JP2024096808A - Water repellent composition for fibers, water repellent textile product, and method for producing water repellent textile product - Google Patents

Abstract

［式（Ａ－１）中、Ｒ^１は水素又はメチル基を表し、Ｒ^２は置換基を有していてもよい炭素数１２以上の１価の炭化水素基を表す。］
【選択図】なし[Problem] To provide a water repellent composition for fibers that can impart excellent initial water repellency, durable water repellency, and water penetration resistance to a fiber substrate, and that can enable the fiber substrate to which such properties have been imparted to have sufficient peel strength, and to provide a water repellent fiber product and a method for producing a water repellent fiber product using the same.
[Solution] The water repellent composition contains an acrylic resin having a constituent unit derived from a (meth)acrylic acid ester monomer (A) represented by the following general formula (A-1) and/or a urethane resin having a structural unit derived from a polyfunctional compound and a structural unit derived from an isocyanate compound, an organo-modified silicone, and a wax.

[In formula (A-1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.]
[Selection diagram] None

Description

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

Conventionally, fluorine-based water repellents having fluoroalkyl groups have been known as water repellents used in water repellent processing, and textile products with water repellency can be obtained by treating the surface of textiles with such fluorine-based water repellents. However, although textile products treated with fluorine-based water repellents exhibit excellent water repellency, concerns about the environmental impact of the long-chain fluoroalkyl compounds used have become apparent, and there has been an international demand for non-fluorine-based water repellents that do not contain any fluorine-based compounds and yet exhibit high water repellency comparable to that of fluorine-based water repellents.

In recent years, therefore, research has been conducted into non-fluorine-based water repellents that do not contain fluorine. For example, the following Patent Document 1 discloses a fiber processing agent that contains at least one of a silicon-based compound, a wax-based compound, and a wax-zirconium-based compound. The following Patent Document 2 proposes a softening water repellent that contains an amino-modified silicone and a polyfunctional isocyanate. Furthermore, the following Patent Document 3 proposes a water repellent made of a specific non-fluorine-based polymer that contains, as a monomer unit, a (meth)acrylic acid ester whose ester portion has 12 or more carbon atoms.

JP 2006-124866 A JP 2004-59609 A JP 2006-328624 A

However, although conventional non-fluorinated water repellents are recognized to have an initial water repellency effect in the spray method of JIS L 1092 (2009), which is one of the common water repellency evaluation tests, they have not always achieved sufficient results in evaluation tests that assume practical use and actual wear of textile products. For practical use, durable water repellency that does not decrease even with repeated washing is required. For actual wear, it is required to be able to prevent water penetration for a long period of time. If the water penetration prevention ability is insufficient, when water droplets remain on the fiber surface for a certain period of time, some of the water droplets may penetrate into the fiber over time, causing the opposite surface to become wet. Conventional non-fluorinated water repellents still have insufficient performance in practical use and on actual wear surfaces compared to fluorinated water repellents.

In some cases, water-repellent textile products and the like are treated by coating specific areas with urethane resin, acrylic resin, or the like. In such cases, the textile products are required to have sufficient water repellency, but the areas to which the coating is applied must be difficult to peel off. The difficulty of a coating to peel off can be evaluated by measuring the stress (peel strength) required to peel off the coating film from the water-repellent textile substrate. However, such peel strength has not been fully studied for conventional non-fluorine-based water repellents, and there is room for further improvement in order to achieve a higher level of both the above-mentioned practical and adhesive performance and peel strength.

The present invention has been made in consideration of the above circumstances, and aims to provide a water repellent composition for fibers that can impart excellent initial water repellency, durable water repellency, and water penetration resistance to a fiber substrate, and that can provide a fiber substrate to which such properties have been imparted with sufficient peel strength, as well as a water repellent fiber product and a method for producing a water repellent fiber product using the same.

As a result of intensive research conducted by the present inventors to solve the above problems, they discovered that fabrics treated with a water repellent composition containing a specific resin, a specific silicone, and a wax not only exhibit excellent initial water repellency, but also show good results in evaluations of durable water repellency after washing, resistance to water penetration, and peel strength, and they have completed the present invention based on this finding.

One aspect of the present invention relates to a water repellent composition for fibers that contains an acrylic resin having a structural unit derived from a (meth)acrylic acid ester monomer (A) represented by the following general formula (A-1) and/or a urethane resin having a structural unit derived from a polyfunctional compound represented by the following general formula (I-1) and a structural unit derived from an isocyanate compound represented by the following general formula (II-1), an organo-modified silicone represented by the following general formula (L-1), and a wax.

［式（Ａ－１）中、Ｒ^１は水素又はメチル基を表し、Ｒ^２は置換基を有していてもよい炭素数１２以上の１価の炭化水素基を表す。］

[In formula (A-1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.]

R ³¹ [-W ¹ -R ³² ] _d [-V ¹ ] _e (I-1)
In formula (I-1), d represents an integer of 1 or more, e represents an integer of 2 or more, (d+e) is 3 to 6, and R ³¹ represents a (d+e)-valent organic group; W ¹ represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group; R ³² represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms; V ¹ represents a hydroxyl group; represents a hydroxy group, an amino group, or a carboxy group, provided that at least two of the e V ^1s are hydroxy groups and/or amino groups.

R ³³ [-NCO] _f (II-1)
[In formula (II-1), R ³³ represents an f-valent organic group, and f represents an integer of 2 to 7.]

［式（Ｌ－１）中、Ｒ^２２０、Ｒ^２２１及びＲ^２２２はそれぞれ独立に、水素原子、メチル基、エチル基又は炭素数１～４のアルコキシ基を表し、Ｒ^２２３は、芳香族環を有する炭素数８～４０の炭化水素基、又は炭素数３～２２のアルキル基を表し、Ｒ^２３０、Ｒ^２３１、Ｒ^２３２、Ｒ^２３３、Ｒ^２３４及びＲ^２３５はそれぞれ独立に、水素原子、メチル基、エチル基、炭素数１～４のアルコキシ基、芳香族環を有する炭素数８～４０の炭化水素基、又は炭素数３～２２のアルキル基を表し、ａ１は０以上の整数を表し、ａ２は１以上の整数を表し、（ａ１＋ａ２）は１０～２００であり、ａ１が２以上の場合、複数存在するＲ^２２０及びＲ^２２１はそれぞれ同一であっても異なっていてもよく、ａ２が２以上の場合、複数存在するＲ^２２２及びＲ^２２３はそれぞれ同一であっても異なっていてもよい。］

[In formula (L-1), R ²²⁰ , R ²²¹ and R ²²² each independently represent a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms; R ²²³ represents a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; a1 represents an integer of 0 or more; a2 represents an integer of 1 or more; (a1+a2) is 10 to 200; when a1 is 2 or more, a plurality of R ²²⁰ and R ²²¹ may be the same or different, and when a2 is 2 or more, a plurality of R ²²² and R ²²³ may be the same or different.

The water repellent composition for fibers of the present invention can impart excellent initial water repellency, durable water repellency, and water penetration resistance to a fiber substrate, and can also provide a fiber substrate that has sufficient peel strength while still having these properties. This makes it possible to realize a water-repellent fiber product that has performance suited to practical use and wearability.

The water repellent composition for fibers of the present invention is a water repellent composition that does not contain a fluoroalkyl group or a compound having fluorine, but can still provide excellent water repellency (the effect of increasing the contact angle with water), and can therefore be used as an alternative to fluorine-based water repellents, eliminating concerns about the impact on the environment, etc. Furthermore, the water repellent composition for fibers of the present invention can provide a fiber substrate that has sufficient peel strength while being provided with the above-mentioned excellent initial water repellency, durable water repellency, and water penetration resistance, while fully maintaining the texture of the fiber substrate.

In the water repellent composition for fibers of the present invention, the acrylic resin may further have a structural unit derived from at least one monomer (E) selected from vinyl chloride and vinylidene chloride.

The water repellent composition for fibers of the present invention may further contain a crosslinking agent.

Another aspect of the present invention relates to a water-repellent textile product comprising a textile substrate and the water repellent composition for textiles according to the present invention adhered to the textile substrate.

The water-repellent textile product of the present invention is endowed with excellent initial water repellency, durable water repellency, and water penetration resistance by the water repellent composition for textiles of the present invention, and furthermore, when a coating process is applied, it can have sufficient peel strength. Therefore, the water-repellent textile product of the present invention can have performance suited to practical use and wearability.

Yet another aspect of the present invention relates to a method for producing a water-repellent textile product, comprising a step of contacting a textile substrate with a treatment liquid containing the water-repellent composition according to the present invention.

The method for producing a water-repellent textile product of the present invention makes it possible to obtain a water-repellent textile product that has excellent initial water repellency, durable water repellency, and water penetration resistance, and also has sufficient peel strength.

The present invention provides a water repellent composition for fibers that can impart excellent initial water repellency, durable water repellency, and water penetration resistance to a fiber substrate, and can provide a fiber substrate imparted with such properties with sufficient peel strength, as well as a water repellent fiber product and a method for producing a water repellent fiber product using the same.

A preferred embodiment of the present invention is described below.

In this specification, "(meth)acrylic acid ester" means "acrylic acid ester" or the corresponding "methacrylic acid ester", and is synonymous with "(meth)acrylic acid", "(meth)acrylamide", etc.

In this specification, an ester group refers to a group represented by -O-CO-. An amide group refers to a group represented by -NH-CO-. A urethane group refers to a group represented by -O-CO-NH-. A urea group refers to a group represented by -NH-CO-NH-. An isocyanate group refers to a group represented by -N=C=O. A carbonyl group refers to a group represented by -CO-.

In this specification, a textile substrate is an object to be treated with a water repellent composition to be water repellent, and may be a textile product or a textile material that constitutes a textile product.

The water repellent composition for fibers according to this embodiment contains an acrylic resin (hereinafter also referred to as "acrylic resin") having a structural unit derived from a (meth)acrylic acid ester monomer (A) represented by the following general formula (A-1) and/or a urethane resin (hereinafter also referred to as "urethane resin") having a structural unit derived from a polyfunctional compound represented by the following general formula (I-1) and a structural unit derived from an isocyanate compound represented by the following general formula (II-1), an organo-modified silicone (hereinafter also referred to as "organo-modified silicone") represented by the following general formula (L-1), and a wax.

［式（Ａ－１）中、Ｒ^１は水素又はメチル基を表し、Ｒ^２は置換基を有していてもよい炭素数１２以上の１価の炭化水素基を表す。］

[In formula (A-1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.]

R ³¹ [-W ¹ -R ³² ] _d [-V ¹ ] _e (I-1)
In formula (I-1), d represents an integer of 1 or more, e represents an integer of 2 or more, (d+e) is 3 to 6, and R ³¹ represents a (d+e)-valent organic group; W ¹ represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group; R ³² represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms; V ¹ represents a hydroxyl group; represents a hydroxy group, an amino group, or a carboxy group, provided that at least two of the e V ^1s are hydroxy groups and/or amino groups.

R ³³ [-NCO] _f (II-1)
[In formula (II-1), R ³³ represents an f-valent organic group, and f represents an integer of 2 to 7.]

［式（Ｌ－１）中、Ｒ^２２０、Ｒ^２２１及びＲ^２２２はそれぞれ独立に、水素原子、メチル基、エチル基又は炭素数１～４のアルコキシ基を表し、Ｒ^２２３は、芳香族環を有する炭素数８～４０の炭化水素基、又は炭素数３～２２のアルキル基を表し、Ｒ^２３０、Ｒ^２３１、Ｒ^２３２、Ｒ^２３３、Ｒ^２３４及びＲ^２３５はそれぞれ独立に、水素原子、メチル基、エチル基、炭素数１～４のアルコキシ基、芳香族環を有する炭素数８～４０の炭化水素基、又は炭素数３～２２のアルキル基を表し、ａ１は０以上の整数を表し、ａ２は１以上の整数を表し、（ａ１＋ａ２）は１０～２００であり、ａ１が２以上の場合、複数存在するＲ^２２０及びＲ^２２１はそれぞれ同一であっても異なっていてもよく、ａ２が２以上の場合、複数存在するＲ^２２２及びＲ^２２３はそれぞれ同一であっても異なっていてもよい。］

[In formula (L-1), R ²²⁰ , R ²²¹ and R ²²² each independently represent a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms; R ²²³ represents a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; a1 represents an integer of 0 or more; a2 represents an integer of 1 or more; (a1+a2) is 10 to 200; when a1 is 2 or more, a plurality of R ²²⁰ and R ²²¹ may be the same or different, and when a2 is 2 or more, a plurality of R ²²² and R ²²³ may be the same or different.

Hereinafter, the above acrylic resin and urethane resin may be referred to as the "(α) component", the above organo-modified silicone as the "(β) component", and the wax as the "(γ) component".

The component (α) contained in the water repellent composition according to this embodiment is described in detail below.

The (α) component is preferably an acrylic resin. When the (α) component is an acrylic resin, it becomes easier to improve the initial water repellency or the durable water repellency, or both (hereinafter, simply referred to as "water repellency"), and the water penetration prevention property.

The following explains acrylic resin.

The (meth)acrylic acid ester monomer (A) (hereinafter also referred to as "monomer (A)") used in this embodiment and represented by the above general formula (A-1) has a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent. This hydrocarbon group may be linear or branched, may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic or aromatic ring. Among these, from the viewpoint of water repellency and water penetration prevention properties, a linear one is preferable, and a linear alkyl group is more preferable. When the monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, the substituent may be one or more of a hydroxy group, an amino group, a carboxy group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloyloxy group. In this embodiment, in the above general formula (A-1), R ² is preferably an unsubstituted hydrocarbon group.

The number of carbon atoms in the hydrocarbon group is preferably 12 to 24, and more preferably 12 to 22. When the number of carbon atoms in the hydrocarbon group is within this range, it becomes easy to improve the water repellency and water penetration prevention properties imparted to the fiber substrate while adequately maintaining the texture of the fiber substrate. From the same viewpoint as above, it is more preferable that the hydrocarbon group is a linear alkyl group having 15 to 22 carbon atoms, and even more preferable that it is a linear alkyl group having 15 to 20 carbon atoms.

Examples of the monomer (A) include stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, behenyl (meth)acrylate, ceryl (meth)acrylate, and melissyl (meth)acrylate.

The monomer (A) may have at least one functional group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an epoxy group, and an isocyanate group that can react with a crosslinking agent described later. In this case, it becomes easier to improve the water repellency and water penetration prevention properties imparted to the fiber substrate. The isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. In addition, when the monomer (A) has an amino group, the texture of the obtained fiber product can be further improved.

The monomer (A) is preferably a monofunctional (meth)acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

The monomer (A) may be used alone or in combination of two or more.

From the viewpoint of improving the water repellency and water penetration prevention properties imparted to the fiber substrate, it is preferable to use the above-mentioned monomer (A) in combination with an acrylic acid ester monomer (a1) (hereinafter also referred to as "(a1) component") and a methacrylic acid ester monomer (a2) (hereinafter also referred to as "(a2) component"). The ratio (a1)/(a2) of the mass of the (a1) component to the mass of the (a2) component to be blended is preferably 30/70 to 90/10, more preferably 40/60 to 85/15, even more preferably 50/50 to 80/20, and particularly preferably 60/40 to 80/20. When (a1)/(a2) is within the above range, it is easy to improve the water repellency and water penetration prevention properties imparted to the fiber substrate.

When the water repellent composition of this embodiment contains an acrylic resin as component (α), the total composition ratio of the monomer (A) in the acrylic resin may be 50 to 100% by mass, and from the viewpoint of improving the water repellency and water penetration prevention properties imparted to the fiber substrate, it is preferably 50 to 99% by mass, more preferably 60 to 99% by mass, and even more preferably 70 to 99% by mass, based on the total amount of the monomer components constituting the acrylic resin.

The weight average molecular weight of the acrylic resin is preferably 100,000 or more. When the weight average molecular weight is 100,000 or more, the water repellency of the resulting water-repellent textile product tends to be improved. Furthermore, from the viewpoint of further increasing the water repellency of the resulting water-repellent textile product, the weight average molecular weight of the acrylic resin is more preferably 500,000 or more. The upper limit of the weight average molecular weight of the acrylic resin is preferably about 5 million. In this specification, the weight average molecular weight refers to a value measured by GPC (gel permeation chromatography) and converted into standard polystyrene.

In this embodiment, the melt viscosity of the acrylic resin at 105°C is preferably 1000 Pa·s or less. When the melt viscosity at 105°C is 1000 Pa·s or less, a water-repellent textile product with excellent feel tends to be obtained. In addition, when the melt viscosity at 105°C is 1000 Pa·s or less, when the acrylic resin is emulsified or dispersed to prepare a water-repellent composition, the acrylic resin can be prevented from precipitating or settling, and the storage stability of the water-repellent composition tends to be improved. Furthermore, it is more preferable that the melt viscosity of the acrylic resin at 105°C is 500 Pa·s or less. In this case, the obtained water-repellent textile product has sufficient water repellency and also has a better feel.

From the viewpoint of improving water repellency and water penetration prevention properties, as well as emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the acrylic resin, the acrylic resin preferably contains, in addition to the monomer (A), at least one reactive emulsifier (B) (hereinafter also referred to as "reactive emulsifier (B)") selected from (B1) a compound represented by the following general formula (B-1) having an HLB of 7 to 18, (B2) a compound represented by the following general formula (B-2) having an HLB of 7 to 18, and (B3) a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil having a hydroxy group and a polymerizable unsaturated group and has an HLB of 7 to 18.

［式（Ｂ－１）中、Ｒ^３は水素又はメチル基を表し、Ｘは炭素数１～６の直鎖もしくは分岐のアルキレン基を表し、Ｙ^１は炭素数２～４のアルキレンオキシ基を含む２価の基を表す。］

[In formula (B-1), ^R3 represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and ^Y1 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.]

［式（Ｂ－２）中、Ｒ^４は重合性不飽和基を有する炭素数１３～１７の１価の不飽和炭化水素基を表し、Ｙ^２は炭素数２～４のアルキレンオキシ基を含む２価の基を表す。］

[In formula (B-2), ^R4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, and ^Y2 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.]

A "reactive emulsifier" is an emulsifying dispersant with radical reactivity, i.e., a surfactant that has one or more polymerizable unsaturated groups in the molecule, and can be copolymerized with a monomer such as a (meth)acrylic acid ester.

In this specification, unless otherwise specified, "HLB" refers to the HLB value calculated by the Griffin method, assuming that the ethyleneoxy group is a hydrophilic group and all other groups are lipophilic groups.

The HLB of the above compounds (B1) to (B3) is 7 to 18, and from the viewpoint of emulsion stability during and after emulsion polymerization or dispersion polymerization of the acrylic resin (hereinafter simply referred to as emulsion stability), it is preferably 9 to 15. Furthermore, from the viewpoint of storage stability of the water repellent composition, it is more preferable to use two or more reactive emulsifiers (B) having different HLBs within the above range in combination.

In the reactive emulsifier (B1) represented by the above general formula (B-1), R ³ is hydrogen or a methyl group, and is more preferably a methyl group in terms of copolymerizability with the monomer (A). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of the acrylic resin. Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The type, combination and number of additions of the alkyleneoxy group in Y ¹ can be appropriately selected so as to be within the above HLB range. In addition, when there are two or more types of alkyleneoxy groups, they can have a block addition structure or a random addition structure.

As the compound represented by the above general formula (B-1), the compound represented by the following general formula (b-1) is preferred.

［式（ｂ－１）中、Ｒ^３は水素又はメチル基を表し、Ｘは炭素数１～６の直鎖もしくは分岐のアルキレン基を表し、Ａ^１Ｏは炭素数２～４のアルキレンオキシ基を表し、ｍは上記ＨＬＢの範囲内になるように適宜選択することができ、具体的には、１～８０の整数が好ましく、ｍが２以上のときｍ個のＡ^１Ｏは同一であっても異なっていてもよい。］

[In formula (b-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, A ¹ O represents an alkyleneoxy group having 2 to 4 carbon atoms, and m can be appropriately selected so as to be within the above-mentioned HLB range, and specifically, an integer of 1 to 80 is preferable, and when m is 2 or more, m A ¹ O may be the same or different.]

In the compound represented by the general formula (b-1), R ³ is hydrogen or a methyl group, and more preferably a methyl group in terms of copolymerizability with the monomer (A). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of the acrylic resin. A ¹ O is an alkyleneoxy group having 2 to 4 carbon atoms. The type and combination of A ¹ O and the number of m can be appropriately selected so as to be within the above HLB range. In terms of emulsion stability of the acrylic resin, m is preferably an integer of 1 to 80, more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ O may be the same or different. In addition, when there are two or more types of A ¹ O, they can have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the above general formula (b-1) can be obtained by a conventionally known method and is not particularly limited. It can also be easily obtained from commercial products, such as "Latemul PD-420", "Latemul PD-430", and "Latemul PD-450" manufactured by Kao Corporation.

In the reactive emulsifier (B2) represented by the above general formula (B-2), ^R4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, such as a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, and a heptadecatrienyl group, etc. From the viewpoint of emulsion stability of the acrylic resin, ^R4 is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

^Y2 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The type, combination and number of added alkyleneoxy groups in ^Y2 can be appropriately selected so as to fall within the above-mentioned HLB range. In addition, when there are two or more types of alkyleneoxy groups, they can have a block addition structure or a random addition structure. In terms of emulsion stability of the acrylic resin, the alkyleneoxy group is more preferably an ethyleneoxy group.

As the compound represented by the above general formula (B-2), the compound represented by the following general formula (b-2) is preferred.

［式（ｂ－２）中、Ｒ^４は重合性不飽和基を有する炭素数１３～１７の１価の不飽和炭化水素基を表し、Ａ^２Ｏは炭素数２～４のアルキレンオキシ基を表し、ｎは上記ＨＬＢの範囲内になるように適宜選択することができ、具体的には、１～５０の整数が好ましく、ｎが２以上のときｎ個のＡ^２Ｏは同一であっても異なっていてもよい。］

[In formula (b-2), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, A ² O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n can be appropriately selected so as to be within the above-mentioned HLB range, and specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, the n A ² O may be the same or different.]

Examples of R ⁴ in the compound represented by the above general formula (b-2) include the same as R ⁴ in the above general formula (B-2).

A ² O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of emulsion stability of the acrylic resin, the type and combination of A ² O and the number of n can be appropriately selected so as to be within the above HLB range. In terms of emulsion stability of the acrylic resin, A ² O is more preferably an ethyleneoxy group, and n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and even more preferably an integer of 8 to 14. When n is 2 or more, the n A ² O may be the same or different. In addition, when there are two or more types of A ² O, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B2) represented by the above general formula (b-2) can be synthesized by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group using a conventionally known method, and is not particularly limited. For example, it can be synthesized by adding a predetermined amount of alkylene oxide under pressure at 120 to 170°C using an alkali catalyst such as caustic soda or caustic potassium.

The above-mentioned phenols having the corresponding unsaturated hydrocarbon group include not only pure products or mixtures produced industrially, but also those that exist as pure products or mixtures extracted and purified from plants, etc. Examples include 3-[8(Z),11(Z),14-pentadecatrienyl]phenol, 3-[8(Z),11(Z)-pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, and 3-[11(Z)-pentadecenyl]phenol, which are extracted from cashew nut shells, etc. and are collectively called cardanol.

The reactive emulsifier (B3) is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil having a hydroxy group and a polymerizable unsaturated group, and has an HLB of 7 to 18. Examples of the oil having a hydroxy group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids that may contain unsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), and triglycerides of fatty acids that contain at least one hydroxyunsaturated fatty acid (ricinoleic acid, ricinoelaidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of emulsion stability of the acrylic resin, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one hydroxy unsaturated fatty acid is preferred, an alkylene oxide adduct of castor oil (triglyceride of a fatty acid containing ricinoleic acid) having 2 to 4 carbon atoms is more preferred, and an ethylene oxide adduct of castor oil is even more preferred. Furthermore, the number of moles of the alkylene oxide added can be appropriately selected so as to be within the above-mentioned HLB range, and from the viewpoint of emulsion stability of the acrylic resin, 20 to 50 moles is more preferred, and 25 to 45 moles is even more preferred. Furthermore, when there are two or more types of alkylene oxide, they can have a block addition structure or a random addition structure.

The reactive emulsifier (B3) can be synthesized by adding an alkylene oxide to an oil or fat having a hydroxyl group and a polymerizable unsaturated group using a conventionally known method, and is not particularly limited. For example, it can be synthesized by adding a predetermined amount of alkylene oxide to a triglyceride of a fatty acid containing ricinoleic acid, i.e., castor oil, using an alkali catalyst such as caustic soda or caustic potassium, under pressure at 120 to 170°C.

From the viewpoint of improving the water repellency and emulsion stability of the acrylic resin, the composition ratio of the reactive emulsifier (B) in the acrylic resin is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass, based on the total amount of the monomer components constituting the acrylic resin.

When the water repellent composition contains an acrylic resin as component (α), from the viewpoint of water repellency, the acrylic resin preferably contains, in addition to monomer (A), at least one second (meth)acrylic acid ester monomer (C) (hereinafter also referred to as "monomer (C)") selected from the group consisting of (C1), (C2), (C3), (C4) and (C5) below as a monomer component.

(C1) is a (meth)acrylic acid ester monomer represented by the following general formula (C-1) other than (C5).

［式（Ｃ－１）中、Ｒ^５は水素又はメチル基を表し、Ｒ^６はヒドロキシ基、アミノ基、カルボキシ基、エポキシ基、イソシアネート基及び（メタ）アクリロイルオキシ基からなる群より選ばれる少なくとも１種の官能基を有する炭素数１～１１の１価の鎖状炭化水素基を表す。ただし、分子内における（メタ）アクリロイルオキシ基の数は２以下である。］

[In formula (C-1), ^R5 represents hydrogen or a methyl group, and ^R6 represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having at least one functional group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group, provided that the number of (meth)acryloyloxy groups in the molecule is 2 or less.]

(C2) is a (meth)acrylic acid ester monomer represented by the following general formula (C-2):

［式（Ｃ－２）中、Ｒ^７は水素又はメチル基を表し、Ｒ^８は置換基を有していてもよい炭素数１～１１の１価の環状炭化水素基を表す。］

[In formula (C-2), ^R7 represents a hydrogen atom or a methyl group, and ^R8 represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent.]

(C3) is a methacrylic acid ester monomer represented by the following general formula (C-3):

［式（Ｃ－３）中、Ｒ^９は無置換の炭素数１～４の１価の鎖状炭化水素基を表す。］

[In formula (C-3), R ⁹ represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms.]

(C4) is a (meth)acrylic acid ester monomer represented by the following general formula (C-4):

［式（Ｃ－４）中、Ｒ^１０は水素又はメチル基を表し、ｐは２以上の整数を表し、Ｓは（ｐ＋１）価の有機基を表し、Ｔは重合性不飽和基を有する１価の有機基を表す。］

[In formula (C-4), R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents a (p+1)-valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group.]

(C5) is a (meth)acrylic acid ester monomer represented by the following general formula (C-5):

［式（Ｃ－５）中、Ｒ^１５は水素又はメチル基を表し、Ｒ^１６はクロロ基及びブロモ基からなる群より選ばれる少なくとも１種の官能基とヒドロキシ基とを有する炭素数３～６の１価の鎖状飽和炭化水素基を表す。］

[In formula (C-5), R ¹⁵ represents a hydrogen atom or a methyl group, and R ¹⁶ represents a monovalent linear saturated hydrocarbon group having 3 to 6 carbon atoms and having at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxy group.]

The monomer (C1) is a (meth)acrylic acid ester monomer having a monovalent chain hydrocarbon group having 1 to 11 carbon atoms, which has at least one functional group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group in the ester portion, and is a (meth)acrylic acid ester monomer other than the above (C5). In terms of being capable of reacting with a crosslinking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an epoxy group, and an isocyanate group. When a fiber substrate is treated with a composition containing an acrylic resin containing the monomer (C1) having a group capable of reacting with these crosslinking agents together with the crosslinking agent, the water repellency can be improved while maintaining the texture of the fiber substrate. The isocyanate group may be a blocked isocyanate group protected with a blocking agent.

The chain hydrocarbon group may be linear or branched, and may be a saturated or unsaturated hydrocarbon group. The chain hydrocarbon group may further have a substituent in addition to the functional group. Among these, from the viewpoints of water repellency and texture, it is preferable that the chain hydrocarbon group is linear and/or that the chain hydrocarbon group is a saturated hydrocarbon group.

Specific examples of the monomer (C1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. These monomers may be used alone or in combination of two or more. Among them, from the viewpoint of water repellency, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred. Furthermore, from the viewpoint of water repellency, dimethylaminoethyl (meth)acrylate is preferred.

From the viewpoint of water repellency, the composition ratio of the monomer (C1) in the acrylic resin is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %, based on the total amount of the monomer components constituting the acrylic resin.

The monomer (C2) is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester portion, and examples of the cyclic hydrocarbon group include an isobornyl group, a cyclohexyl group, and a dicyclopentanyl group. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group in which the total number of carbon atoms of the substituent and the cyclic hydrocarbon group is 11 or less is selected. In addition, from the viewpoint of water repellency, it is preferable that these cyclic hydrocarbon groups are directly bonded to an ester bond. The cyclic hydrocarbon group may be alicyclic or aromatic, and when it is alicyclic, it may be a saturated or unsaturated hydrocarbon group. Specific examples of the monomer include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. These monomers may be used alone or in combination of two or more. Among these, from the viewpoint of water repellency, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferred, and isobornyl methacrylate is more preferred.

From the viewpoint of water repellency, the composition ratio of the monomer (C2) in the acrylic resin is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %, based on the total amount of the monomer components constituting the acrylic resin.

The monomer (C3) is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester portion. As the chain hydrocarbon group having 1 to 4 carbon atoms, a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable. As the chain hydrocarbon group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group can be mentioned. As specific compounds, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate can be mentioned. These monomers may be used alone or in combination of two or more kinds. Among these, from the viewpoint of water repellency, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferred, with methyl methacrylate being more preferred.

From the viewpoint of water repellency, the composition ratio of the monomer (C3) in the acrylic resin is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %, based on the total amount of the monomer components constituting the acrylic resin.

The monomer (C4) is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In this embodiment, a polyfunctional (meth)acrylic acid ester monomer having three or more (meth)acryloyloxy groups in one molecule, in which T in the above general formula (C-4) is a (meth)acryloyloxy group, is preferred. In formula (C-4), the p Ts may be the same or different. Specific examples of compounds include ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. These monomers may be used alone or in combination of two or more. Among these, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred from the viewpoint of water repellency.

From the viewpoint of water repellency, the composition ratio of the monomer (C4) in the acrylic resin is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %, based on the total amount of the monomer components constituting the acrylic resin.

The monomer (C5) has a monovalent linear saturated hydrocarbon group having 3 to 6 carbon atoms and having at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxy group. In the monomer (C5), R ¹⁵ is hydrogen or a methyl group. From the viewpoint of water repellency, R ¹⁵ is preferably a methyl group.

R ¹⁶ is a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxy group. The chain saturated hydrocarbon group may be linear or branched. From the viewpoint of water repellency, it is preferable that the chain saturated hydrocarbon group is linear. From the viewpoint of water repellency, the number of carbon atoms of the chain saturated hydrocarbon group is preferably 3 to 4, and more preferably 3.

From the viewpoint of water repellency, the chain saturated hydrocarbon group preferably has one or two chloro groups and one hydroxy group, and more preferably has one chloro group and one hydroxy group. Furthermore, from the viewpoint of water repellency, the chain saturated hydrocarbon group further preferably has a hydroxy group at the β-position (the carbon atom adjacent to the carbon atom bonded to CH ₂ ═CR ¹⁵ (CO)O-). Specific examples of the chain saturated hydrocarbon group include a 3-chloro-2-hydroxylpropyl group, a 3-chloro-2-hydroxybutyl group, a 5-chloro-2-hydroxypentyl group, a 3-chloro-2-hydroxy-2-methylpropyl group, and a 3-bromo-2-hydroxypropyl group.

Specific examples of the monomer (C5) include 3-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxybutyl (meth)acrylate, 5-chloro-2-hydroxypentyl (meth)acrylate, and 3-bromo-2-hydroxypropyl (meth)acrylate. Among these, from the viewpoint of water repellency, 3-chloro-2-hydroxypropyl (meth)acrylate and 3-chloro-2-hydroxypropyl methacrylate are preferred, and 3-chloro-2-hydroxypropyl methacrylate is more preferred.

From the viewpoint of water repellency, the composition ratio of the monomer (C5) in the acrylic resin is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %, based on the total amount of the monomer components constituting the acrylic resin.

From the viewpoint of water repellency, the total composition ratio of the above monomer (C) in the acrylic resin is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %, based on the total amount of the monomer components constituting the acrylic resin.

When the water repellent composition contains an acrylic resin as component (α), the acrylic resin may contain, in addition to monomer (A), reactive emulsifier (B), and monomer (C), a monofunctional monomer (D) (hereinafter also referred to as "monomer (D)") that is copolymerizable with these, within a range that does not impair the effects of the present invention.

Examples of the monomer (D) include (meth)acryloylmorpholine, (meth)acrylic acid esters having a hydrocarbon group other than the monomer (A) and the monomer (C), (meth)acrylic acid, fumaric acid esters, maleic acid esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylol acrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other vinyl monomers not containing fluorine other than the monomer (E) described below. Note that the (meth)acrylic acid esters having a hydrocarbon group other than the monomer (A) and the monomer (C) may have a substituent such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, or a blocked isocyanate group in the hydrocarbon group, or may have a substituent other than a group capable of reacting with a crosslinking agent such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond, or a urethane bond. Examples of (meth)acrylic acid esters other than monomer (A) and monomer (C) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol di(meth)acrylate.

From the viewpoint of water repellency, the proportion of the monomer (D) in the acrylic resin is preferably 10% by mass or less based on the total amount of the monomer components constituting the acrylic resin.

When the water repellent composition contains an acrylic resin as component (α), it is preferable from the viewpoint of water repellency that the acrylic resin has at least one functional group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an epoxy group, and an isocyanate group that can react with a crosslinking agent. The isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. It is also preferable from the viewpoint of water repellency that the acrylic resin has an amino group.

When the water repellent composition contains an acrylic resin, from the viewpoint of peel strength, the acrylic resin preferably contains, in addition to the monomer (A), at least one monomer (E) selected from vinyl chloride and vinylidene chloride (hereinafter also referred to as "monomer (E)") as a monomer component.

In this embodiment, at least one of the monomers (E) of vinyl chloride and vinylidene chloride is preferably vinyl chloride from the viewpoint of maintaining the texture of the fiber substrate.

The monomer composition ratio of the monomer (E) in the acrylic resin may be 1 to 50% by mass, and from the viewpoint of water repellency and peel strength, it is preferably 1 to 45% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 35% by mass, based on the total amount of the monomer components constituting the acrylic resin.

The acrylic resin can be synthesized by a conventionally known method, and is not particularly limited, but can be synthesized, for example, by a radical polymerization method. Among these radical polymerization methods, it is preferable to use an emulsion polymerization method or a dispersion polymerization method in terms of the performance of the resulting water repellent and the environment.

For example, an acrylic resin can be obtained by emulsion polymerization or dispersion polymerization of the (meth)acrylic acid ester monomer (A) represented by the above general formula (A-1) in a medium. More specifically, for example, the monomer (A) and, if necessary, the reactive emulsifier (B), the monomer (C), the monomer (D), and the monomer (E), as well as an emulsifying aid or a dispersing aid, are added to the medium, and the mixture is emulsified or dispersed to obtain an emulsion or dispersion. A polymerization initiator is added to the obtained emulsion or dispersion to initiate a polymerization reaction, and the monomer and the reactive emulsifier can be polymerized. Examples of means for emulsifying or dispersing the above-mentioned mixture include a homomixer, a high-pressure emulsifier, and ultrasonic waves.

As the above-mentioned emulsifying aid or dispersing aid, etc. (hereinafter also referred to as "emulsifying aid, etc."), one or more selected from nonionic surfactants other than the reactive emulsifier (B), cationic surfactants, anionic surfactants, and amphoteric surfactants can be used. From the viewpoint of storage stability, the emulsifying aid, etc. is preferably a nonionic surfactant.

Nonionic surfactants include alkylene oxide adducts of alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, oils and fats, and polypropylene glycol.

Examples of alcohols include linear or branched alcohols or alkenols having 8 to 24 carbon atoms, and acetylene alcohols represented by the following general formula (AL-1) or (AL-2).

［式（ＡＬ－１）中、Ｒ^２１及びＲ^２２はそれぞれ独立に、炭素数１～８の直鎖若しくは分岐鎖を有するアルキル基又は炭素数２～８の直鎖若しくは分岐鎖を有するアルケニル基を表す。］

[In formula (AL-1), R ²¹ and R ²² each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 2 to 8 carbon atoms.]

［式（ＡＬ－２）中、Ｒ^２３は、炭素数１～８の直鎖若しくは分岐鎖を有するアルキル基又は炭素数２～８の直鎖若しくは分岐鎖を有するアルケニル基を表す。］

[In formula (AL-2), R ²³ represents a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 2 to 8 carbon atoms.]

Examples of polycyclic phenols include monohydric phenols such as phenol and naphthol that may have a hydrocarbon group having 1 to 12 carbon atoms, or their styrene (styrene, α-methylstyrene, vinyltoluene) adducts or their benzyl chloride reactants. Examples of amines include linear or branched aliphatic amines having 8 to 44 carbon atoms.

Examples of amides include linear or branched fatty acid amides having 8 to 44 carbon atoms.

Examples of fatty acids include straight-chain or branched-chain fatty acids with 8 to 24 carbon atoms.

Examples of polyhydric alcohol fatty acid esters include condensation products of polyhydric alcohols and linear or branched fatty acids having 8 to 24 carbon atoms.

Examples of fats and oils include vegetable fats and oils, animal fats and oils, vegetable waxes, animal waxes, mineral waxes, and hardened oils.

Among these, from the viewpoints of having little effect on water repellency and water repellency durability, having little effect on light resistance, and having good emulsification properties of the acrylic resin, linear or branched alcohols or alkenols having 8 to 24 carbon atoms and acetylene alcohols represented by the above general formula (AL-1) are preferred, and linear or branched alcohols having 8 to 24 carbon atoms and acetylene alcohols represented by the above general formula (AL-1) are more preferred.

Examples of alkylene oxides include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide, and epichlorohydrin. From the viewpoints of having little effect on water repellency and improving the emulsifiability of the copolymer, ethylene oxide and 1,2-propylene oxide are preferred as alkylene oxides, and ethylene oxide is more preferred.

The number of moles of alkylene oxide added is preferably 1 to 200, more preferably 3 to 100, and even more preferably 5 to 50. When the number of moles of alkylene oxide added is within the above range, the water repellency and emulsifiability of the copolymer tend to be further improved.

In the copolymer according to this embodiment, a better aqueous dispersion can be obtained when a nonionic surfactant having an HLB value of 4 to 17 as defined by the following formula (H) is used as the nonionic surfactant. The HLB defined by the following formula (H) is based on Griffin's HLB, and is obtained by modifying the Griffin formula to the following formula (H). Here, the hydrophilic group refers to an ethylene oxide group.
HLB=(hydrophilic group x 20)/molecular weight (H)

The HLB of the nonionic surfactant as defined by the above formula (H) is preferably 5 to 15 in terms of emulsion stability during emulsion polymerization or dispersion polymerization of component (A) and in the composition after polymerization (hereinafter simply referred to as emulsion stability). Furthermore, in terms of the storage stability of the water repellent composition, it is more preferable to use two or more nonionic surfactants having different HLBs within the above range in combination. Also, from the viewpoints of emulsion stability and water repellency, it is preferable to use a cationic surfactant and a nonionic surfactant in combination.

The content of the emulsification aid, etc. is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of all monomers constituting the acrylic resin. When the content of the emulsification aid, etc. is 0.5 parts by mass or more, the dispersion stability of the mixed liquid tends to be further improved compared to when the content of the emulsification aid is less than 0.5 parts by mass, and when the content of the emulsification aid, etc. is 30 parts by mass or less, the water repellency of the resulting water repellent composition tends to be improved compared to when the content of the emulsification aid, etc. exceeds 30 parts by mass.

As a medium for emulsion polymerization or dispersion polymerization, water is preferred, and water may be mixed with an organic solvent as necessary. Examples of organic solvents include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. It is preferable to use glycols because they further improve the water repellency and water penetration prevention properties imparted to the fiber substrate. The ratio of water to organic solvent is not particularly limited.

As the polymerization initiator, known polymerization initiators such as azo, peroxide, or redox initiators can be used as appropriate. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass per 100 parts by mass of the total monomers constituting the acrylic resin. When the content of the polymerization initiator is within the above range, an acrylic resin having a weight average molecular weight of 100,000 or more can be efficiently produced.

In addition, chain transfer agents such as dodecyl mercaptan and t-butyl alcohol may be used in the polymerization reaction to adjust the molecular weight.

A polymerization inhibitor may be used to adjust the molecular weight. By adding a polymerization inhibitor, an acrylic resin having the desired weight average molecular weight can be easily obtained.

The temperature of the polymerization reaction is preferably 20°C to 150°C. If the temperature is below 20°C, the polymerization tends to be insufficient compared to when the temperature is within the above range, and if the temperature exceeds 150°C, it may be difficult to control the reaction heat.

In the polymerization reaction, the weight average molecular weight of the resulting acrylic resin can be adjusted by increasing or decreasing the content of the polymerization initiator, chain transfer agent, and polymerization inhibitor described above, and the melt viscosity at 105°C can be adjusted by increasing or decreasing the content of the polyfunctional monomer and the content of the polymerization initiator. If you want to lower the melt viscosity at 105°C, you can reduce the content of the monomer having two or more polymerizable functional groups or increase the content of the polymerization initiator.

From the viewpoint of storage stability and handleability of the composition, the content of the acrylic resin in the emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass, based on the total amount of the emulsion or dispersion.

In the polymerization reaction, instead of using a polymerization initiator, the polymerization reaction may be carried out by photopolymerization, for example, by irradiating the material with ionizing radiation such as ultraviolet light, electron beams, or gamma rays.

Next, we will explain urethane resin.

The urethane resin as component (α) is obtained by reacting at least a polyfunctional compound represented by the above general formula (I-1) with an isocyanate compound represented by the above general formula (II-1).

The polyfunctional compound represented by the above general formula (I-1) will be described.

In the above general formula (I-1), when d is 2 or more, multiple W ¹ 's may be the same or different. Multiple R ³² 's may be the same or different. Multiple V ¹ 's may be the same or different.

R ³¹ represents an organic group having a valence of (d+e). From the viewpoint of water repellency and water penetration prevention, the number of carbon atoms in R ³¹ is preferably 2 to 40, and more preferably 4 to 12. R ³¹ is preferably a group represented by the following chemical formula (1), a group represented by the following chemical formula (2), or a group represented by the following chemical formula (3). From the viewpoint of ease of handling of the urethane resin, (d+e) is preferably 3 to 4.

［式（３）中、ｒは、１以上の整数を表す。］

[In formula (3), r represents an integer of 1 or more.]

r represents an integer of 1 or more, preferably 1 to 3.

R ³¹ may be a residue obtained by removing (d+e) functional groups from a polyfunctional compound having (d+e) functional groups selected from the group consisting of a hydroxy group, an amino group, and a carboxy group (hereinafter referred to as "polyfunctional compound A"), provided that two or more of the (d+e) functional groups are hydroxy groups and/or amino groups.

Examples of polyfunctional compounds A include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, glycerin, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aminoethylethanolamine, diethanolamine, and triethanolamine. Among these, trimethylolpropane, ditrimethylolpropane, diethanolamine, and diethylenetriamine are preferred from the viewpoints of water repellency and water penetration prevention properties, as well as emulsion dispersion stability of the resulting urethane resin.

W ¹ represents a divalent group which is an ester group, an amide group, a urethane group or a urea group. From the viewpoint of water repellency and water penetration prevention properties, W ¹ is preferably an ester group or a urethane group.

R ³² represents a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms. The hydrocarbon group may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic or aromatic ring. From the viewpoint of water repellency and water penetration prevention, the hydrocarbon group is preferably linear, and more preferably a linear alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 10 to 24, more preferably 12 to 22, and particularly preferably 12 to 18. When the number of carbon atoms is within this range, it is easy to improve the water repellency and water penetration prevention properties imparted to the fiber substrate while sufficiently maintaining the texture of the fiber substrate. The hydrocarbon group is particularly preferably a linear alkyl group having 12 to 18 carbon atoms.

Examples of R ³² include a nonyl group, a decyl group, an undecyl group, a dodecyl group (a lauryl group), a myristyl group, a pentadecyl group, a cetyl group, a heptadecyl group, a stearyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, and a behenyl group.

R ³² may be a residue obtained by removing the reactive group from a reactive hydrocarbon compound having a reactive group capable of reacting with a functional group possessed by the polyfunctional compound A. Examples of the reactive hydrocarbon compound include higher fatty acids having 8 to 24 carbon atoms (note that the carbon number includes the carbon of the carbonyl group), higher aliphatic alcohols, higher aliphatic monoisocyanates, and higher aliphatic amines.

Examples of higher fatty acids include lauric acid, myristic acid, pentadecylic acid, palmitic acid, heptadecanoic acid, stearic acid, oleic acid, eicosanoic acid, and docosanoic acid.

Examples of higher aliphatic alcohols include lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, stearyl alcohol, oleyl alcohol, eicosanol, heneicosanol, and behenyl alcohol.

Examples of higher aliphatic monoisocyanates include decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, myristyl isocyanate, pentadecyl isocyanate, cetyl isocyanate, stearyl isocyanate, eicosyl isocyanate, and behenyl isocyanate.

Examples of higher aliphatic amines include decylamine, laurylamine, myristylamine, stearylamine, and behenylamine.

^V1 represents a hydroxy group, an amino group, or a carboxy group. From the viewpoint of water repellency, ^V1 is preferably a hydroxy group or an amino group.

The polyfunctional compound represented by the above general formula (I-1) can be produced, for example, by introducing d hydrophobic groups represented by [-W ¹ -R ³² ] into a polyfunctional compound (polyfunctional compound A) having (d+e) functional groups selected from the group consisting of hydroxyl groups, amino groups, and carboxy groups.

The hydrophobic group represented by [-W ¹ -R ³² ] can be introduced, for example, by reacting 1 mole or more of the reactive hydrocarbon compound with 1 mole of the polyfunctional compound A so that the number e of unreacted functional groups in the polyfunctional compound A is 2 or more, using a conventionally known synthesis method, i.e., esterification reaction, amidation reaction or urethane reaction.

The polyfunctional compound represented by the above general formula (I-1) is not particularly limited, but is preferably at least one selected from the group consisting of polyfunctional compounds represented by the following general formula (I-2), polyfunctional compounds represented by the following general formula (I-3), and polyfunctional compounds represented by the following general formula (I-4).

C[-R ⁴¹ ] _g [-R ⁴² -V ² ] _h [-R ⁴³ -W ² -R ⁴⁴ ] _i (I-2)
[In formula (I-2), g is an integer of 0 or 1, h is an integer of 2 or 3, i is an integer of 1 or 2, (g+h+i) is 4, and R ⁴¹ is R ⁴² represents a divalent alkylene group having 1 to 2 carbon atoms; R ⁴³ represents a divalent alkylene group having 1 to 4 carbon atoms; R ⁴⁴ represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms; W ² represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group; V ² represents represents a hydroxy group, an amino group, or a carboxy group, provided that two or more ^V2s are hydroxy groups and/or amino groups.

［式（Ｉ－３）中、Ｒ^５１及びＲ^５２はそれぞれ独立に炭素数１～４の直鎖又は分岐の炭化水素基を表し、Ｒ^５４及びＲ^５５はそれぞれ独立に炭素数１～４の２価のアルキレン基を表し、Ｒ^５３、Ｒ^５６、Ｒ^５７及びＲ^５８はそれぞれ独立に下記一般式（４）又は下記一般式（５）で表される１価の基を示す。
－Ｒ^５９－Ｖ^３ （４）
｛Ｒ^５９は炭素数１～４の２価のアルキレン基を表し、Ｖ^３はヒドロキシ基、アミノ基又はカルボキシ基を表す。｝
－Ｒ^６０－Ｗ^３－Ｒ^６１ （５）
｛Ｒ^６０は炭素数１～４の２価のアルキレン基を表し、Ｒ^６１は炭素数８～２４の直鎖又は分岐の１価の炭化水素基を表し、Ｗ^３はエステル基、アミド基、ウレタン基又はウレア基である２価の基を表す。｝、
ただし、Ｒ^５３、Ｒ^５６、Ｒ^５７及びＲ^５８のうち少なくとも２つは、Ｖ^３がヒドロキシ基又はアミノ基である、上記一般式（４）で表される基である。］

[In formula (I-3), R ⁵¹ and R ⁵² each independently represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms, R ⁵⁴ and R ⁵⁵ each independently represent a divalent alkylene group having 1 to 4 carbon atoms, and R ⁵³ , R ⁵⁶ , R ⁵⁷ , and R ⁵⁸ each independently represent a monovalent group represented by the following general formula (4) or the following general formula (5).
-R ⁵⁹ -V ³ (4)
{R ⁵⁹ represents a divalent alkylene group having 1 to 4 carbon atoms, and V ³ represents a hydroxy group, an amino group, or a carboxy group.}
-R ⁶⁰ -W ³ -R ⁶¹ (5)
{R ⁶⁰ represents a divalent alkylene group having 1 to 4 carbon atoms, R ⁶¹ represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms, and W ³ represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group.}
However, at least two of R ⁵³ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ are groups represented by the above general formula (4) in which V ³ is a hydroxy group or an amino group.]

［式（Ｉ－４）中、ｊは１～４の整数を表し、Ｒ^７１及びＲ^７３はそれぞれ独立に炭素数１～４の２価のアルキレン基を表し、Ｒ^７２及びＲ^７４はそれぞれ独立にヒドロキシ基、アミノ基又は下記一般式（６）で表される１価の基を表し、Ｒ^７５は水素、下記一般式（７）、下記一般式（８）又は下記一般式（９）で表される１価の基を表す。
－Ｗ^４－Ｒ^７６ （６）
｛式（６）中、Ｗ^４はエステル基、アミド基、ウレタン基又はウレア基である２価の基を表し、Ｒ^７６は炭素数８～２４の直鎖又は分岐の１価の炭化水素基を表す。｝
－Ｒ^７７－ＯＨ （７）
｛式（７）中、Ｒ^７７は炭素数２～３のアルキレン基を表す。｝
－Ｒ^７８－Ｗ^５－Ｒ^７９ （８）
｛式（８）中、Ｒ^７８は炭素数２～３のアルキレン基を表し、Ｒ^７９は炭素数８～２４の直鎖又は分岐の１価の炭化水素基を表し、Ｗ^５はエステル基、アミド基、ウレタン基又はウレア基である２価の基を示す。｝
－Ｗ^６－Ｒ^８０ （９）
｛式（９）中、Ｗ^６はカルボニル基又はアミド基を表し、Ｒ^８０は炭素数８～２４の直鎖又は分岐の１価の炭化水素基を表す。｝、
ただし、Ｒ^７２、Ｒ^７４及びｊ個のＲ^７５のうち少なくとも２つはヒドロキシ基、アミノ基、水素、上記一般式（７）で表される１価の基であり、Ｒ^７２及びＲ^７４はヒドロキシ基又はアミノ基、Ｒ^７５は水素又は上記一般式（７）で表される１価の基である。］

[In formula (I-4), j represents an integer of 1 to 4, R ⁷¹ and R ⁷³ each independently represent a divalent alkylene group having 1 to 4 carbon atoms, R ⁷² and R ⁷⁴ each independently represent a hydroxyl group, an amino group, or a monovalent group represented by the following general formula (6), and R ⁷⁵ represents hydrogen or a monovalent group represented by the following general formula (7), (8), or (9).
-W ⁴ -R ⁷⁶ (6)
In formula (6), ^W4 represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group, and ^R76 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms.
-R ⁷⁷ -OH (7)
In formula (7), R ⁷⁷ represents an alkylene group having 2 to 3 carbon atoms.
-R ⁷⁸ -W ⁵ -R ⁷⁹ (8)
In formula (8), R ⁷⁸ represents an alkylene group having 2 to 3 carbon atoms, R ⁷⁹ represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms, and W ⁵ represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group.
-W ⁶ -R ⁸⁰ (9)
{In formula (9), ^W6 represents a carbonyl group or an amide group, and ^R80 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms.}
However, at least two of R ⁷² , R ⁷⁴ and j R ⁷⁵ are a hydroxy group, an amino group, hydrogen, or a monovalent group represented by the above general formula (7), R ⁷² and R ⁷⁴ are a hydroxy group or an amino group, and R ⁷⁵ is hydrogen or a monovalent group represented by the above general formula (7).

In the polyfunctional compound represented by the above general formula (I-2), when i is 2, the multiple W ^2s may be the same or different. When i is 2, the multiple R ^43s may be the same or different. When i is 2, the multiple R ^44s may be the same or different. R ⁴⁴ corresponds to R ³² in the above general formula (I-1). The multiple R ^42s may be the same or different. The multiple V ^2s may be the same or different.

In the polyfunctional compound represented by the general formula (I-2), ^W2 is a divalent group which is an ester group, an amide group, a urethane group, or a urea group. From the viewpoint of water repellency and water penetration prevention, ^W2 is preferably an ester group or a urethane group.

In the polyfunctional compound represented by the above general formula (I-2), ^V2 is a hydroxy group, an amino group, or a carboxy group. From the viewpoint of water repellency, ^V2 is preferably a hydroxy group or an amino group.

In the group represented by the above general formula (4), ^V3 is a hydroxy group, an amino group, or a carboxy group. From the viewpoint of water repellency, ^V3 is preferably a hydroxy group or an amino group.

In the group represented by the above general formula (5), R ⁶¹ is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. R ⁶¹ corresponds to R ³² in the above general formula (I-1).

In the group represented by the above general formula (5), ^W3 is a divalent group which is an ester group, an amide group, a urethane group, or a urea group. From the viewpoint of water repellency and water penetration prevention, ^W3 is preferably an ester group or a urethane group.

In the group represented by the above general formula (6), R ⁷⁶ is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. R ⁷⁶ corresponds to R ³² in the above general formula (I-1).

In the group represented by the above general formula (6), ^W4 is a divalent group which is an ester group, an amide group, a urethane group, or a urea group. From the viewpoint of water repellency and water penetration prevention, ^W4 is preferably an ester group, an amide group, or a urethane group.

In the group represented by the above general formula (8), R ⁷⁹ is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. R ⁷⁹ corresponds to R ³² in the above general formula (I-1).

In the group represented by the above general formula (8), ^W5 is a divalent group which is an ester group, an amide group, a urethane group, or a urea group. From the viewpoint of water repellency and water penetration prevention, ^W5 is preferably an ester group, an amide group, or a urethane group.

In the group represented by the above general formula (9), R ⁸⁰ is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. R ⁸⁰ corresponds to R ³² in the above general formula (I-1).

Next, we will explain the isocyanate compound represented by the above general formula (II-1).

R ³³ represents an f-valent organic group. From the viewpoints of water repellency and water penetration resistance, the carbon number of R ³³ is preferably 4 to 40, and more preferably 6 to 18. R ³³ is preferably a hexylene group. f may be an integer of 2 to 7, and from the viewpoints of water repellency and water penetration resistance, it is preferably 2 to 3.

The isocyanate compound represented by the general formula (II-1) above may be a polyisocyanate compound. Examples of polyisocyanate compounds include diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid MDI represented by polyphenyl polymethyl polyisocyanate, crude MDI, hexamethylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and isophorone diisocyanate, as well as trimers of these isocyanurate rings. Among these, hexamethylene diisocyanate is preferred from the viewpoints of water repellency and water penetration prevention.

Examples of urethane resins obtained by reacting a polyfunctional compound represented by the above general formula (I-1) with an isocyanate compound represented by the above general formula (II-1) include urethane resins having partial structures represented by the following general formulas (III-1), (III-2), and (III-3).

［式（ＩＩＩ－１）中、ｋ１は、２以上の整数を表し、Ｒ^１１１及びＲ^１１２は、それぞれ独立に炭素数１０～２４の直鎖又は分岐の１価の炭化水素基を表す。］

[In formula (III-1), k1 represents an integer of 2 or more, and R ¹¹¹ and R ¹¹² each independently represent a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms.]

k1 represents an integer of 2 or more, and is preferably 2 to 100, more preferably 2 to 50, from the viewpoint of water repellency and water penetration prevention, as well as further improving the emulsion dispersion stability of the urethane resin and making the urethane resin easier to handle.

［式（ＩＩＩ－２）中、ｋ２は、２以上の整数を表し、ｋ３は、１以上の整数を表し、Ｒ^１１３は、それぞれ独立に炭素数１０～２４の直鎖又は分岐の１価の炭化水素基を表す。］

[In formula (III-2), k2 represents an integer of 2 or more, k3 represents an integer of 1 or more, and R ¹¹³ each independently represents a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms.]

k2 represents an integer of 2 or more, and is preferably 2 to 200, more preferably 2 to 100, from the viewpoint of water repellency and water penetration prevention, as well as further improving the emulsion dispersion stability of the urethane resin and making the urethane resin easier to handle.

k3 represents an integer of 1 or more, and is preferably an integer from 1 to 3, more preferably 1, from the viewpoint of water repellency and water penetration prevention, and from the viewpoint of further improving the emulsion dispersion stability of the urethane resin.

［式（ＩＩＩ－３）中、ｋ４は、２以上の整数を表し、Ｒ^１１４は、それぞれ独立に炭素数１０～２４の直鎖又は分岐の１価の炭化水素基を表す。］

[In formula (III-3), k4 represents an integer of 2 or more, and R ¹¹⁴ each independently represent a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms.]

k4 represents an integer of 2 or more, and is preferably 2 to 200, more preferably 2 to 100, from the viewpoint of water repellency and water penetration prevention, as well as further improving the emulsion dispersion stability of the urethane resin and making the urethane resin easier to handle.

An example of a urethane resin having a partial structure represented by the above general formula (III-1) is a compound represented by the following formula (III-4).

［式（ＩＩＩ－４）中、ｋ５は、２以上の整数を表し、Ｒ_Ｘは、下記式（Ｒ－１）で表される一価の有機基を表す。］

[In formula (III-4), k5 represents an integer of 2 or more, and R _X represents a monovalent organic group represented by the following formula (R-1).]

k5 represents an integer of 2 or more, and is preferably 2 to 100, more preferably 2 to 50, from the viewpoint of water repellency and water penetration prevention, as well as further improving the emulsion dispersion stability of the urethane resin and making the urethane resin easier to handle.

An example of a urethane resin having a partial structure represented by the above general formula (III-2) is a compound represented by the following formula (III-5).

［式（ＩＩＩ－５）中、ｋ６は、２以上の整数を表し、ｋ７は、１以上の整数を表す。Ｒ_Ｘは、上記式（Ｒ－１）で表される一価の有機基を表す。］

[In formula (III-5), k6 represents an integer of 2 or more, and k7 represents an integer of 1 or more. _{R X} represents a monovalent organic group represented by formula (R-1) above.]

k6 represents an integer of 2 or more, and is preferably 2 to 200, more preferably 2 to 100, from the viewpoint of water repellency and water penetration prevention, as well as further improving the emulsion dispersion stability of the urethane resin and making the urethane resin easier to handle.

k7 represents an integer of 1 or more, and is preferably 1 to 3, more preferably 1, from the viewpoint of water repellency and water penetration prevention, as well as further improving the emulsion dispersion stability of the urethane resin and making the urethane resin easier to handle.

An example of a urethane resin having a partial structure represented by the above general formula (III-3) is a compound represented by the following formula (III-6).

［式（ＩＩＩ－６）中、ｋ８は、２以上の整数を表し、Ｒ_Ｘは、上記式（Ｒ－１）で表される一価の有機基を表す。］

[In formula (III-6), k8 represents an integer of 2 or more, and R _X represents a monovalent organic group represented by formula (R-1) above.]

k8 represents an integer of 2 or more, and is preferably 2 to 200, more preferably 2 to 100, from the viewpoint of water repellency and water penetration prevention, as well as further improving the emulsion dispersion stability of the urethane resin and making the urethane resin easier to handle.

The urethane resin preferably has blocked isocyanate groups protected with a blocking agent, since this further improves chemical resistance. From the viewpoint of chemical resistance, the ratio of blocked isocyanate groups to the total number of isocyanate groups and blocked isocyanate groups contained in the urethane resin is preferably 80% or more, more preferably 90% or more, and even more preferably 100%.

An example of a blocked isocyanate group protected with a blocking agent is a group represented by the following general formula (10).

(-NH-CO-B) (10)
[In formula (10), B is a group derived from 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; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol; phenols such as phenol, methylphenol, chlorophenol, p-isobutylphenol, p-tert-butylphenol, p-isoamylphenol, p-octylphenol, and p-nonylphenol; Examples of the blocking agent include active methylene compounds such as dimethyl malonate, diethyl malonate, acetylacetone, methyl acetoacetate, and ethyl acetoacetate; oximes such as formaldoxime, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; lactams such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam; N-substituted amides such as N-methylacetamide and acetanilide; imide compounds such as succinimide and phthalimide; and imidazole compounds such as imidazole and 2-methylimidazole. One type of blocking agent may be used alone, or two or more types may be used in combination. Among these, from the viewpoints of versatility, reactivity of the blocked isocyanate group, and ease of blocking, it is preferable to use at least one compound selected from the group consisting of pyrazoles, oximes, and lactams, and among these, it is more preferable to use at least one compound selected from the group consisting of dimethylpyrazole, methyl ethyl ketone oxime, and caprolactam.

The weight average molecular weight of the urethane resin may be preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 2,000 to 20,000, from the viewpoint of water repellency and water penetration prevention, as well as to further improve the emulsion dispersion stability of the urethane resin.

The amount of the compound represented by the general formula (II-1) when reacting the polyfunctional compound represented by the general formula (I-1) having e ¹ hydroxyl group and/or amino group with the compound represented by the general formula (II-1) is preferably (0.8 to 1.20) x 2/e 1 mole, more preferably (0.80 to 0.99) x 2/e ¹ mole, and even more preferably (0.85 to 0.95) x 2/e ¹ mole, relative to 1 mole of the polyfunctional compound represented by the general formula (I ^{-1). Or, (1.01 to 1.20) x 2/e 1 mole} is more preferable, and (1.05 to 1.15) x 2/e ¹ is even more preferable.

From the standpoint of water repellency and the environment, it is preferable to use the urethane resin of this embodiment by emulsifying or dispersing it with an emulsifying aid or a dispersing aid. The emulsion or dispersion containing the urethane resin of this embodiment can be produced, for example, as follows.

The urethane resin of this embodiment is homogenized by adding a surfactant as an emulsifying agent or dispersing agent, and water is gradually added thereto while stirring to obtain an emulsion or dispersion.

The surfactant may be one or more selected from conventionally known nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. The content of the emulsification aid, etc., relative to 100 parts by mass of the urethane resin of this embodiment is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 20 to 30 parts by mass. When the content of the emulsification aid, etc., is within the above range, it becomes easy to improve the emulsion dispersion stability of the urethane resin while maintaining water repellency.

As the medium for emulsification or dispersion, water is preferred, and water may be mixed with an organic solvent as necessary. Examples of organic solvents include alcohols such as methanol and ethanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether; and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. The ratio of water and organic solvent to be mixed is not particularly limited. The organic solvent may be distilled off under reduced pressure during or after the preparation of the aqueous dispersion, or may be left as it is.

The particles of the obtained aqueous dispersion of urethane resin can be homogenized using a high-pressure emulsifier such as a Homomixer (manufactured by Primix Corporation), a Homogenizer (manufactured by NIROSO AVI or APV GAULIN), a Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), an Ultimizer (manufactured by Sugino Machine Ltd.), or a Starburst (manufactured by Sugino Machine Ltd.), or an ultrasonic emulsifier.

The component (β) contained in the water repellent composition according to this embodiment is described in detail below.

In the above general formula (L-1), the structural units may be arranged in blocks, randomly, or alternately.

In the component (β) of this embodiment, the alkoxyl group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. From the viewpoint of ease of industrial production and availability, R ²²⁰ , R ²²¹ , and R ²²² are each preferably independently a hydrogen atom or a methyl group, and more preferably a methyl group.

Examples of the above-mentioned hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring include aralkyl groups having 8 to 40 carbon atoms and groups represented by the following general formula (L-2) or (L-3).

［式（Ｌ－２）中、Ｒ^２４０は、炭素数２～６のアルキレン基を表し、Ｒ^２４１は、単結合又は炭素数１～４のアルキレン基を表し、ａ３は０～３の整数を表す。ａ３が２又は３の場合、複数存在するＲ^２４１は同一であっても異なっていてもよい。］

[In formula (L-2), R ²⁴⁰ represents an alkylene group having 2 to 6 carbon atoms, R ²⁴¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and a3 represents an integer of 0 to 3. When a3 is 2 or 3, the multiple R ²⁴¹ may be the same or different.]

The alkylene group may be linear or branched.

［式（Ｌ－３）中、Ｒ^２４２は、炭素数２～６のアルキレン基を表し、Ｒ^２４３は、単結合又は炭素数１～４のアルキレン基を表し、ａ４は０～３の整数を表す。ａ４が２又は３の場合、複数存在するＲ^２４３は同一であっても異なっていてもよい。］

[In formula (L-3), R ²⁴² represents an alkylene group having 2 to 6 carbon atoms, R ²⁴³ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and a4 represents an integer of 0 to 3. When a4 is 2 or 3, the multiple R ^243s may be the same or different.]

The alkylene group may be linear or branched.

Examples of the aralkyl group having 8 to 40 carbon atoms include a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, and a naphthylethyl group. Among these, the phenylethyl group and the phenylpropyl group are preferred because they are easy to produce industrially and are readily available.

In the group represented by the above general formula (L-2), R ²⁴⁰ is preferably an alkylene group having 2 to 4 carbon atoms, and a3 is preferably 0 or 1, and more preferably 0, in terms of ease of industrial production and availability.

In the group represented by the above general formula (L-3), R ²⁴² is preferably an alkylene group having 2 to 4 carbon atoms, and a4 is preferably 0 or 1, and more preferably 0, in terms of ease of industrial production and availability.

As the above-mentioned hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms, the above-mentioned aralkyl group having 8 to 40 carbon atoms and the group represented by the above-mentioned general formula (L-2) are preferred in terms of ease of industrial production and availability, and the above-mentioned aralkyl group having 8 to 40 carbon atoms is more preferred from the viewpoint of imparting water repellency and water penetration prevention properties to the fiber substrate.

The alkyl group having 3 to 22 carbon atoms may be linear or branched. Examples of the alkyl group having 3 to 22 carbon atoms include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, and stearyl. From the viewpoint of imparting water repellency and water penetration prevention to the fiber substrate, the alkyl group having 8 to 20 carbon atoms is preferable, and the alkyl group having 12 to 18 carbon atoms is more preferable.

In the component (β) of this embodiment, R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ are each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms, or an alkyl group having 3 to 22 carbon atoms. From the viewpoint of ease of industrial production and availability, R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and among these, a methyl group is more preferable.

In the (β) component of this embodiment, a1 is an integer of 0 or more. From the viewpoints of ease of industrial production, ease of availability, and imparting water repellency and water penetration prevention properties to the fiber substrate, a1 is preferably 40 or less, and more preferably 30 or less.

In the (β) component of this embodiment, (a1+a2) is 10 to 200. From the viewpoint of ease of industrial production and availability, (a1+a2) is preferably 20 to 100, and more preferably 40 to 60. When (a1+a2) is within the above range, the silicone itself tends to be easier to produce and handle.

The component (β) of this embodiment can be synthesized by a conventionally known method. For example, the component (β) of this embodiment can be obtained by subjecting silicone having a SiH group to a hydrosilylation reaction with an aromatic compound having a vinyl group and/or an α-olefin.

Examples of silicones having SiH groups include methylhydrogensilicones with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicones are preferred because they are easy to produce industrially and are readily available.

The aromatic compound having a vinyl group is a compound from which the hydrocarbon group having an aromatic ring and 8 to 40 carbon atoms in R ²²³ in the general formula (L-1) is derived. Examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumyl phenyl ether, allyl-o-phenyl phenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.

The above α-olefin is a compound from which the alkyl group having 3 to 22 carbon atoms in R ²²³ in the above general formula (L-1) is derived. Examples of the α-olefin include α-olefins having 3 to 22 carbon atoms such as propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.

The hydrosilylation reaction may be carried out by reacting the silicone having a SiH group with the aromatic compound having a vinyl group and the α-olefin in a stepwise or all-at-once reaction, if necessary, in the presence of a catalyst.

The amounts of the silicone having a SiH group, the aromatic compound having a vinyl group, and the α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight of the silicone having a SiH group, the number average molecular weight, etc.

Catalysts used in the hydrosilylation reaction include, for example, platinum and palladium compounds, with platinum compounds being preferred. Examples of platinum compounds include platinum(IV) chloride.

The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted as appropriate. 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 in an inert gas atmosphere. Examples of inert gas include nitrogen and argon. The reaction proceeds without a solvent, but a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

From the viewpoint of water repellency, the content ratio of the (α) component to the (β) component in this embodiment is preferably 95:5 to 50:50 by mass, more preferably 90:10 to 60:40, and even more preferably 80:20 to 70:30.

The (γ) component contained in the water repellent composition according to this embodiment is described in detail below.

The (γ) component according to this embodiment is not particularly limited, but examples thereof include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, animal and vegetable wax, and mineral wax. From the viewpoints of water repellency and texture, the (γ) component is preferably paraffin wax.

The compound constituting the (γ) component according to this embodiment is not particularly limited, but examples thereof include normal alkanes and normal alkenes. From the viewpoints of water repellency and texture, it is preferable that the (γ) component is a normal alkane.

Normal alkanes include, for example, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane. From the viewpoints of water repellency and texture, the normal alkanes are preferably triacontane, hentriacontane, and dotriacontane.

Examples of normal alkenes include 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosene, triacontene, hentriacontene, dotriacontene, tritriacontene, tetratriacontene, pentatriacontene, and hexatriacontene. From the viewpoints of water repellency and texture, it is preferable that the normal alkenes are triacontene, hentriacontene, and dotriacontene.

The number of carbon atoms in the (γ) component according to this embodiment is not particularly limited, but may be 20 to 60, and from the viewpoint of water repellency and texture, it is preferably 25 to 45.

The weight average molecular weight of the (γ) component in this embodiment is not particularly limited, but may be 300 to 850, and from the viewpoint of water repellency and texture, it is preferably 300 to 700.

The melting point of the (γ) component according to this embodiment is not particularly limited, but may be, for example, 40 to 90°C. From the viewpoint of water repellency and texture, it is preferably 55 to 85°C, more preferably 60 to 80°C, even more preferably 65 to 78°C, and particularly preferably 70 to 78°C. The melting point of the (γ) component refers to a value measured in accordance with JIS K 2235-1991.

The penetration of the (γ) component according to this embodiment is not particularly limited, but may be, for example, 30 or less, and from the viewpoint of water repellency, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The penetration of the (γ) component according to this embodiment is not particularly limited, but may be, for example, 0.1 or more, or 1 or more. The penetration of the (γ) component refers to a value measured using the same method as JIS K 2235-1991.

The content ratio of the (α) component to the (γ) component in this embodiment is preferably 90:10 to 40:60 by mass, more preferably 80:20 to 50:50, and even more preferably 70:30 to 60:40. When the content ratio of the (α) component to the (γ) component is within the above range, it is possible to impart excellent water repellency and water penetration prevention properties while adequately maintaining the texture of the fiber substrate.

In terms of water repellency and the environment, the (γ) component of this embodiment is preferably emulsified or dispersed with an emulsifying aid or a dispersing aid before use. The aqueous dispersion of the (γ) component according to this embodiment can be produced by dispersing the (γ) component in water in the presence of an emulsifier for wax. The aqueous dispersion of the (γ) component is preferably produced by mixing the (γ) component, water, and the emulsifier for wax. The temperature during mixing is not particularly limited, but may be, for example, 60 to 90°C. The time during mixing is not particularly limited, but may be, for example, 10 seconds to 10 hours. Mixing is preferably performed using a homomixer.

From the viewpoint of water repellency, the water repellent composition according to this embodiment may further contain a crosslinking agent (hereinafter also referred to as the "(δ)" component). The (δ) component will be described in detail below.

The (δ) component according to this embodiment is not particularly limited, and examples thereof include melamine resins, glyoxal resins, and compounds having one or more isocyanate groups or blocked isocyanate groups. The (δ) component, which is a compound having one or more isocyanate groups or blocked isocyanate groups, does not include urethane resins having a structural unit derived from a polyfunctional compound represented by the above general formula (I-1) and a structural unit derived from an isocyanate compound represented by the above general formula (II-1). The (δ) component can be used alone or in combination of two or more types.

As the melamine resin, a compound having a melamine skeleton can be used, for example, polymethylol melamine such as trimethylol melamine and hexamethylol melamine; alkoxymethyl melamine in which some or all of the methylol groups of polymethylol melamine are alkoxymethyl groups having an alkyl group with 1 to 6 carbon atoms; and acyloxymethyl melamine in which some or all of the methylol groups of polymethylol melamine are acyloxymethyl groups having an acyl group with 2 to 6 carbon atoms. These melamine resins may be either monomers or polymers of dimers or more, or a mixture 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.

As the glyoxal resin, a conventionally known one 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 Conc, 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.

When a melamine resin and a glyoxal resin are used as the (δ) component, it is preferable that the water repellent composition according to this embodiment further contains a catalyst from the viewpoint of promoting the reaction. Such a catalyst is not particularly limited as long as it is a commonly used catalyst, and examples thereof include borofluoride compounds such as ammonium borofluoride and borofluoridium salt; neutral metal salt catalysts such as magnesium chloride and magnesium sulfate; and inorganic acids such as phosphoric acid, hydrochloric acid, and boric acid. These catalysts can also be used in combination with organic acids such as citric acid, tartaric acid, malic acid, maleic acid, and lactic acid as co-catalysts, if necessary. 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.

Examples of compounds having one or more isocyanate groups or blocked isocyanate groups include monofunctional isocyanate compounds such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate, as well as polyfunctional isocyanate compounds.

The polyfunctional isocyanate compound is not particularly limited as long as it has 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 diisocyanates, aryl diisocyanates, and cycloalkyl diisocyanates, and modified polyisocyanate compounds such as dimers or trimers of these diisocyanate compounds. The number of carbon atoms in the alkylene diisocyanate is preferably 1 to 12.

Examples of diisocyanate compounds include 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(phenylisocyanate), 2,4'-methylene-bis(phenylisocyanate), 3,4'-methylene-bis(phenylisocyanate), 4,4'-ethylene-bis(phenylisocyanate), ω,ω'-diisocyanate-1,3-dimethylbenzene 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, dimethyltriphenylmethane tetraisocyanate, and tris(isocyanatophenyl)-thiophosphate.

The modified polyisocyanate compound derived from the diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups, and examples thereof include polyisocyanates having a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, an allophanate structure, a trimer structure, etc., and adducts of aliphatic isocyanates of trimethylolpropane. Polymeric MDI (MDI = diphenylmethane diisocyanate) can also be used as a polyfunctional isocyanate compound.

The polyfunctional isocyanate compounds can be used alone or in combination of two or more.

The isocyanate groups contained in the polyfunctional isocyanate compound may be either intact or blocked with a blocking agent to form blocked isocyanate groups. Examples of the blocking agent 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 water repellency.

As the polyfunctional isocyanate compound, a water-dispersible isocyanate can be used, which is a polyisocyanate that has been given water dispersibility by introducing a hydrophilic group into the polyisocyanate structure to give it a surface active effect. In addition, known catalysts such as organotin and organozinc can be used in combination to promote the reaction.

The content ratio of the (α) component to the (δ) component in this embodiment is preferably 95:5 to 60:40 by mass, more preferably 95:5 to 70:30, and even more preferably 90:10 to 80:20. When the content ratio of the (α) component to the (δ) component is within the above range, the texture of the fiber substrate is adequately maintained, while excellent water repellency and water penetration prevention properties are imparted, and it becomes easy to obtain a fiber substrate having sufficient peel strength.

The water repellent composition according to this embodiment may contain additives, etc., as necessary. Examples of additives include other water repellents, surfactants, defoamers, pH adjusters, antibacterial agents, antifungal agents, colorants, antioxidants, deodorants, various organic solvents, chelating agents, antistatic agents, antibacterial and deodorant agents, flame retardants, softeners, and wrinkle inhibitors.

As the surfactant, known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used. The surfactants can be used alone or in combination of two or more.

Examples of defoaming agents 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 di-t-amylphenoxyethanol 3-heptyl cellosolve nonyl cellosolve 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 amide and acylate polyamine; sulfate ester-based defoaming agents such as sodium lauryl sulfate; and mineral oil. The defoaming agent can be used alone or in combination of two or more.

Examples of pH adjusters include organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, citric acid, malic acid, sulfonic acid, methanesulfonic acid, and toluenesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; and bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolamines, pyridine, and morpholine. The pH adjusters can be used alone or in combination of two or more.

Examples of organic solvents include aliphatic alcohols having 1 to 8 carbon atoms, such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, hexyl alcohol, and 2-ethylhexyl alcohol; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and diacetone alcohol; esters, such as ethyl acetate, methyl acetate, butyl acetate, methyl lactate, and ethyl lactate; ethers, such as diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tertiary butyl ether, and butyl carbitol; ethylene glycol, diethylene glycol, triethylene glycol, and the like. Examples of the organic solvent include glycols such as ethanol, propylene glycol, and dipropylene glycol; glycol ethers such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, and 3-methoxy-3-methyl-1-butanol; glycol esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate; and amides such as formamide, acetamide, benzamide, N,N-dimethylformamide, and acetanilide. The organic solvents can be used alone or in combination of two or more.

It is preferable to use an antistatic agent that does not easily impair water repellency. Examples of antistatic agents include cationic surfactants such as higher alcohol sulfates, sulfated oils, sulfonates, quaternary ammonium salts, and imidazoline quaternary salts, nonionic surfactants such as polyethylene glycol and polyhydric alcohol ester types, amphoteric surfactants such as imidazoline quaternary salts, alanine and betaine types, antistatic polymers of high molecular weight compounds, and polyalkylamines. Antistatic agents can be used alone or in combination of two or more.

The water-repellent textile product according to this embodiment will be described.

The water-repellent textile product according to this embodiment comprises a textile substrate and the water-repellent composition according to this embodiment adhered to the textile substrate.

The fiber substrate may be a fiber product or a fiber material that constitutes a fiber product.

The material of the fiber substrate is not particularly limited, but examples include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, and synthetic fibers such as nylon, polyester, polyurethane, and polypropylene, as well as composite fibers and blended fibers thereof.

The form of the fiber substrate is not particularly limited, but may be, for example, any of fibers, threads, cloth, nonwoven fabric, paper, etc.

The water-repellent textile product according to this embodiment may further include a coating film. The coating film may contain, for example, at least one resin selected from urethane resin, acrylic resin, and polyester resin other than those contained in the water repellent composition of the present invention.

The manufacturing method for the water-repellent textile product according to this embodiment will be explained.

The method for producing a water-repellent textile product according to this embodiment includes a step of contacting a textile substrate with a treatment liquid containing the water-repellent composition according to this embodiment.

Methods for treating the fiber substrate with the treatment liquid include, for example, processing methods such as immersion, spraying, and coating. In addition, when the water repellent composition contains water, it is preferable to dry the composition after it is applied to the fiber substrate in order to remove the water.

The water-repellent textile product of this embodiment can be coated on a predetermined portion. Examples of coating processes include moisture-permeable waterproofing and windproofing for sports and outdoor use. For example, moisture-permeable waterproofing can be achieved by applying a coating liquid containing a urethane resin, an acrylic resin, or the like other than those contained in the water repellent composition of the present invention and a medium to one side of the water-repellent treated textile product and drying it.

The amount of the water repellent composition applied to the fiber substrate can be adjusted as appropriate depending on the level of water repellency required, but from the viewpoint of imparting water repellency and water penetration resistance while adequately maintaining the texture of the fiber substrate and also ensuring sufficient peel strength, it is preferable to adjust the total amount of the (α) component, (β) component, and (γ) component contained in the water repellent composition applied to 100 g of the fiber substrate to 0.01 to 10 g, and more preferably to adjust the total amount to 0.05 to 5 g.

After the water repellent composition of this embodiment is applied to the fiber substrate, it is preferable to heat treat it appropriately. There are no particular limitations on the temperature conditions, but when the water repellent composition of this embodiment is used, the fiber substrate can exhibit sufficiently good water repellency under mild conditions of 100 to 130°C. The temperature conditions may be high-temperature treatment at 130°C or higher (preferably up to 200°C), and in such cases, it is possible to shorten the treatment time compared to the conventional case in which a fluorine-based water repellent is used. Therefore, according to the manufacturing method of the water-repellent fiber product of this embodiment, the deterioration of the fiber substrate due to heat is suppressed, the texture of the fiber substrate during the water repellent treatment becomes soft, and sufficient water penetration prevention properties can be imparted to the fiber substrate under mild heat treatment conditions, i.e., low-temperature curing conditions.

When the water repellent composition of this embodiment contains the (δ) component, from the viewpoint of more effectively imparting water repellency and water penetration prevention properties by sufficiently proceeding with the reaction of the crosslinking agent, and from the viewpoint of effectively improving the peel strength, it is preferable to heat the fiber substrate to which the (δ) component is attached at 110 to 180°C for 1 to 5 minutes. The amount of the (δ) component attached to the fiber substrate is preferably 0.1 to 50 mass% based on the weight of the fiber substrate, and more preferably 0.1 to 10 mass%.

The components contained in the water repellent composition according to this embodiment may be contained in multiple treatment liquids. For example, the treatment liquid may be divided into a treatment liquid containing the (α) component, the (β) component, and the (γ) component, and a treatment liquid containing the (δ) component.

The water-repellent textile products obtained by the manufacturing method of this embodiment can exhibit sufficient water repellency even when used outdoors for a long period of time, have excellent texture, and are environmentally friendly because they do not use fluorine-based compounds.

Although the above describes a preferred embodiment of the present invention, the present invention is not limited to the above embodiment.

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

<Preparation of acrylic resin dispersion>
The materials shown in Tables 1 and 2 (in the tables, the numerical values indicate (g)) were polymerized according to the procedure described below to obtain acrylic resin dispersions.

(Synthesis Example 1)
In a 0.5 L autoclave, 15 g of stearyl acrylate, 5 g of stearyl methacrylate, 0.5 g of Surfynol 465 (manufactured by Nissin Chemical Co., Ltd., HLB = 13), 1 g of Surfynol 440 (manufactured by Nissin Chemical Co., Ltd., HLB = 8), 0.5 g of Noigen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5), 1 g of stearyl trimethylammonium sulfate, 15 g of tripropylene glycol, and 54.9 g of water were placed, and mixed and stirred at 45°C to obtain a mixed solution. Ultrasonic waves were irradiated to this mixed solution to emulsify and disperse all the monomers. Next, 0.15 g of azobis(isobutylamidine) dihydrochloride was added to the mixed liquid, and 7 g of vinyl chloride was continuously injected into the autoclave under a nitrogen atmosphere so as to maintain the internal pressure of the autoclave at 0.3 MPa. The temperature was kept at 61° C. while the mixture was reacted for 6 hours, thereby obtaining an acrylic resin dispersion containing 27% by mass of acrylic resin.

(Synthesis Examples 2 to 13)
An acrylic resin dispersion was obtained in the same manner as in Synthesis Example 1, except that the materials shown in Tables 1 and 2 were used.
<Preparation of urethane resin dispersion>

(Synthesis Example 14)
A 1000 ml flask was charged with 206.74 g of ditrimethylolpropane, 469.87 g of stearic acid, and 3.4 g of p-toluenesulfonic acid. The mixture was then heated to 140°C under a nitrogen atmosphere, and a dehydration reaction was then carried out for 5 hours at 140-190°C under a nitrogen stream with a heating rate of about 0.4°C/min. The nitrogen flow rate was 5 ml per minute. After the reaction was completed, the acid value of the synthesized product was measured. The acid value was 2.0 mgKOH/g.

Next, 101.12 g of the above reaction product was placed in a 300 ml flask, and 23.78 g of hexamethylene diisocyanate, 25 g of methyl ethyl ketone, and 0.125 g of a bismuth catalyst (Neostan U-600: manufactured by Nitto Kasei Co., Ltd.) were added and reacted at 80°C for 7 hours. The reaction was continued until the NCO% reached 0.64%. After the reaction, the temperature was lowered to 40°C, and then 2.36 g of 3,5-dimethylpyrazole was added and reacted at 40°C for 1 hour to obtain a urethane resin dispersion containing 83% by mass of urethane resin. The weight average molecular weight of the obtained urethane resin was measured using gel permeation chromatography (HLC-8320GPC (TOSOH CORPORATION)), and the weight average molecular weight was 11,700.

The urethane resin contained in the obtained urethane resin dispersion is a compound obtained by reacting a polyfunctional compound in which R ³¹ is a residue obtained by removing four hydroxy groups from ditrimethylolpropane, d is 2, e is 2, W ¹ is an ester group, R ³² is a heptadecyl group, and V ¹ is a hydroxy group, with an isocyanate compound in which R ³³ is a hexylene group and f is 2 in the above general formula (II-1), and then blocking the remaining unreacted isocyanate groups with 3,5-dimethylpyrazole.

40 g of the urethane resin (isolated product) obtained above, 50 g of methyl ethyl ketone, 5 g of Decaglin 1-L (nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku), 5 g of Decaglin 1-SV (nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku), and 5 g of Arcard T-28 (cationic surfactant, manufactured by Lion Specialty Chemicals) were placed in a 500 mL stainless steel container and dissolved by heating to 50°C. Next, 295 g of hot water at 80°C was added, and the mixture was emulsified for 20 minutes while maintaining the temperature at 80°C using an ultrasonic emulsifier US-600E (manufactured by Nippon Seiki Seisakusho Co., Ltd.). The mixture was then cooled to obtain a dispersion containing 10% by mass of urethane resin.

(Synthesis Example 15)
A 1000 ml flask was charged with 255.88 g of trimethylolpropane, 542.51 g of stearic acid, and 1.6 g of p-toluenesulfonic acid. The mixture was then heated to 140°C under a nitrogen atmosphere, and a dehydration reaction was then carried out for 5 hours at 140-190°C under a nitrogen stream at a heating rate of about 0.4°C/min. The nitrogen flow rate was 5 ml per minute. After the reaction was completed, the acid value of the synthesized product was measured. The acid value was 2.0 mgKOH/g.

Next, 87.83 g of the above reaction product was placed in a 300 ml flask, and 37.11 g of hexamethylene diisocyanate, 25 g of methyl ethyl ketone, and 0.125 g of bismuth catalyst were added and reacted at 80°C for 7 hours. The reaction was continued until the NCO% reached 0.69%. After the reaction, the temperature was lowered to 40°C, and then 2.37 g of 3,5-dimethylpyrazole was added and reacted at 40°C for 1 hour, obtaining a urethane resin dispersion containing 83% by mass of urethane resin. The weight average molecular weight of the obtained urethane resin was measured using gel permeation chromatography, and was found to be 17,500.

The urethane resin contained in the obtained urethane resin dispersion is a compound obtained by reacting a polyfunctional compound in which R ³¹ is a residue obtained by removing three hydroxy groups from trimethylolpropane, d is 1, e is 2, W ¹ is an ester group, R ³² is a heptadecyl group, and V ¹ is a hydroxy group, with an isocyanate compound in which R ³³ is a hexylene group and f is 2 in the above general formula (II-1), and then blocking the remaining unreacted isocyanate groups with 3,5-dimethylpyrazole.

40 g of the urethane resin (isolated product) obtained above, 50 g of methyl ethyl ketone, 5 g of Decaglin 1-L (nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku), 5 g of Decaglin 1-SV (nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku), and 5 g of Arcard T-28 (cationic surfactant, manufactured by Lion Specialty Chemicals) were placed in a 500 mL stainless steel container and dissolved by heating to 50°C. Next, 295 g of hot water at 80°C was added, and the mixture was emulsified for 20 minutes while maintaining the temperature at 80°C using an ultrasonic emulsifier US-600E (manufactured by Nippon Seiki Seisakusho Co., Ltd.). The mixture was then cooled to obtain a dispersion containing 10% by mass of urethane resin.

<Preparation of Organo-Modified Silicone Emulsion>
(Synthesis Example 16)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube, and a dropping funnel, 63.2 g of methyl hydrogen silicone having an SiH group equivalent of 63.2 g/mol and a degree of polymerization of 50 was placed, and nitrogen was passed through and the mixture was heated to a temperature of 65° C. while mixing until it became uniform. As a hydrosilylation catalyst, a mixed solution of platinum chloride (IV) in ethylene glycol monobutyl ether and toluene was added so that the platinum concentration in the reactants in the system was 5 ppm. When the temperature of the reactants reached 120° C., 168.3 g of 1 mole of 1-dodecene was dropped, and the reaction was carried out at 120° C. for 6 hours. The completion of the addition reaction was confirmed by performing FT-IR analysis of the obtained organo-modified silicone and confirming that the absorption spectrum derived from the SiH group of the methyl hydrogen silicone had disappeared. In this way, an organo-modified silicone was obtained in which a1 in the above general formula (L-1) was 0, a2 was 50, R ²²² was a methyl group, R ²²³ was a dodecyl group, and R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ , and R ²³⁵ were methyl groups. Furthermore, 3 parts by mass of an ethylene oxide 9 mole adduct of a branched higher alcohol having 12 to 14 carbon atoms was added to 20 parts by mass of the obtained organo-modified silicone and mixed. Next, 77 parts by mass of water was added little by little while mixing, and emulsified in water to obtain an organo-modified silicone emulsion containing 20% by mass of the organo-modified silicone.

(Synthesis Example 17)
An organo-modified silicone and an organo-modified silicone emulsion were obtained in the same manner as in Synthesis Example 16, except that 84.2 g of 1 mole of 1-hexene was used instead of 168.3 g of 1 mole of 1-dodecene. The organo-modified silicone obtained was an organo-modified silicone in which a1 was 0, a2 was 50, R ²²² was a methyl group, R ²²³ was a hexyl group, and R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ were methyl groups in the above general formula (L-1).

(Synthesis Example 18)
An organo-modified silicone and an organo-modified silicone emulsion were obtained in the same manner as in Synthesis Example 16, except that 252.5 g of 1 mole of 1-octadecene was used instead of 168.3 g of 1 mole of 1-dodecene. The organo-modified silicone obtained was an organo-modified silicone in which a1 in the above general formula (L-1) was 0, a2 was 50, R ²²² was a methyl group, R ²²³ was an octadecyl group, and R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ were methyl groups.

(Synthesis Example 19)
An organo-modified silicone and an organo-modified silicone emulsion were obtained in the same manner as in Synthesis Example 16, except that 84.2 g of 0.5 mol of 1-dodecene and 126.2 g of 0.5 mol of 1-octadecene were used instead of 168.3 g of 1 mol of 1-dodecene. The organo-modified silicone obtained was an organo-modified silicone in which a1 in the above general formula (L-1) was 0, a2 was 50, R ²²² was a methyl group, R ²²³ was a dodecyl group or octadecyl group, and R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ were methyl groups.

(Synthesis Example 20)
An organo-modified silicone and an organo-modified silicone emulsion were obtained in the same manner as in Synthesis Example 17, except that 140.5 g of a copolymer of dimethylsiloxane and methylhydrogensiloxane was used instead of 63.2 g of methylhydrogensilicone, and 252.5 g of 1 mole of 1-octadecene was used instead of 168.3 g of 1 mole of 1-dodecene. The SiH group equivalent of the copolymer of dimethylsiloxane and methylhydrogensiloxane was 140.5 g/mol, and the degree of polymerization was 50. The organo-modified silicone obtained was an organo-modified silicone in which a1 in the above general formula (L-1) was 25, a2 was 25, R ²²⁰ and R ²²¹ were methyl groups, R ²²² was a methyl group, R ²²³ was an octadecyl group, and R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ were methyl groups.

<Production Example of Wax Emulsion>
(Production Example 1)
150 g of paraffin wax (melting point 69°C, penetration 12 (25°C)), 350 g of pure water, 8.5 g of polyoxyethylene stearyl ether (HLB = 10.7), and 6.5 g of polyoxyalkylene branched decyl ether (HLB = 14.7) were placed in a high-pressure reaction vessel and sealed. The vessel was then heated to 110-120°C while stirring. After that, the vessel was kept at high pressure for 30 minutes and high-pressure emulsified to obtain an aqueous dispersion of paraffin wax. The wax content was further adjusted to 30 mass% with pure water to obtain a wax emulsion.

(Production Example 2)
An aqueous dispersion of paraffin wax and a wax emulsion were obtained in the same manner as in Production Example 1, except that 150 g of paraffin wax {melting point 77° C., needle penetration 4 (25° C.)} was used instead of 150 g of paraffin wax {melting point 69° C., needle penetration 12 (25° C.)}.

(Production Example 3)
An aqueous dispersion of paraffin wax and a wax emulsion were obtained in the same manner as in Production Example 1, except that 150 g of paraffin wax {melting point 50° C., needle penetration 22 (25° C.)} was used instead of the paraffin wax {melting point 69° C., needle penetration 12 (25° C.)}.

<Preparation of test solution>
Example 1
A test liquid was obtained by mixing the acrylic resin dispersion obtained in Synthesis Example 1, the organo-modified silicone emulsion obtained in Synthesis Example 18, the wax emulsion obtained in Production Example 2, butyl diglycol as a medium, and Nicepol FE-26 (manufactured by Nicca Chemical Co., Ltd.) as an antistatic agent to obtain the composition (parts by mass) shown in Table 3. The blending amounts of the acrylic resin, organo-modified silicone, and wax in the test liquid of Example 1 are calculated as 20 parts by mass x 27% by mass = 5.4 parts by mass, 10 parts by mass x 20% by mass = 2 parts by mass, and 10 parts by mass x 30% by mass = 3 parts by mass, respectively.

Details of the materials shown in Tables 3 to 6 are given below.
IE-7045 (product name, manufactured by Toray Dow Corning Co., Ltd., dimethyl silicone)
・Nicepol FE-26 (product name, manufactured by Nicca Chemical Co., Ltd.)

(Examples 2 to 23 and Comparative Examples 1 to 9)
Test solutions were obtained in the same manner as in Example 1, except that the materials shown in Tables 3 to 6 were used.

I. Initial water repellency evaluation of water-repellent textile products by spray method Tests were conducted using the same method as the spray method of JIS L 1092 (2009) with a shower water temperature of 20 ° C. In this test, the test liquid prepared with the composition of the examples and comparative examples was diluted with water so that the total content of acrylic resin, other acrylic resin, urethane resin, organo-modified silicone, dimethyl silicone, wax and other wax was 1 mass % to obtain a treatment liquid. Next, a dyed 100% polyester cloth or a 100% nylon cloth was immersed in the obtained treatment liquid (pickup rate 60 mass %). Next, the immersed cloth was dried at 130 ° C for 2 minutes and further heat-treated at 170 ° C for 1 minute to obtain a water-repellent textile product. The water repellency of the water-repellent textile product was evaluated. The results were visually evaluated according to the following grades. The evaluation results are shown in Tables 3 to 6.
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

II. Durable water repellency evaluation of water-repellent textile products by spray method NK Assist NY-30 (manufactured by Nicca Chemical Co., Ltd.) was added as a crosslinking agent to the test liquid prepared with the composition of the examples and comparative examples so as to be 3 g/L. Next, the test liquid was diluted with water so that the total content of acrylic resin, other acrylic resin, urethane resin, organo-modified silicone, dimethyl silicone, wax, other wax and crosslinking agent was 1 mass % to prepare a treatment liquid. A dyed 100% polyester cloth or 100% nylon cloth was immersed in the treatment liquid (pickup rate 60 mass %). Next, the immersed cloth was dried at 130 ° C for 2 minutes and further heat-treated at 170 ° C for 1 minute to obtain a water-repellent textile product. The obtained water-repellent textile product was washed 10 times (L-10) according to the 103 method of JIS L 0217 (1995), and the water repellency after air drying was evaluated in the same manner as the water repellency evaluation method described above. The evaluation results are shown in Tables 3 to 6.

III. Measurement of contact angle for water-repellent textile products II. Evaluation of durable water repellency of water-repellent textile products Water-repellent textile products were obtained in the same manner as described above. 20 μl of ion-exchanged water was dropped onto the obtained water-repellent textile products, and the contact angle of the water droplet formed was measured. A KRUSS automatic contact angle meter DSA25 was used to measure the contact angle. The evaluation results are shown in Tables 3 to 6.

IV. Evaluation of Water-Soaking Prevention Property of Water-Repellent Textile Products II. Water-repellent textile products were obtained in the same manner as in the evaluation of durable water repellency of water-repellent textile products. The obtained water-repellent textile products were placed on a horizontal and flat surface, and three 200 μl drops of water were dropped onto the water-repellent textile products and left at room temperature. The number of droplets remaining on the water-repellent textile products with a contact angle of 90° or more after 10 minutes, 30 minutes, 60 minutes, and 120 minutes was regarded as the evaluation result. The evaluation results are shown in Tables 3 to 6.

V. Evaluation of the Feel of Water-Repellent Textile Products The 100% polyester water-repellent textile products described in II were evaluated by handling on the following 5-point scale. The evaluation criteria were set so that the feel of the water-repellent textile product in Comparative Example 1 was 2, and the feel of the water-repellent textile product in Comparative Example 2 was 5. The evaluation results are shown in Tables 3 to 6.
1: Hard ~ 5: Soft

VI. Peel strength evaluation for water-repellent textile products Tests were conducted in accordance with JIS K 6404-5 (1999). First, NK Assist NY-30 (manufactured by Nicca Chemical Co., Ltd.) was added as a crosslinking agent to the test liquid prepared with the composition of the examples and comparative examples so that the amount was 3 g/L. Next, the test liquid was diluted with water so that the total content of acrylic resin, other acrylic resin, urethane resin, organo-modified silicone, dimethyl silicone, wax, other wax and crosslinking agent was 3% by mass, and a treatment liquid was prepared. Next, a dyed 100% nylon cloth was immersed in the obtained treatment liquid (pickup rate 60% by mass). The immersed cloth was then dried at 130 ° C for 2 minutes and further heat-treated at 160 ° C for 30 seconds to obtain a base cloth. The resulting base fabric was thermally bonded to a seam tape ("MELCO Tape" manufactured by Sun Chemical Industry Co., Ltd.) at 150°C for 1 minute using a thermocompression device, and the peel strength between the base fabric and the seam tape was measured using an autograph (AG-IS manufactured by Shimadzu Corporation). The gripper was pulled at a moving speed of 100 mm/min, and the average stress was recorded as the peel strength [N/inch]. The results are shown in Tables 3 to 6.

Claims (5)

an acrylic resin having a structural unit derived from a (meth)acrylic acid ester monomer (A) represented by the following general formula (A-1) and/or a urethane resin having a structural unit derived from a polyfunctional compound represented by the following general formula (I-1) and a structural unit derived from an isocyanate compound represented by the following general formula (II-1);
An organo-modified silicone represented by the following general formula (L-1),
A water repellent composition for fibers, comprising:

[In formula (A-1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.]
R ³¹ [-W ¹ -R ³² ] _d [-V ¹ ] _e (I-1)
[In formula (I-1), d represents an integer of 1 or more, e represents an integer of 2 or more, (d+e) is 3 to 6, R ³¹ represents a (d+e)-valent organic group, W ¹ represents a divalent group which is an ester group, an amide group, a urethane group or a urea group, R ³² represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms, and V ¹ represents a hydroxy group, an amino group or a carboxy group, with the proviso that two or more of the e V ^1s are hydroxy groups and/or amino groups.]
R ³³ [-NCO] _f (II-1)
[In formula (II-1), R ³³ represents an f-valent organic group, and f represents an integer of 2 to 7.]

[In formula (L-1), R ²²⁰ , R ²²¹ and R ²²² each independently represent a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms; R ²²³ represents a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; a1 represents an integer of 0 or more; a2 represents an integer of 1 or more; (a1+a2) is 10 to 200; when a1 is 2 or more, a plurality of R ²²⁰ and R ²²¹ may be the same or different, and when a2 is 2 or more, a plurality of R ²²² and R ²²³ may be the same or different. The water repellent composition for fibers according to claim 1, wherein the acrylic resin further has a structural unit derived from at least one monomer (E) selected from vinyl chloride and vinylidene chloride. The water repellent composition for fibers according to claim 1 or 2, further comprising a crosslinking agent. A water-repellent textile product comprising a textile substrate and the textile water repellent composition according to any one of claims 1 to 3 attached to the textile substrate. A method for producing a water-repellent textile product, comprising a step of contacting a textile substrate with a treatment liquid containing the water repellent composition for textiles according to any one of claims 1 to 3.