulps such as deinking pulp (DIP) and waste pulp (WP), and semi-chemical pulp (CP).

[0222] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymer polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0223] Alternatively, the textile may be leather, and the manufacturing polymer may be applied to the leather from an aqueous solution or emulsion at various stages of leather processing, for example, during wet processing of the leather or during finishing of the leather, to render the leather hydrophobic and oleophobic. Alternatively, the textile product may be paper. The manufacturing polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example, during the drying period of the paper.

[0224] The term "treatment" means applying the water repellent composition to a substrate by immersion, spraying, coating, etc. The treatment allows the polymer, which is the active ingredient of the water repellent composition, to penetrate into the substrate and / or adhere to the surface of the substrate.

[0225] [Pretreatment of textile products] The textile product may be pretreated before being treated with the water repellent composition of the present disclosure. Pretreatment of the textile product can impart excellent durability to the textile product after treatment with the water repellent composition.

[0226] Examples of pretreatments for textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphate, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0227] The method for pretreating textile products is not limited, and textile products can be pretreated by conventionally known methods. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the surface of the textile product by known methods such as dip coating, spray coating, foam coating, etc., followed by drying. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of a method for pretreating textile products, a method for pretreating textile products with a hydrocarbon-based water repellent will be described in detail below.

[0228] The pretreatment method for textile products is to add -SO3M to the fibers. 1 (In the formula, M 1 represents a monovalent cation), -COOM 2 (In the formula, M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(wherein, X 1 and X 2and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as a "specific functional group").

[0229] M 1 Examples of M include H, K, Na, and ammonium ions which may have a substituent. 2 Examples of X include H, K, Na, and an ammonium ion which may have a substituent. 1 or X 2 When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0230] The fibers containing the specific functional groups (hereinafter, sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following method. (i) A compound having the specific functional group is attached to a fiber material. The attachment of the compound may be in a state where a part of the compound is chemically bonded to a part of the fiber, to the extent that a sufficient amount of the specific functional group remains. (ii) A fiber is prepared in which the specific functional group is directly introduced into the material that constitutes the fiber.

[0231] In the case of (i), for example, functional group-containing fibers can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the above-mentioned specific functional groups.

[0232] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, paper, etc.

[0233] In this embodiment, from the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use textile materials containing polyamide and polyester as raw materials, and it is particularly preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate and polylactic acid, and mixed fibers containing these.

[0234] Above -SO3M 1 A phenolic polymer can be used as the compound having the formula:

[0033] Such a phenolic polymer can be, for example, one containing at least one compound represented by the following general formula:

[0235] TIFF0007824536000006.tif4678 [In formula (2), X 2 Ha-SO3M 3 (In the formula, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0236] TIFF0007824536000007.tif2661 [In the formula, M 4 represents a monovalent cation.]

[0237] The above M 3 Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0238] The above M 4 Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0239] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0240] Above - COOM 2 Examples of compounds having the formula include polycarboxylic acid polymers.

[0241] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0242] Examples of methods for producing polycarboxylic acid polymers include adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt and reacting the mixture at 30 to 150°C for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, or isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite; hydrogen peroxide; and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0243] In addition to the above-mentioned monomers, copolymerizable monomers can be used in radical polymerization. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Preferred acrylates and methacrylates have a hydrocarbon group having 1 to 3 carbon atoms, which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination.

[0244] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0245] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0246] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (trade name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0247] Above -OP(O)(OX 1 )(OX 2 ) includes, for example, phosphate ester compounds represented by the following general formula: TIFF0007824536000008.tif3243[where, X 1 or X 2 is the same as above, and X 3 represents an alkyl group having 1 to 22 carbon atoms.]

[0248] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0249] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0250] As the phosphate ester compound, for example, commercially available products such as "Phosphanol ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0251] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the compounds described above. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0252] Methods for treating textile materials with the pretreatment solution include, for example, padding, immersion, spraying, and coating. Examples of padding include methods using padding devices, such as those described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include methods using coating machines, such as those described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion include methods using batch dyeing machines, such as those described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). These machines include jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatments include air spraying, which sprays the treatment liquid in a mist form using compressed air, and methods using hydraulic atomization air spraying. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be appropriately adjusted taking into account various conditions, such as the purpose and performance. Furthermore, if the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after application to the fiber material to remove the water. The drying method is not particularly limited, and can be either a dry heat method or a wet heat method. The drying temperature is also not particularly limited, and can be, for example, drying at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment at a temperature of 100 to 180°C for 10 seconds to 5 minutes may be performed after drying.

[0253] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the above-mentioned specific functional group (e.g., a phenolic polymer compound) adsorbed during the process may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0254] The treatment temperature in the immersion treatment can be set to 60 to 130° C. The treatment time can be set to 5 to 60 minutes.

[0255] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can both be achieved at high levels.

[0256] The pH of the pretreatment liquid is preferably adjusted to 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0257] The pretreatment solution may contain a salt in order to effectively adsorb the compound having the specific functional group onto the fiber material by the salting-out effect. Examples of salts that can be used include sodium chloride. Examples of suitable ammonium carbonate include sodium carbonate, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0258] In the functional group introduction step using a pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By performing sufficient removal, it is possible to prevent the development of water repellency in the subsequent water repellent treatment from being hindered, and in addition, the feel of the resulting textile product is improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with a hydrocarbon-based water repellent.

[0259] (ii) An example of a fiber in which the specific functional group is directly introduced into the material that constitutes the fiber is cationic dyeable polyester (CD-PET).

[0260] From the viewpoint of improving the water repellency of the resulting textile product, the functional group-containing fiber preferably has a surface zeta potential of −100 to −0.1 mV, more preferably −50 to −1 mV. The zeta potential of the fiber surface can be measured, for example, using a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.). [Example]

[0261] Examples of the present disclosure will be specifically described below, but the present disclosure is not limited to these examples.

[0262] The test procedure is as follows: [Hydrophilic particle size] The particle size of hydrophilic particles was measured as the primary particle size by the following method: A dispersion containing hydrophilic particles was sprayed onto a carbon support film, the evaporated sample was observed under a transmission electron microscope, the particle sizes of all particles present within the field of view were measured, and the field of view was changed and the particle sizes were measured again. This process was repeated until particle sizes were measured at 10 or more points, and the average value was taken as the average primary particle size.

[0263] [Turbidity] The turbidity of an aqueous dispersion prepared by dispersing hydrophilic particles in water at a concentration of 10 g / l and adjusting the pH to 7 was calculated using an integrating sphere turbidity meter PT200 manufactured by Nitto Seiko Analytech Co., Ltd. A calibration curve (range 0 to 1000 ppm) was prepared for the turbidity of kaolin (pigment), a standard sample, based on JIS K0101, drinking water testing method, and the calibration curve was used to calculate the turbidity.

[0264] [Zeta potential] The hydrophilic particles were dispersed in water at a concentration of 10 g / l and the zeta potential of the aqueous dispersion prepared at 25° C. and pH 7 was measured using a zeta potential meter (ELSZ-2000, manufactured by Otsuka Electronics Co., Ltd.).

[0265] [Water repellency test] The water repellency of the treated test fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22). The water repellency was evaluated according to the following criteria, where a higher score indicates better water repellency.

[0266] 100 No wetting or water droplets were observed on the surface. 90 The surface did not wet, but small water droplets were observed to adhere. Wetting was observed on small individual water droplets on the surface. 70 Half of the surface showed wetting, with small individual wettings observed penetrating the fabric. 50 Wetting was observed over the entire surface. 0 Wetting was observed on the entire front and back surfaces.

[0267] [Slip resistance] The test fabric was tested for warp slippage in accordance with JIS L 1096-99.8.21.1 seam slippage method B at a load of 117.2N (12kgw) to measure seam slippage (mm). The smaller the seam slippage value, the better the slip resistance.

[0268] [Storage stability] A water repellent composition test liquid having a solid content adjusted to 30% by weight is left to stand at 50°C for one week, and then the state of the liquid is visually observed and evaluated according to the following criteria. 〇: No change in appearance △: Precipitation in the upper layer ×: Sediment present

[0269] [Preparation of raw materials] (Production Example of Acrylic Polymer-Containing Aqueous Dispersion) Manufacturing Example 1 A 500 ml plastic container was charged with 30 g of a water-soluble glycol solvent as an organic solvent, 120 g of pure water as a liquid medium, 40 g of stearyl acrylate as a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, 2 g of sorbitan fatty acid ester as a surfactant, 0.1 g of acetic acid as an organic acid, 2 g of a cationic emulsifier, and 6 g of polyoxyethylene alkyl ether, and the mixture was heated to 80°C, stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. Next, this mixture was transferred to a 500 ml autoclave, and after purging with nitrogen, 0.2 g of lauryl mercaptan as a chain transfer agent and 20 g of vinyl chloride as a copolymerizable monomer were added. Furthermore, 1 g of an azo-group-containing water-soluble initiator was added as a polymerization initiator, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of an acrylic polymer (hydrocarbon-based water-repellent resin). This dispersion was further diluted with pure water to prepare an aqueous dispersion of a hydrocarbon-based water-repellent resin with a solids concentration of 30% (more specifically, an aqueous dispersion containing a hydrocarbon-based water-repellent resin, a surfactant, and a liquid medium).

[0270] Manufacturing Examples 2 to 4 An aqueous dispersion containing an acrylic polymer, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 1, except that the formulation was changed according to Table 1.

[0271] TIFF0007824536000009.tif75164

[0272] (Aqueous dispersion containing dendrimer) Ecoplus (manufactured by Rudolph) was used as the aqueous dispersion containing the dendrimer-based water-repellent resin.

[0273] (Production Example of Polyurethane-Containing Aqueous Dispersion) Manufacturing Example 5 1. Synthesis of aliphatic polyisocyanate derivatives In a reactor equipped with a thermometer, stirrer, nitrogen inlet, and condenser, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, Inc., trade name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, a hindered phenol-based antioxidant), and 0.25 parts by mass of tetraphenyl dipropylene glycol diphosphite (organic phosphite ester, cocatalyst) were mixed under a nitrogen atmosphere. 10.7 parts by mass of 1,3-butanediol was then added to the mixture, and nitrogen was introduced into the liquid phase for 1 hour. The mixture was then heated to 80°C and reacted for 3 hours, after which it was cooled to 60°C. 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added as an isocyanurate catalyst, and the mixture was allowed to react for 1.5 hours. Next, 0.04 parts by mass of o-toluenesulfonamide was added to 100 parts by mass of HDI. The reaction mixture was then passed through a thin-film distillation apparatus (temperature 150°C, vacuum degree 93.3 Pa) and distilled until the amount of residual HDI monomer was 0.5% or less, yielding an aliphatic polyisocyanate derivative (an isocyanurate derivative of hexamethylene diisocyanate). The resulting aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average isocyanate functionality of 3.0.

[0274] 2. Production of hydrocarbon-based polyurethanes In a reactor equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, 100.20 g of the aliphatic polyisocyanate derivative, 67.60 g of Kalcol 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound, and 22.30 g of oleic alcohol were mixed and reacted in a nitrogen atmosphere at 110°C for 4 hours until the concentration of isocyanate groups reached 3.67%. Next, the reaction solution was cooled to 80°C, and 9.90 g of N-methyldiethanolamine was added as a cationic active hydrogen compound, followed by reaction at 80°C for 1 hour. Next, 50.00 g of methyl ethyl ketone was added as a solvent, and the mixture was reacted at 80° C. until disappearance of the isocyanate groups was confirmed by infrared absorption spectroscopy. Next, 57.69 g of methyl ether ketone was added to the reaction liquid, and the temperature was raised to 80°C. The reaction liquid was mixed until completely dissolved, and then cooled to 75°C. Thereafter, 18.96 g of acetic acid was added as an acid compound to neutralize the mixture. Next, while the reaction solution was kept at 75°C, 800.0 g of ion-exchanged water heated to 70°C was gradually added to emulsify the reaction solution (internal emulsification). Next, the solvent was removed in an evaporator under reduced pressure with a water bath temperature of 60° C. until the solid content reached 20% by weight or more. Next, the solid concentration excluding the acid compound (acetic acid) was adjusted with ion-exchanged water to 20% by weight, thereby obtaining an aqueous dispersion containing polyurethane.

[0275] Manufacturing Example 6 A 500 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 116 g of sorbitan tristearate and 150 g of 4-methyl-2-pentanone (MIBK). To remove excess water vapor from the mixture, the temperature of the mixture was maintained at 70°C while stirring. The mixture was refluxed for 1 hour and then allowed to cool to 50°C. While continuing to stir, 30 g of Desmodur N-100 (a biuret derivative of hexamethylene diisocyanate, manufactured by Covestro) was added dropwise to the mixture using a dropping funnel. After the addition, one drop of dibutyltin dilaurate was added as a catalyst, and the mixture was allowed to react at 80°C for 1 hour. Next, 25 g of sorbitan monostearate was added, and the mixture was allowed to react for an additional 4 hours at 80°C. The reaction mixture was then cooled to 60°C, and the collected mixture was slowly mixed with 60°C water containing an arbitrary amount of cationic emulsifier and polyoxyethylene alkyl ether. The mixture was stirred at 6000 rpm for 1 minute using a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. The solvent (MIBK) was then removed under reduced pressure, and pure water was added to adjust the concentration, yielding an aqueous dispersion containing polyurethane with a solids concentration of 20%.

[0276] Manufacturing Example 7 A 500 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 150 g of methyl ethyl ketone (MEK) and 51 g of stearyl alcohol. To remove excess water vapor from the mixture, the mixture was stirred and refluxed for 1 hour while maintaining the temperature at 70°C, and then allowed to cool to 50°C. 30 g of Desmodur N3200A (a biuret derivative of hexamethylene diisocyanate, manufactured by Covestro) was added to the mixture, and the mixture was further reacted at 80°C for 4 hours. After cooling to 60°C, the reaction solution was recovered and slowly mixed with water containing an arbitrary amount of polyoxyethylene alkyl ether at 60°C. The mixture was stirred at 6000 rpm for 1 minute using a homomixer, and then emulsified and dispersed using ultrasound for 15 minutes. Next, the solvent (MEK) was removed under reduced pressure, and then pure water was added to adjust the concentration, yielding an aqueous dispersion containing polyurethane with a solids concentration of 20%.

[0277] (Example of production of silicone-containing aqueous dispersion) Manufacturing Example 8 A 200 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 12 g of methyl hydrogen silicone oil (SiH:SiCH molar ratio = 50:50 as measured by 1H NMR) and 0.02 g of platinum catalyst. Next, 36 g of 1-hexacosene was charged to the dropping funnel, and while maintaining the temperature at 70°C, 1-hexacosene was added dropwise from the dropping funnel. After the addition was completed, the reaction was continued for an additional 3 hours at 70°C. The disappearance of the SiH peak was confirmed by infrared spectroscopy (IR), yielding 47 g of solid silicone polymer. Next, 28 g of silicone polymer, 5.6 g of water-soluble glycol solvent, 60 g of pure water, 1.7 g of sorbitan fatty acid ester, 0.7 g of polyoxyethylene alkyl ether, and 0.6 g of cationic emulsifier were placed in a 250 ml glass container, heated to 75°C, stirred at 2000 rpm for 1 minute with a homomixer, and then ultrasonically emulsified and dispersed for 10 minutes to obtain an aqueous dispersion of the silicone polymer. Pure water was then added to prepare an aqueous dispersion of the silicone polymer with a solids concentration of 30 wt%.

[0278] (Example of production of wax-containing aqueous dispersion) Manufacturing Example 9 A pressure reactor was charged with 150 g of paraffin wax (melting point 75°C), 350 g of pure water, 4.5 g of polyoxyethylene alkyl ether, and 3 g of sorbitan fatty acid ester, sealed, and heated to 110-120°C with stirring. After that, high-pressure emulsification was carried out for 30 minutes under high pressure to prepare a water dispersion of wax. Pure water was then added to prepare a water dispersion of wax with a solid content of 30 wt%.

[0279] Manufacturing Example 10 A reaction vessel was charged with 150 g of oxidized polypropylene wax with a melting point of 150°C, an acid value of 44 mgKOH / g, and a density of 0.93, 325 g of ion-exchanged water, 25 g of a surfactant with an HLB of 15, and 5 g of a 48% aqueous potassium hydroxide solution, and the vessel was sealed. The temperature was raised to 160°C with stirring, and then the mixture was emulsified under high pressure for 1 hour and cooled to 90°C to obtain an aqueous dispersion of polypropylene wax. Pure water was then added to prepare an aqueous dispersion of polypropylene wax with a solids content of 30% by weight.

[0280] [Examples 1 to 17, Comparative Examples 1 to 10] Water was added to and mixed with the above-mentioned aqueous dispersion and the hydrophilic particles shown in Table 2 to obtain an aqueous dispersion with a solids concentration of 30% in accordance with the composition weight ratio shown in Table 3. This aqueous dispersion was diluted with tap water to prepare 1000 g of a test liquid with a solids concentration of 1.0 wt %. Next, test cloths (polyester fabric, nylon fabric) were impregnated with this test liquid and passed through a mangle. The test cloths were passed through a pin tenter at 160°C for 1 minute, dried, cured, and then subjected to the above-mentioned tests.

[0281] TIFF0007824536000010.tif42164 TIFF0007824536000011.tif96162

[0282] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

Claims

1. A water repellent composition comprising: the water repellent composition comprises a hydrocarbon-based water repellent resin having a hydrocarbon group having 5 to 40 carbon atoms and hydrophilic particles; the turbidity of an aqueous dispersion prepared by dispersing the hydrophilic particles in water at a concentration of 10 g / L and adjusting the pH to 7 is 20 ppm or less; The water repellent composition has a zeta potential of +34 mV or more when the hydrophilic particles are dispersed in water at a concentration of 10 g / l and the resulting aqueous dispersion is adjusted to pH 7.

2. The water repellent composition according to claim 1, comprising at least one member selected from the group consisting of an organic acid, a surfactant, and an organic solvent.

3. 3. The water repellent composition according to claim 1, wherein the amount of the hydrophilic particles is 2% by weight or more and 12% by weight or less based on the total amount of the hydrocarbon-based water repellent resin and the hydrophilic particles.

4. 3. The water repellent composition according to claim 1, wherein the hydrophilic particles have an average primary particle size of less than 40 nm.

5. The water repellent composition according to claim 1 or 2, wherein the hydrophilic particles are inorganic particles.

6. 3. The water repellent composition according to claim 1, wherein the hydrophilic particles are at least one selected from the group consisting of silica and alumina.

7. The water repellent composition according to claim 1 or 2, which comprises at least one selected from the group consisting of silicones and waxes.

8. The hydrocarbon-based water-repellent resin is represented by the following formula: CH ２ =C(-R １２ )-C(=O)-Y １１ -(R １１ ) ｋ [In the formula, R １１ is a hydrocarbon group having 5 to 40 carbon atoms, R １２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y １１ represents a direct bond, a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - and -NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), k is 1 to 3.

3. The water repellent composition according to claim 1, which is a polymer having repeating units derived from a monomer represented by the formula:

9. the hydrocarbon-based water-repellent resin has an alkyl group having 10 to 30 carbon atoms, the hydrophilic particles are at least one selected from the group consisting of silica and alumina, 3. The water repellent composition according to claim 1, wherein the amount of the hydrophilic particles is 2% by weight or more and 12% by weight or less based on the total amount of the hydrocarbon-based water repellent resin and the hydrophilic particles.

10. 3. A method for producing the water repellent composition according to claim 1, comprising a step of reacting a hydrocarbon-based water repellent resin raw material in a medium containing the hydrocarbon-based water repellent resin raw material and the hydrophilic particles to obtain the hydrocarbon-based water repellent resin.

11. A method for producing a treated product, comprising the step of treating a substrate with the water repellent composition according to claim 1 or 2.

12. A textile product having the solid component of the water repellent composition according to claim 1 or 2 adhered thereto.

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