WO2025225685A1 - Water-repellent composition, method for producing water-repellent fiber product, and water-repellent fiber product - Google Patents

Abstract

The present invention provides: a water-repellent composition from which it is possible to obtain a water-repellent fiber product which exhibits excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, and texture; a method for producing a water-repellent fiber product using the same; and a water-repellent fiber product using the same. Provided is a water-repellent composition containing an amino-modified silicone, a silicone resin, and an alkyl polysiloxane, wherein: the blending amount of the silicone resin is 1,000-5,000 parts by mass relative to 100 parts by mass of the blending amount of the amino-modified silicone; and the blending amount of the silicone resin is 60-130 parts by mass relative to 100 parts by mass of the total blending amount of both the amino-modified silicone and the alkyl polysiloxane.

Description

Water repellent composition, method for producing water repellent textile product, and water repellent textile product

The present invention relates to a water repellent composition, a method for producing a water repellent textile product, and a water repellent textile product.

Conventionally, fluorine-based water repellents containing fluorine groups have been known, and textile products have been known to have their surfaces imparted with water repellency by treating them with such fluorine-based water repellents. Such fluorine-based water repellents are generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group. While textile products treated with fluorine-based water repellents exhibit excellent water repellency, the monomer having a fluoroalkyl group is difficult to decompose, posing environmental problems.

In recent years, therefore, research has been ongoing into silicone-based water repellents that do not contain fluorine (i.e., are non-fluorine-based), such as those proposed in Patent Documents 1 and 2 below.

Japanese Patent Application Laid-Open No. 2017-226946 International Publication No. 2019/131456

In recent years, water-repellent textile products have increasingly been used for outdoor purposes, and these textile products are being required to have higher water pressure resistance and abrasion resistance than before. However, the water repellents described in Patent Documents 1 and 2 above leave room for improvement, particularly in terms of water pressure resistance, abrasion resistance, and their durability.

The present invention has been made in consideration of the above circumstances, and aims to provide a water repellent composition that can be used to obtain water-repellent textile products that have excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, and texture; a method for producing water-repellent textile products using the same; and water-repellent textile products using the same.

As a result of intensive research into solving the above problems, the inventors discovered that by combining a specific silicone compound, a silicone resin, and an alkyl polysiloxane, and adjusting the mass ratio between the amount of silicone resin and the amount of the specific silicone compound, as well as the mass ratio between the amount of silicone resin and the total amount of the specific silicone compound and the alkyl polysiloxane, it is possible to obtain textile products that have high water repellency and durable water repellency, water pressure resistance and durable water pressure resistance, and abrasion resistance and durable abrasion resistance, as well as a soft texture, and based on this finding, they have completed the present invention.

One aspect of the present invention provides a water repellent composition containing an amino-modified silicone, a silicone resin, and an alkylpolysiloxane, wherein the amount of the silicone resin is 1,000 to 5,000 parts by mass per 100 parts by mass of the amino-modified silicone, and the amount of the silicone resin is 60 to 130 parts by mass per 100 parts by mass of the total amount of the amino-modified silicone and the alkylpolysiloxane.

The water repellent composition according to one embodiment of the present invention makes it possible to obtain water-repellent textile products that have excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, and texture.

From the standpoints of water repellency, durable water repellency, texture, and seam slippage, the functional group equivalent of the amino-modified silicone may be 100 to 20,000 g/mol. Here, the functional group equivalent of the amino-modified silicone refers to the molecular weight of the amino-modified silicone per 1 mol of nitrogen atoms.

The present invention also provides a method for producing a water-repellent textile product, which includes a step of treating textiles with a treatment liquid containing the water-repellent composition according to one aspect of the present invention described above, and a water-repellent textile product having textiles and the water-repellent composition according to one aspect of the present invention adhered to the textiles.

The method for producing water-repellent textile products according to one aspect of the present invention makes it possible to consistently produce water-repellent textile products that have excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, and texture.

One aspect of the present invention provides a water repellent composition that can be used to obtain water-repellent textile products that have excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, and texture. Furthermore, the water repellent composition according to one aspect of the present invention also has excellent resistance to chemicals used in a process preceding the water repellent treatment of textiles using the water repellent composition. Therefore, even if chemicals used in the preceding process are carried over into the water repellent treatment bath, the water repellency is unlikely to decrease (i.e., the resistance to the introduction of chemicals is good).

A preferred embodiment of the present invention (hereinafter also referred to as the present embodiment) will be described in detail below. However, the present invention is not limited to the following embodiment.

[Water repellent composition]
The water repellent composition of the present embodiment contains a water repellent component including an amino-modified silicone (hereinafter, sometimes referred to as component (I)), a silicone resin (hereinafter, sometimes referred to as component (II)), and an alkylpolysiloxane (hereinafter, sometimes referred to as component (III)).

<Amino-modified silicone>
Amino-modified silicones include compounds having organic groups containing amino and/or imino groups on the side chains and/or terminals of organopolysiloxane. Examples of such organic groups include organic groups represented by -R- _NH2 and organic groups represented by -R-NH-R'- _NH2 . Examples of R and R' include divalent groups such as ethylene and propylene. Some or all of the amino and/or imino groups may be blocked. Blocked amino and/or imino groups can be obtained, for example, by treating the amino and/or imino groups with a blocking agent. Examples of blocking agents include fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, acid halides of fatty acids having 2 to 22 carbon atoms, and aliphatic monoisocyanates having 1 to 22 carbon atoms.

From the viewpoints of water repellency, durable water repellency, texture, and seam slippage, the functional group equivalent weight of the amino-modified silicone is preferably 100 to 20,000 g/mol, more preferably 150 to 12,000 g/mol, and even more preferably 200 to 4,000 g/mol.

The amino-modified silicone is preferably liquid at 25°C. The kinematic viscosity of the amino-modified silicone at 25°C is preferably 10 to 100,000 ^mm2 /s, more preferably 10 to 30,000 ^mm2 /s, and even more preferably 10 to 5,000 ^mm2 /s. When the kinematic viscosity at 25°C is 10 ^mm2 /s or higher, the desired effect of the water repellent composition can be easily achieved, while when it is 100,000 ^mm2 /s or lower, workability and seam slippage tend to be easily ensured. The kinematic viscosity at 25°C refers to the value measured using the method described in JIS K 2283:2000 (Ubbelohde viscometer). Note that the kinematic viscosity at 25°C is sometimes expressed in units of cs (centipoise), particularly for low viscosities, and the two are essentially the same.

Commercially available amino-modified silicones can be used. Examples of commercially available products include KF8005, KF-868, KF-864, and KF-393 (all trade names manufactured by Shin-Etsu Chemical Co., Ltd.), XF42-B1989 (manufactured by Momentive Performance Materials Japan, LLC), and SF-8417 and BY16-853U (all trade names manufactured by Dow-Toray Industries, Inc.).

Amino-modified silicones may be used alone or in combination of two or more types.

Amino-modified silicones may have some or all of their amino and/or imino groups neutralized, or may be unneutralized. Neutralization can be performed with organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, methanesulfonic acid, and toluenesulfonic acid; or inorganic acids such as hydrogen chloride, sulfuric acid, and nitric acid.

<Silicone resin>
The water repellent composition of this embodiment contains a silicone resin. The silicone resin is preferably an organopolysiloxane containing MQ, MDQ, MT, MTQ, MDT, or MDTQ as a constituent, which is solid at 25°C and has a three-dimensional structure. Furthermore, the silicone resin preferably has a hardness of 20 or more, more preferably 60 or more, as measured with a Type A durometer in accordance with JIS K 6249:2003 13. Hardness Test. Here, M, D, T, and Q represent an (R") _3SiO0.5 unit, _an (R") _2SiO unit, an R" _SiO1.5 unit, and an _SiO2 unit, respectively. R" represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

Silicone resins are commonly known as MQ resins, MT resins, or MDT resins, and may also have moieties designated as MDQ, MTQ, or MDTQ.

Silicone resins can be obtained alone or as a solution in an appropriate solvent. The solvent may be alkylpolysiloxane and/or a solvent other than alkylpolysiloxane. Examples of solvents other than alkylpolysiloxane include n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and mixtures of these solvents.

Examples of solutions in which silicone resins are dissolved in alkylpolysiloxanes include KF7312J (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane and decamethylcyclopentasiloxane), KF7312F (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane and octamethylcyclotetrasiloxane), KF9021L (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane and low-viscosity methylpolysiloxane (volatile methylpolysiloxane)), and KF7312L (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane and low-viscosity methylpolysiloxane (viscosity ² mm2/s)) commercially available from Shin-Etsu Chemical Co., Ltd. As will be described later, volatile methylpolysiloxane is not used as the basis for calculating parts by mass, mass ratios, etc. as "alkylpolysiloxane" in this embodiment.

Examples of silicone resins alone include MQ-1600 solid resin (trimethylsilyl group-containing polysiloxane) and MQ-1640 flake resin (a mixture of trimethylsilyl group-containing polysiloxane and polypropylsilsesquioxane), both commercially available from Dow Toray Co., Ltd. The above commercially available products contain trimethylsilyl group-containing polysiloxane and include MQ, MDQ, MT, MTQ, MDT, or MDTQ.

From the viewpoints of water repellency, water pressure resistance, abrasion resistance, and texture, the amount of silicone resin in the water repellent composition of this embodiment is preferably 1,000 to 5,000 parts by mass, more preferably 1,200 to 4,000 parts by mass, and even more preferably 1,500 to 3,500 parts by mass per 100 parts by mass of amino-modified silicone. If the resin amount is below the lower limit, the overall properties, particularly durable water repellency, repellency, water resistance, abrasion resistance, and resistance to carry-in, will decrease. On the other hand, if the resin amount exceeds the upper limit, in addition to the decrease in the above-mentioned performance, the texture of fibers treated with the composition may be significantly deteriorated. Furthermore, from the above viewpoints, the amount of silicone resin is preferably 60 to 130 parts by mass, more preferably 65 to 125 parts by mass, and even more preferably 90 to 120 parts by mass per 100 parts by mass of the total amount of amino-modified silicone and alkylpolysiloxane.

<Alkylpolysiloxane>
The water repellent composition of this embodiment contains an alkyl polysiloxane as a water repellent component. This alkyl polysiloxane may be distinguished from alkyl polysiloxanes used as solvents (for example, solvents for silicone resins) because it has a kinematic viscosity at 25°C of more than 2 mm ² /s. That is, in one aspect, the alkyl polysiloxane of this embodiment has a kinematic viscosity at 25°C of more than 2 mm ² /s, and the alkyl polysiloxane that can be contained as a solvent in the water repellent composition has a kinematic viscosity at 25°C of 2 mm ² /s or less. The alkyl polysiloxane of this embodiment can be distinguished from alkyl polysiloxanes that volatilize from a system (i.e., are volatile) because it is non-volatile. Here, whether an alkyl polysiloxane is non-volatile or volatile can be distinguished as follows.

Nonvolatile alkylpolysiloxanes are liquid or have plasticity at room temperature (25°C) (i.e., their plasticity can be measured according to the method specified in JIS K 6249, where the plasticity is the value (unit: mm) when a load of 1 kgf is applied to a 4.2 g spherical sample at 25°C for 3 minutes). More specifically, nonvolatile alkylpolysiloxanes are those that exhibit a mass loss of 1% or less after 1 g of the alkylpolysiloxane is spread in a glass petri dish with a diameter of 48 mm and left at 25°C and atmospheric pressure for 24 hours. Note that linear or cyclic alkylpolysiloxanes with a siloxane polymerization degree of 10 or more exhibit nonvolatility. On the other hand, linear or cyclic alkylpolysiloxanes with a siloxane polymerization degree of less than 10, particularly 7 or less, exhibit volatility at room temperature, and are therefore preferably used as part of a solvent rather than as the alkylpolysiloxane serving as the water-repellent component of this embodiment. In one aspect, volatile silicones having a siloxane polymerization degree of less than 10, particularly 7 or less, include dimethylpolysiloxanes having a kinematic viscosity of 2 mm ² /s or less at 25° C., and cyclodimethylpolysiloxanes having a polymerization degree of 3 to 7 (D3, D4, D5, D6, and D7). These are expressly excluded from the scope of alkylpolysiloxanes as the water-repellent component of this embodiment.

In one embodiment, the alkyl polysiloxane used as the water-repellent component is a compound in which the side chains and terminals of a linear organo polysiloxane contain saturated hydrocarbon groups, or a compound in which the side chains of a cyclic organo polysiloxane contain saturated hydrocarbon groups. Examples of such alkyl polysiloxanes include those represented by the following general formula (1):

[In formula (1), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each independently represent a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and v represents a number that makes the compound represented by formula (1) nonvolatile.]
and a compound represented by the following general formula (2):

[In formula (2), R ¹⁹ and R ²⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and w represents a number that makes the compound represented by formula (2) nonvolatile.]
Examples of the compound include compounds represented by the following formula:

In the compound represented by the general formula (1) used in this embodiment, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ are each independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. From the viewpoints of facilitating the dissolution of a silicone resin in the compound represented by the general formula (1) and facilitating the acquisition of the compound, the number of carbon atoms in this saturated hydrocarbon group is preferably 1 to 10. The saturated hydrocarbon group may be linear or branched. The saturated hydrocarbon group is preferably linear, and more preferably a linear alkyl group. The saturated hydrocarbon group is preferably a methyl group or an ethyl group, and more preferably a methyl group. v can be appropriately selected so that the compound represented by the general formula (1) is nonvolatile and has a kinematic viscosity of more than 2 mm ² /s, for example, within the kinematic viscosity range described below. From the viewpoint of making the alkylpolysiloxane nonvolatile, v is preferably 3 or greater, or 5 or greater. Note that compounds where v in formula (1) is a number that makes the compound represented by formula (1) volatile, rather than a number that makes the compound nonvolatile (and therefore a compound with a low degree of polymerization), can be used as a solvent for silicone resins, etc. However, such volatile alkyl polysiloxanes are not used in the definition of the "alkyl polysiloxane" in this embodiment, i.e., the parts by mass, mass ratio, etc. of the alkyl polysiloxane as a water-repellent component. The use of a volatile polysiloxane can sometimes improve the stability of the system.

Examples of compounds represented by the above general formula (1) include non-volatile dimethylpolysiloxane and diethylpolysiloxane.

In the compound represented by general formula (2) used in this embodiment, R ¹⁹ and R ²⁰ are each independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. The number of carbon atoms in this saturated hydrocarbon group is preferably 1 to 10. When the number of carbon atoms in the saturated hydrocarbon group is within the above range, silicone resins tend to dissolve easily in the compound represented by general formula (2), and the compound tends to be easily available. The saturated hydrocarbon group may be linear or branched. The saturated hydrocarbon group is preferably linear, and a linear alkyl group is more preferred. The saturated hydrocarbon group is preferably a methyl group or an ethyl group, and a methyl group is more preferred. w is a number that renders the compound represented by general formula (2) nonvolatile. w is preferably in the range of 10 to 1,000, or in the range of 20 to 1,000. However, this does not preclude the use of alkylpolysiloxanes (i.e., low polymerization degrees) in which w is a number that makes the compound represented by general formula (2) volatile rather than nonvolatile, such as low polymerization degree and volatile alkylpolysiloxanes in which w is in the range of 2 to 10, particularly 4 or 5, as solvents for silicone resins, etc. Such cyclic and volatile alkylpolysiloxanes tend to be easily capable of dissolving silicone resins and are easily available, and can be suitably used in this embodiment.

W is the number at which the compound represented by general formula (2) becomes volatile. Examples of compounds suitable as solvents for silicone resins include decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane. However, as noted above, these are not used to define mass ratios, etc., for the "alkylpolysiloxane" of this embodiment.

Alkylpolysiloxanes may be used alone or in combination of two or more.

The alkylpolysiloxane of this embodiment is preferably liquid at 25°C. The kinematic viscosity of the alkylpolysiloxane at 25°C is preferably more than 2 ^mm2 /s and not more than 100,000 ^mm2 /s, more preferably 5 ^mm2 /s or more and 10,000 ^mm2 /s or less, even more preferably 10 ^mm2 /s or more and 1,000 ^mm2 /s or less, even more preferably 10 ^mm2 /s or more and 500 ^mm2 /s or less, and particularly preferably 10 ^mm2 /s or more and 100 ^mm2 /s or less. When the kinematic viscosity at 25°C is within the above range, the silicone resin tends to dissolve easily in the alkylpolysiloxane, and workability tends to be easily ensured. In this disclosure, the kinematic viscosity at 25°C refers to a value measured by the method described in JIS K 2283:2000 (Ubbelohde viscometer). As mentioned above, alkylpolysiloxanes with a kinematic viscosity of ² mm/s or less are not used in defining mass ratios and the like as alkylpolysiloxanes in this embodiment, but this does not prevent their use as solvents for silicone resins in the system, etc. As mentioned above, the use of a volatile cyclic or chain alkylpolysiloxane in combination can sometimes improve the handling and workability of silicone resins, etc., and the stability of the system.

The amount of alkylpolysiloxane in the water repellent composition of this embodiment is 500 to 15,000 parts by mass per 100 parts by mass of amino-modified silicone. From the standpoints of water repellency, texture, and seam slippage, the amount of alkylpolysiloxane is preferably 900 to 6,000 parts by mass per 100 parts by mass of amino-modified silicone. As mentioned above, in addition to the amount (parts by mass) of alkylpolysiloxane mentioned above, a volatile alkylpolysiloxane may be separately blended as a solvent, etc.

The mass ratio [(II):(III)] of the amount of silicone resin to the amount of alkyl polysiloxane in the water repellent composition of this embodiment is preferably 30:70 to 80:20, and more preferably 40:60 to 60:40, from the viewpoints of texture, water repellency, water pressure resistance, and abrasion resistance. As mentioned above, in addition to the above mass ratio of alkyl polysiloxane, a volatile alkyl polysiloxane may also be added separately as a solvent, etc.

<Other ingredients>
In addition to the components described above, the water repellent composition of the present embodiment may further contain solvents (alkyl polysiloxanes other than those mentioned in the above section <Alkyl polysiloxane>, and other solvents), crosslinking agents (for example, polyfunctional isocyanate compounds and other compounds), surfactants, antifoaming agents, organic acids, inorganic acids, alcohols, antibacterial agents, antifungal agents, pH adjusters, colorants, silica, antioxidants, deodorizers, various catalysts, emulsion stabilizers, chelating agents, antistatic agents, organo-modified silicones other than amino-modified silicones, and the like.

(Crosslinking agent)
The polyfunctional isocyanate compound that can be used as a crosslinking agent is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule, and known polyisocyanate compounds can be used. Examples of polyfunctional isocyanate compounds include diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate, and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimers, trimers, or tetramers of these diisocyanate compounds. The alkylene diisocyanate preferably has 1 to 12 carbon atoms.

Diisocyanate compounds include, for example, 2,4 or 2,6-tolylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, phenylene diisocyanate, tolylene or naphthylene diisocyanate, 4,4'-methylene-bis(phenyl isocyanate), 2,4'-methylene-bis(phenyl isocyanate), 3,4'-methylene-bis(phenyl isocyanate), 4,4'-ethylene-bis(phenyl isocyanate), and ω,ω'-diisocyanate-1,3-dimethyl Examples include benzene, ω,ω'-diisocyanate-1,4-dimethylcyclohexane, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanate cyclohexane, 4,4'-methylene-bis(cyclohexyl isocyanate), 3-isocyanate-methyl-3,5,5-trimethylcyclohexyl isocyanate, acid-diisocyanate dimer, ω,ω'-diisocyanate diethylbenzene, ω,ω'-diisocyanate dimethyltoluene, ω,ω'-diisocyanate diethyltoluene, fumaric acid bis(2-isocyanate ethyl)ester, 1,4-bis(2-isocyanate-prop-2-yl)benzene, and 1,3-bis(2-isocyanate-prop-2-yl)benzene.

Examples of triisocyanate compounds include triphenylmethane triisocyanate and tris(isocyanatophenyl)-thiophosphate. Examples of tetraisocyanate compounds include dimethyltriphenylmethane tetraisocyanate.

Modified polyisocyanate compounds derived from diisocyanate compounds are not particularly limited as long as they have two or more isocyanate groups. Examples include polyisocyanates having a biuret structure, isocyanurate structure, urethane structure, uretdione structure, allophanate structure, trimer structure, etc., and adducts of aliphatic isocyanates of trimethylolpropane. Polymeric MDI (MDI = diphenylmethane diisocyanate) can also be used as a polyisocyanate compound. Polyisocyanate compounds can be used alone or in combination of two or more.

The isocyanate groups contained in the polyfunctional isocyanate compound may be left as they are, or may be blocked isocyanate groups blocked with a blocking agent. Examples of blocking agents include pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole, and pyrazole; phenols such as phenol, methylphenol, chlorophenol, iso-butylphenol, tert-butylphenol, iso-amylphenol, octylphenol, and nonylphenol; lactams such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam; active methylene compounds such as malonic acid dimethyl ester, malonic acid diethyl ester, acetylacetone, methyl acetoacetate, and ethyl acetoacetate; oximes such as formaldoxime, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; imidazole compounds such as imidazole and 2-methylimidazole; and sodium bisulfite. Among these, pyrazoles and oximes are preferred from the viewpoint of durable water repellency.

As a polyfunctional isocyanate compound, it is also possible to use a water-dispersible isocyanate, which is a polyisocyanate that has been given water-dispersibility by introducing a hydrophilic group into the polyisocyanate structure to give it a surfactant effect. Furthermore, known catalysts such as organotin and organozinc can also be used in combination to promote the reaction between the amino group and the isocyanate group.

From the viewpoints of water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, and texture, the amount of polyfunctional isocyanate compound in the water repellent composition of this embodiment is preferably 10 to 600 parts by mass, and more preferably 30 to 300 parts by mass, per 100 parts by mass of the total amount of amino-modified silicone and silicone resin.

Crosslinking agents other than the above-mentioned polyfunctional isocyanate compounds include, for example, melamine resins and glyoxal resins.

Melamine resins can be compounds with a melamine skeleton, such as polymethylolmelamines such as trimethylolmelamine and hexamethylolmelamine; alkoxymethylmelamines in which some or all of the methylol groups in polymethylolmelamine are alkoxymethyl groups with an alkyl group having 1 to 6 carbon atoms; and acyloxymethylmelamines in which some or all of the methylol groups in polymethylolmelamine are acyloxymethyl groups with an acyl group having 2 to 6 carbon atoms. These melamine resins may be either monomers or polymers of dimers or higher, or mixtures of these may be used. Furthermore, melamine resins in which urea or the like is co-condensed with a portion of the melamine can also be used. Examples of such melamine resins include Beckamine APM, Beckamine M-3, Beckamine M-3 (60), Beckamine MA-S, Beckamine J-101, and Beckamine J-101LF manufactured by DIC Corporation, Unika Resin 380K manufactured by Union Chemical Industry Co., Ltd., and Riken Resin MM series manufactured by Miki Riken Kogyo Co., Ltd.

Conventionally known glyoxal resins can be used. Examples of glyoxal resins include 1,3-dimethylglyoxal urea resins, dimethylol dihydroxyethylene urea resins, and dimethylol dihydroxypropylene urea resins. The functional groups of these resins may be substituted with other functional groups. Examples of such glyoxal resins include Beckamine N-80, Beckamine NS-11, Beckamine LF-K, Beckamine NS-19, Beckamine LF-55P Concentrate, Beckamine NS-210L, Beckamine NS-200, and Beckamine NF-3 manufactured by DIC Corporation; Uniresin GS-20E manufactured by Union Chemical Industry Co., Ltd.; and Rikenresin RG series and Rikenresin MS series manufactured by Miki Riken Kogyo Co., Ltd.

It is preferable to use a catalyst with melamine resin and glyoxal resin to promote the reaction. Such catalysts are not particularly limited as long as they are commonly used, and examples include borofluoride compounds such as ammonium borofluoride and zinc borofluoride; neutral metal salt catalysts such as magnesium chloride and magnesium sulfate; and inorganic acids such as phosphoric acid, hydrochloric acid, and boric acid. If necessary, these catalysts can be used in combination with organic acids such as citric acid, tartaric acid, malic acid, maleic acid, and lactic acid as co-catalysts. Examples of such catalysts include Catalyst ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, and Catalyst NFC-1 manufactured by DIC Corporation; Unika Catalyst 3-P and Unika Catalyst MC-109 manufactured by Union Chemical Industry Co., Ltd.; and Riken Fixer RC series, Riken Fixer MX series, and Riken Fixer RZ-5 manufactured by Miki Riken Kogyo Co., Ltd.

(Surfactant)
As the surfactant, for example, a polyalkylene oxide adduct can be used, and other surfactants may be further combined. For example, the other surfactant may be one that serves to expand the temperature range in which the emulsion state is stably maintained and to adjust the amount of foaming that occurs when the emulsion is mixed with water to prepare a diluted solution. The other surfactant may be any one of a nonionic surfactant, anionic surfactant, cationic surfactant, and amphoteric surfactant. The other surfactants may be used alone or in combination of two or more.

(Antifoaming agent)
The defoaming agent is not particularly limited, and examples thereof include oil-based defoaming agents such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; fatty acid-based defoaming agents such as stearic acid, oleic acid, and palmitic acid; fatty acid ester-based defoaming agents such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, and butyl stearate; alcohol-based defoaming agents such as polyoxyalkylene monohydric alcohol, di-t-amylphenoxyethanol, 3-heptanol, and 2-ethylhexanol; ether-based defoaming agents such as 3-heptyl cellosolve, nonyl cellosolve, and 3-heptyl carbitol; phosphate ester-based defoaming agents such as tributyl phosphate and tris(butoxyethyl)phosphate; amine-based defoaming agents such as diamylamine; amide-based defoaming agents such as polyalkylene amides and acylate polyamines; sulfate ester-based defoaming agents such as sodium lauryl sulfate; and mineral oil. The antifoaming agents can be used alone or in combination of two or more.

(organic acid)
The organic acid is not particularly limited, and examples thereof include lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, methanesulfonic acid, toluenesulfonic acid, etc. The organic acids can be used alone or in combination of two or more.

(Inorganic acid)
The inorganic acid is not particularly limited, and examples thereof include hydrogen chloride, sulfuric acid, nitric acid, etc. The inorganic acids may be used alone or in combination of two or more.

(alcohol)
The alcohol is not particularly limited, and examples thereof include ethanol, isopropanol, glycerin, trimethylolpropane, diethylene glycol, triethylene glycol, dipropylene glycol, propylene glycol, etc. The alcohols can be used alone or in combination of two or more.

(Antistatic Agent)
It is preferable to use an antistatic agent that does not easily impair water-repellent performance. Examples of antistatic agents include cationic surfactants such as higher alcohol sulfate salts, sulfated oils, sulfonates, quaternary ammonium salts, and imidazoline-type quaternary salts, nonionic surfactants such as polyethylene glycol-type and polyhydric alcohol ester-type, amphoteric surfactants such as imidazoline-type quaternary salts, alanine-type and betaine-type, and polymer compound-type agents such as the antistatic polymers and polyalkylamines described above. Antistatic agents can be used alone or in combination of two or more.

The water repellent composition according to the present embodiment described above can be suitably used in applications such as textile product processing agents, paper product processing agents, and leather product processing agents.

[Method of producing water repellent composition]
The method for producing the water repellent composition of this embodiment will be described below.

The water repellent composition of this embodiment can be obtained by mixing the amino-modified silicone, silicone resin, and alkylpolysiloxane described above. The content of each of the above-mentioned components in the water repellent composition of this embodiment can be the preferred blending amount described above.

The water repellent composition of this embodiment may be a one-component type in which the amino-modified silicone (component (I)), silicone resin (component (II)), and alkylpolysiloxane (component (III)) are pre-mixed; a two-component type in which one component is a mixture of two of the three components and the other component is pre-mixed; or a three-component type in which each of the three components is separate. From the perspective of ease of handling, it is preferable that the water repellent composition of this embodiment has the three components dispersed (including emulsified and dissolved) in an aqueous medium.

When the components (I), (II), and (III) are premixed to form a single-component formulation, the water repellent composition of this embodiment can be obtained by simultaneously dispersing (including emulsifying and dissolving) the components (I), (II), and (III) in an aqueous medium, or by mixing a dispersion in which at least one of the three components is dispersed in an aqueous medium with a dispersion in which the other components are dispersed in an aqueous medium, or by mixing dispersions of the components (I), (II), and (III).

One method for dispersing each of the above components in an aqueous medium is, for example, mixing and stirring each component with the aqueous medium and, if necessary, a dispersant. When mixing and stirring, a conventional emulsifying and dispersing machine such as a milder, high-speed mixer, homogenizer, ultrasonic homogenizer, homomixer, bead mill, pearl mill, dyno mill, aspek mill, basket mill, ball mill, nanomizer, ultimizer, or starburst may be used. These emulsifying and dispersing machines may be used alone or in combination of two or more.

The aqueous medium is preferably water or a mixed solvent of water and a hydrophilic solvent that is miscible with water. Examples of hydrophilic solvents include methanol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, hexylene glycol, glycerin, butyl glycol, butyl diglycol, sorbite, N-methylpyrrolidone, dimethylformamide, and dimethyl sulfoxide.

From the viewpoint of dispersion stability, it is preferable that the dispersion liquid further contains a surfactant. Such surfactants are not particularly limited as long as they can improve emulsion dispersion stability, and examples include known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. These can be used alone or in combination of two or more.

The above dispersion may be used as a treatment liquid directly in the water-repellent treatment, or it may be further diluted with an aqueous medium or a hydrophobic organic solvent to form a treatment liquid. The dispersion may be used unneutralized (without neutralization), or the pH may be adjusted by a method such as neutralizing the amino-modified silicone. When adjusting the pH, the pH of the treatment liquid can be adjusted to 5.5 to 6.5.

[Water-repellent textile products]
The present embodiment also provides a water-repellent textile product having fibers and the water repellent composition of the present embodiment attached to the fibers. A method for producing the water-repellent textile product of the present embodiment will be described below.

Water-repellent textile products can be produced by a method including a step of treating textiles with a treatment liquid containing the water-repellent composition of this embodiment described above.

There are no particular restrictions on the fiber material, and examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as nylon, polyester, polyurethane, and polypropylene; and composite and blended fibers of these. The fiber may be in any form, such as yarn, cloth, nonwoven fabric, or paper. The fiber may also be a textile product.

Methods for treating fibers with a treatment liquid containing the water repellent composition of this embodiment include, for example, a one-step treatment method using a treatment liquid containing components (I), (II), and (III), a two-step treatment method using a treatment liquid containing two of the above three components and a treatment liquid containing another component, and a three-step treatment method using three dispersions each containing the above three components separately. When treating with a two-step or three-step method, the order in which the components are treated can be any order.

The above-mentioned treatment liquids and dispersions may be used unneutralized (without being neutralized), or may have their pH adjusted to 5.5 to 6.5. The pH can be adjusted using, for example, organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, methanesulfonic acid, and toluenesulfonic acid; inorganic acids such as hydrogen chloride, sulfuric acid, and nitric acid; hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate, and sodium sesquicarbonate; organic amines such as monoethanolamine, diethanolamine, triethanolamine, and triethylamine; and ammonia.

Methods for treating fibers with the treatment solution include, for example, padding, immersion, spraying, and coating. Furthermore, if the water repellent composition contains water, it is preferable to dry the fiber after applying it to remove the water.

The amount of water repellent composition applied to the fibers in this embodiment can be adjusted as appropriate depending on the required level of water repellency, but it is preferable to adjust the amount of water repellent composition applied to 100 g of fibers to 0.1 to 5 g, and more preferably 0.1 to 3 g. When the amount of water repellent composition applied is 0.1 g or more, the fibers tend to more easily exhibit sufficient water repellency, while when it is 5 g or less, the texture of the fibers tends to be further improved and is also economically advantageous.

Furthermore, after the water repellent composition of this embodiment has been applied to the fibers, it is preferable to perform an appropriate heat treatment. There are no particular restrictions on the temperature conditions, but from the standpoints of water repellency, durable water repellency, and texture, it is preferable to perform the treatment at 110 to 180°C for 1 to 5 minutes.

The water-repellent textile product of this embodiment exhibits excellent water repellency and a soft texture, making it suitable for textile applications such as down jacket coverings, coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, gloves, hats, futon coverings, futon drying rack covers, curtains, and tents, as well as other clothing and non-clothing applications.

The present invention will be further explained below using examples, but the present invention is not limited to these examples in any way.

<Preparation of Amino-Modified Silicone Dispersion>
(Preparation example A1)
30 parts by mass of KF8005 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as an amino-modified silicone, 0.3 parts by mass of formic acid, and 1 part by mass of an ethylene oxide 5-mol adduct of a branched alcohol having 12 to 14 carbon atoms were mixed. Next, 68.7 parts by mass of water was added little by little to the obtained mixture while mixing, and a dispersion containing 30% by mass of amino-modified silicone was obtained.

(Preparation examples A2 to A7)
A dispersion containing 30% by mass of amino-modified silicone was obtained in the same manner as in Preparation Example A1, except that the amino-modified silicone was changed from KF8005 to the amino-modified silicone shown in Table 1. Note that KF-868, KF-864, and KF-393 are trade names manufactured by Shin-Etsu Chemical Co., Ltd., SF-8417 and BY16-853U are trade names manufactured by Dow-Toray Co., Ltd., and XF42-B1989 is a trade name manufactured by Momentive Performance Materials Japan, LLC.

<Physical properties of amino-modified silicone>
Table 1 shows the functional group equivalent weight (unit: g/mol) and kinematic viscosity at 25° C. (unit: mm ² /s) of the amino-modified silicone used above.
The kinematic viscosity at 25°C is a value measured by the method described in JIS K 2283:2000 (Ubbelohde viscometer).

(Preparation example A8)
30 parts by mass of the above-mentioned SF-8417 (trade name, manufactured by Dow Toray Industries, Inc.) as an amino-modified silicone was mixed with 1 part by mass of an ethylene oxide 5-mol adduct of a branched alcohol having 12 to 14 carbon atoms. Next, 69.0 parts by mass of water was added little by little to the resulting mixture while mixing, to obtain a dispersion containing 30% by mass of the amino-modified silicone.

<Preparation of Alkylpolysiloxane Dispersion>
(Preparation example B)
30 parts by mass of dimethylsilicone (kinematic viscosity at 25°C: ¹⁰⁰ mm/s, manufactured by Dow Toray Co., Ltd.) as an alkylpolysiloxane was mixed with 1 part by mass of an ethylene oxide 5-mol adduct of a branched alcohol having 12 to 14 carbon atoms. Next, 69 parts by mass of water was added little by little with mixing to obtain a dispersion containing 30% by mass of alkylpolysiloxane.

<Preparation of Silicone Resin Dispersion>
(Preparation example C1)
25 parts by mass of MQ-1600 (trimethylsilyl group-containing polysiloxane, product name, manufactured by Dow Toray Industries, Inc.) as a silicone resin was mixed with 25 parts by mass of volatile dimethyl silicone (kinematic viscosity at 25°C ¹ mm/s, manufactured by Dow Toray Industries, Inc.) as a solvent until the silicone resin was dissolved, and then 5 parts by mass of an ethylene oxide 5-mol adduct of a C10 branched alcohol and 1 part by mass of Arcard T-28 (stearyltrimethylammonium chloride) were further mixed in. Next, 44 parts by mass of water was added little by little with mixing to obtain a dispersion containing 25% by mass of silicone resin.

(Preparation example C2, C5 to C9)
A dispersion containing 25% by mass of silicone resin was obtained in the same manner as in Preparation Example C1, except that the silicone resin was changed from MQ-1600 to a silicone resin shown in Table 2.

(Preparation examples C3, C4)
A dispersion containing 25% by mass of silicone resin was obtained in the same manner as in Preparation Example C1, except that the silicone resin was changed from MQ-1600 to a mixture of a silicone resin and an alkylpolysiloxane (as a solvent) shown in Table 2.
The "non-volatile content" values in Table 2 are those listed in the product catalog for MQ-1600, KF-9021L, and KF7312L, and for the other products, they are shown as 100% based on the description in the product catalog that they are in powder form.

The above silicone resin preparation examples are summarized in Table 2.

<Preparation of Polyfunctional Isocyanate Compound Dispersion>
(Preparation Example D1: Dispersion of methyl ethyl ketoxime-blocked reaction product of trimethylolpropane and toluene diisocyanate)
First, Polurene AD (trade name, manufactured by SAPIC Corporation, containing 75% by mass of a reaction product of trimethylolpropane and toluene diisocyanate (2,4 isomer to 2,6 isomer in a mass ratio of 80:20), solvent: ethyl acetate) was prepared as a reaction product of trimethylolpropane and toluene diisocyanate.

One mole (308.4 g) of the reaction product of trimethylolpropane and toluene diisocyanate prepared above was heated to 60-70°C. Next, 3 moles (261.4 g) of methyl ethyl ketoxime was slowly added, and the mixture was allowed to react at 60-70°C until the isocyanate content, as confirmed by infrared spectrophotometer, reached zero. Ethyl acetate was then added, yielding a colorless, transparent, viscous liquid composition containing 98.7% by mass of a methyl ethyl ketoxime-blocked polyisocyanate compound.

180 parts by mass of the composition obtained above was mixed with 20 parts by mass of a 30 mole ethylene oxide adduct of 3-styrenated phenol as a nonionic surfactant and homogenized. Water was gradually added while stirring, and the mixture was then homogenized at a pressure of 30 MPa to obtain a dispersion containing 40% by mass of a methyl ethyl ketoxime-blocked product of the reaction product of trimethylolpropane and toluene diisocyanate.

(Preparation Example D2: Dispersion of methyl ethyl ketoxime-blocked isocyanurate-type hexamethylene diisocyanate)
To a reaction vessel, 1 mole (504.6 g) of Duranate THA-100 (an isocyanurate type of hexamethylene diisocyanate, NCO functionality: 3, content: 100% by mass, product name: Asahi Kasei Chemicals Corporation) and methyl isobutyl ketone were added and heated to 60 to 70° C. Next, 3 moles (261.4 g) of methyl ethyl ketoxime were slowly added, and the reaction was carried out at 60 to 70° C. until the isocyanate content, as confirmed by infrared spectrophotometer, reached zero, thereby obtaining a colorless, transparent, viscous liquid composition containing 98.7% by mass of a methyl ethyl ketoxime-blocked polyisocyanate compound.

180 parts by mass of the composition obtained above, 20 parts by mass of methyl ethyl ketone as an organic solvent, and 20 parts by mass of 3-styrenated phenol ethylene oxide 30 mole adduct as a nonionic surfactant were mixed and homogenized. Water was gradually added while stirring, and then the mixture was homogenized at a pressure of 30 MPa to obtain a dispersion containing 40% by mass of methyl ethyl ketoxime-blocked isocyanurate-type hexamethylene diisocyanate.

<Production of water-repellent textile products>
Example 1
A treatment bath was obtained by diluting these with water to contain 0.13 mass% of the amino-modified silicone dispersion obtained in Preparation Example A1, 3.16 mass% of the alkylpolysiloxane dispersion obtained in Preparation Example B, 4.05 mass% of the silicone resin dispersion obtained in Preparation Example C1, 0.50 mass% of Nicepol FE-26 (antistatic agent, product name of NICCA Chemical Co., Ltd.), and 0.50 mass% of Textport BG-290 (penetrating agent, product name of NICCA Chemical Co., Ltd.). Using this treatment bath, a 100% polyester fabric that had been dyed was pad-treated at 15 to 40°C (pickup rate 60 mass%) and then heat-treated at 180°C for 1 minute to obtain a water-repellent textile product. The table also shows the mass ratio of the amount of silicone resin to the amount of amino-modified silicone, and the mass ratio of the amount of silicone resin to the total amount of amino-modified silicone and alkylpolysiloxane.

(Examples 2 to 35, Comparative Examples 1 to 7)
Water-repellent textile products were obtained in the same manner as in Example 1, except that the amino-modified silicone dispersion shown in Table 1 was used instead of the amino-modified silicone dispersion obtained in Preparation Example A1, and the blending amounts (mass %) of the alkylpolysiloxane dispersion shown in Preparation Example B and the silicone resin dispersions shown in Preparation Examples C1 to C9 in Table 2 were changed as shown in Tables 3 to 7.
The water-repellent textile products obtained above were measured for water repellency, repellency, water pressure resistance, abrasion resistance, durable water repellency (i.e., water repellency after washing), durable repellency (i.e., repellency after washing), durable water pressure resistance (i.e., water pressure resistance after washing), durable abrasion resistance (i.e., abrasion resistance after washing), texture, carry-in resistance, and seam slippage using the following methods. The results are shown in Tables 3 to 7.

(Evaluation of water repellency of textile products)
The test was conducted in accordance with the spray method of JIS L 1092 (2009) with a shower water temperature of 20°C. The results were visually evaluated using the following grades. Note that if the characteristics were slightly better, a "+" was added to the grade, and if the characteristics were between grades 4 and 5, for example, the grade was rated as "4-5."
Water repellency: Condition 5: No adhesion or wetting on the surface 4: Slight adhesion or wetting on the surface 3: Partial wetting on the surface 2: Wetting on the surface 1: Wetting on the entire surface 0: Complete wetting on both the front and back surfaces

(Evaluation of durable water repellency of textile products)
The water-repellent textile product was washed 20 times (L-20) according to the C4M method 1930 of JIS L 1930 (2014), and the water repellency after air drying was evaluated in the same manner as the water repellency evaluation method described above.

(Evaluation of repellency and durable repellency of textile products)
The test was conducted in accordance with the spray method of JIS L 1092 (2009) with a shower water temperature of 20°C. The results were visually evaluated using the following grades. Note that if the characteristics were slightly better, a "+" was added to the grade, and if the characteristics were between grades 4 and 5, for example, the grade was rated as "4-5."
Repellency: Condition 5: Water droplets are repelled from the fabric at an angle of 45° or more; 4: Water droplets are repelled from the fabric at an angle of less than 45°; 3: Water droplets are not repelled but flow in a straight line; 2: Water droplets flow in a meandering pattern; 1: The entire surface is wet; 0: Both the front and back surfaces are completely wet. Durable repellency was evaluated by washing 20 times (L-20) according to the C4M method of JIS L 1930 (2014) and measuring the repellency after air drying.

(Evaluation of water pressure resistance and durable water pressure resistance of textile products)
The water pressure resistance of a textile product was measured by applying pressure to a 210 mm x 210 mm test piece cut out of the textile product using a high-pressure water pressure tester WP-100K (manufactured by Daiei Scientific Instruments) at an acceleration rate of 60 cmAq/min, and measuring the water pressure at which three drops of water leaked from the test piece. Furthermore, the durable water pressure resistance was measured by washing the test piece 20 times (L-20) according to the C4M method of JIS L 1930 (2014) and then air-drying it.

(Evaluation of abrasion resistance and durable abrasion resistance of textile products)
Water repellency after Martindale abrasion (load: 9 kPa, cycle: 1000) was evaluated according to the aforementioned (Water Repellency Evaluation of Textile Products). Durable abrasion resistance was evaluated by washing 20 times (L-20) according to the C4M method of JIS L 1930 (2014), air drying, and then Martindale abrasion (load: 9 kPa, cycle: 1000) according to the aforementioned (Water Repellency Evaluation of Textile Products). Martindale abrasion was evaluated in accordance with ISO 12947.2-1998: Test for abrasion and pilling resistance of fabrics by the Martindale method - Part 2: Measurement of specimen damage.

(Evaluation of resistance to import of textile products)
A treatment bath described in the Examples and Comparative Examples was prepared by dissolving 200 ppm of Dispatex K (anionic polymer, water, manufactured by Nicca Chemical Co., Ltd.), 200 ppm of Nikka Sunsalt 1200K (anionic polymer, nonionic surfactant, water, manufactured by Nicca Chemical Co., Ltd.), and 200 ppm of Glauber's salt. Using this treatment bath, textile products were pad-treated at 15 to 40°C, followed by heat treatment at 180°C for 1 minute to obtain water-repellent textile products. The water repellency of the resulting water-repellent textile products was evaluated according to the above-mentioned (Evaluation of water repellency of textile products).

(Textile product texture evaluation)
The water-repellent textile products were evaluated by handling according to the following five-point scale.
1: Hard to 5: Soft

(Seam slippage of textile products)
The seam slippage resistance of the water-repellent textile product was measured according to JIS L 1096:2010, 8.23 Slippage Resistance, 8.23.1 Seam Slippage Method b) Method B. The smaller the value, the better the seam slippage resistance, and a value of 4 mm or less was judged to be good.

The water-repellent textile products treated with the water-repellent compositions of Examples 1 to 35 were confirmed to have excellent water repellency, durable water repellency, repellency, durable repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, feel, and resistance to contamination.

The present invention provides a water repellent composition that can be used to obtain water-repellent textile products that have excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, texture, and resistance to carry-in.

Claims (4)

A water repellent composition containing an amino-modified silicone, a silicone resin, and an alkylpolysiloxane, wherein the amount of the silicone resin is 1,000 to 5,000 parts by mass per 100 parts by mass of the amino-modified silicone, and the amount of the silicone resin is in the range of 60 to 130 parts by mass per 100 parts by mass of the total amount of the amino-modified silicone and the alkylpolysiloxane. The water repellent composition according to claim 1, wherein the functional group equivalent weight of the amino-modified silicone is 100 to 20,000 g/mol. A method for producing a water-repellent textile product, comprising a step of treating textiles with a treatment liquid containing the water repellent composition according to claim 1 or 2. A water-repellent textile product comprising fibers and the water-repellent composition according to claim 1 or 2 attached to the fibers.