JP2020105363A - Water repellant composition, water-repellent fiber product, and method for manufacturing water-repellent fiber product - Google Patents

Abstract

To provide: a water-repellent fiber product which is excellent in water repellency, water repellency durability and water repulsion, gives good feeling and hardly causes chalkiness; and a water repellant composition that can realize the water-repellent fiber product.SOLUTION: The water repellant composition includes: a non-fluorinated polymer (α) containing constituent units derived from a (meth)acrylic acid ester monomer (A1) represented by the specified general formula (A-1) and constituent units derived from a compound (A2) represented by the specified general formula (A-2); and a silicone resin (β).SELECTED DRAWING: None

Description

The present invention relates to a water repellent composition, a water repellent composition using the same, and a method for producing a water repellent fiber product.

Conventionally, a fluorine-based water repellent containing a fluorine-based compound has been known, and a fiber product having a water-repellent surface provided by treating the fluorine-based water repellent with a fiber product is known. .. Such a fluorine-based water repellent is generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group. Although textiles treated with a fluorine-based water repellent agent exhibit excellent water repellency, the concern about environmental impact has become clear with the monomer having a fluoroalkyl group. There has been an international demand for a non-fluorine-based water repellent that exhibits high-performance water repellent performance comparable to that of a water repellent.

Therefore, in recent years, research has been conducted on a non-fluorine-based water repellent containing no fluorine-based compound. For example, Patent Document 1 below discloses an aqueous emulsion containing a non-fluorine polymer having a repeating unit derived from a specific (meth)acrylate ester monomer, a specific surfactant, and a liquid medium containing water. Surface treatment agents are disclosed. In Patent Document 2 below, as a polymerizable monomer containing no fluorine, a polymerizable monomer containing a specific (meth)acrylate and a specific aromatic ring, or a specific cycloalkane is polymerized in a specific ratio. Disclosed is a water repellent composition containing the acrylic copolymer. Patent Document 3 below discloses a fiber processing agent containing at least one of a silicon compound, a wax compound, and a wax-zirconium compound.

JP, 2015-172198, A JP, 2005-221952, A JP, 2006-124866, A

In order to impart sufficient water repellency to a textile product, the conventional non-fluorine-based water repellent needs to treat the textile product under the condition that the water-repellent component has a high concentration. The textile product treated under such conditions has a problem that the texture becomes hard and nail marks (also called chalk marks) are likely to appear when the fiber surface is rubbed with a nail.

Further, the textile product has a problem that water penetrates if water droplets attached to the surface remain for a long time. Therefore, the water-repellent fiber product is required to have not only water repellency and durable water repellency, but also water repellency in which water droplets attached to the fiber surface immediately roll off.

The present invention has been made in view of the above circumstances, and is excellent in water repellency, durable water repellency, and water repellency, has a good texture, and is unlikely to cause chalk marks. It is an object of the present invention to provide a water repellent composition that enables the above and a method for producing a water repellent fiber product.

The present invention includes a structural unit derived from a (meth)acrylic acid ester monomer (A1) represented by the following general formula (A-1) and a compound (A2) represented by the following general formula (A-2). A water repellent composition comprising a non-fluorine-containing polymer (α) containing a structural unit derived from (3) and a silicone resin (β).

［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１２〜３０の１価の炭化水素基を表す。］

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. ]

［式（Ａ−２）中、Ｒ^１１は水素又はメチル基を表し、Ｒ^１２は炭素数１〜６の２価の炭化水素基を表し、Ｚはエステル基またはアミド基を表し、Ｗは−ＣＯ−Ｒ^１３（式中、Ｒ^１３は炭素数１〜４の１価の炭化水素基を表す）で表される基、−ＮＨ−ＣＯ−ＮＨ_２で表される基、又は下記式（Ａ−３）で表される基を表す。

］

[In the formula (A-2), R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, and W represents -. ^{CO-R 13 (wherein, R 13} is a monovalent hydrocarbon represents a group having 1 to 4 carbon atoms) groups represented by the group represented by -NH-CO-NH _2, or the following formula (a -3) represents a group represented by.

]

According to the water repellent composition of the present invention, by containing the specific non-fluorine-based polymer (α) and the silicone resin (β) in combination, water repellency, durable water repellency, water repellency and texture are obtained. It is possible to obtain an excellent water-repellent fiber product, and the resulting fiber product is unlikely to cause chalk marks. The present inventors presume the reason why such an effect is obtained as follows. It is considered that the non-fluorine-based polymer (α) has a property of easily aggregating by having an ester group or an amide group and a ureido group or a ketone group as a constitutional unit derived from the compound (A2), It is considered that the fiber treated with the composition containing the non-fluorine-based polymer (α) and the silicone resin (β) having such characteristics is likely to have an uneven structure on the fiber surface. Therefore, even if the non-fluorinated polymer (α) and the silicone resin (β) are adhered onto the fiber under the treatment conditions at a low concentration where the texture of the fiber is not impaired and chalk marks are less likely to occur, the uneven structure is formed. The present inventors believe that the water repellent property, the durable water repellent property and the water repellent property can be imparted by the above treatment.

By the way, a water-repellent textile product or the like may be coated with urethane resin or acrylic resin on a predetermined portion. In this case, the textile product is required to have sufficient water repellency, but the coating is difficult to be peeled off at the portion to be coated. The difficulty of peeling the coating can be evaluated by measuring the stress (peeling strength) required to peel the coating film from the water-repellent treated textile. According to the water repellent composition of the present invention, the resulting fiber product can have sufficient peel strength for coating.

From the viewpoint of water repellency, durable water repellency and peel strength, the non-fluorine-based polymer (α) further contains a structural unit derived from at least one monomer (VC) of vinyl chloride and vinylidene chloride. You can

The present invention also provides a water repellent fiber product comprising a fiber product to which the water repellent composition according to the present invention is attached.

The water-repellent fiber product of the present invention is excellent in water repellency, durable water repellency, water repellency and texture, and is unlikely to cause chalk marks. Further, the water-repellent textile product of the present invention can have sufficient peel strength for coating.

The present invention also provides a method for producing a water repellent fiber product, which comprises a step of treating a fiber product with a treatment liquid containing the water repellent composition according to the present invention.

According to the method for producing a water-repellent fiber product of the present invention, it is possible to obtain a water-repellent fiber product which is excellent in water repellency, durable water repellency, water repellency, and texture and which is unlikely to cause chalk marks. In addition, the water-repellent textile product produced by the method of the present invention can have sufficient peel strength for coating.

According to the present invention, a water-repellent fiber product which is excellent in water repellency, durable water repellency and water repellency, has a good texture, and is unlikely to cause chalk marks, and a water repellent composition capable of realizing the same. And the manufacturing method of a water-repellent textile can be provided.

The water repellent composition of the present embodiment contains a non-fluorine-based polymer (α) and a silicone resin (β).

<Non-fluorine-based polymer (α)>
The non-fluorine-based polymer (α) is a structural unit derived from a (meth)acrylic acid ester monomer (A1) represented by the following general formula (A-1) (hereinafter, also referred to as “component (A1)”). And a structural unit derived from the compound (A2) represented by the following general formula (A-2) (hereinafter, also referred to as “component (A2)”).

［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１２〜３０の１価の炭化水素基を表す。］

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. ]

［式（Ａ−２）中、Ｒ^１１は水素又はメチル基を表し、Ｒ^１２は炭素数１〜６の２価の炭化水素基を表し、Ｚはエステル基またはアミド基を表し、Ｗは−ＣＯ−Ｒ^１３（Ｒ^１３は炭素数１〜４の１価の炭化水素基を表す）で表される基、−ＮＨ−ＣＯ−ＮＨ_２で表される基、又は下記式（Ａ−３）で表される基を表す。

］

[In the formula (A-2), R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, and W represents -. ^{CO-R 13 (R} 13 is a monovalent hydrocarbon represents a group having 1 to 4 carbon atoms) groups represented by the group represented by -NH-CO-NH _2, or the following formula (a-3) Represents a group represented by.

]

Here, "(meth)acrylic acid ester" means "acrylic acid ester" or the corresponding "methacrylic acid ester", and is synonymous with "(meth)acrylic acid", "(meth)acrylamide" and the like. is there.

The component (A1) has a monovalent hydrocarbon group having 12 to 30 carbon atoms, which may have a substituent. This hydrocarbon group may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be an alicyclic or aromatic cyclic group. May have. Among these, from the viewpoints of water repellency and texture, linear ones are preferable, and linear alkyl groups are more preferable. In this case, the water repellency will be more excellent. When the monovalent hydrocarbon group having 12 to 30 carbon atoms has a substituent, the substituent includes a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group and (meth)acryloyloxy. One or more of the groups and the like can be mentioned. In this embodiment, in the general formula (A-1), R ² is preferably an unsubstituted hydrocarbon group.

The number of carbon atoms of the hydrocarbon group is preferably 12 to 24 from the same viewpoint as above.

More preferably, the hydrocarbon group has 12 to 22 carbon atoms. When the carbon number is in this range, the water repellency and the feel are particularly excellent. Particularly preferred as the hydrocarbon group is a linear alkyl group having 18 to 22 carbon atoms.

Examples of the component (A1) include stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, and (meth)acrylic acid. Examples include heptadecyl, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate and behenyl (meth)acrylate.

The component (A1) can have at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group, which can react with a crosslinking agent. In this case, the durable water repellency of the obtained textile product can be further improved. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. When the component (A1) has an amino group, the texture of the resulting fiber product can be further improved.

The component (A1) is preferably a monofunctional (meth)acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

As the component (A1), one type may be used alone, or two or more types may be used in combination.

In the above formula (A-2), R ¹² may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and further may be a fat. It may have a cyclic ring.

When Z is an ester group in the above formula (A-2), R ¹² is a hydrocarbon group having 2 to 4 carbon atoms, and W is a group represented by —NH—CO—NH ₂ or the above formula. It is preferably a group represented by (A-3). When Z is an amide group, R ¹² is a hydrocarbon group having 2 to 4 carbon atoms, W is a group represented by —CO—R ¹³ , and R ¹³ has 1 to 2 carbon atoms. It is preferable.

The component (A2) is not particularly limited, and examples thereof include diacetone acrylamide, 2-methylpropenoic acid [2-(2-oxo-2-imidazolidinyl)ethyl], N-[2-(2-oxoimidazolidine). -3-yl)ethyl]methacrylamide. Among these, as the component (A2), diacetone acrylamide and [2-(2-oxo-2-imidazolidinyl)ethyl] 2-methylpropenoate are preferable from the viewpoint of durable water repellency of the textile product.

As the component (A2), one type may be used alone, or two or more types may be used in combination.

The content ratio of the structural unit derived from the component (A1) and the structural unit derived from the component (A2) in the non-fluorine-based polymer (α) of the present embodiment is such that the mass of the component (A1) and the component (A2) to be blended together. The ratio (A1)/(A2) to the mass of is preferably 99.9/0.1 to 70/30, more preferably 99.8/0.2 to 80/20, and 99 More preferably, it is 0.7/0.3 to 90/10. When (A1)/(A2) is within the above range, the resulting water-repellent product has better durability and water repellency.

The total mass of the component (A1) and the component (A2) to be blended is preferably 60 to 100% by mass with respect to the total amount of the monomer components constituting the non-fluorine-based polymer (α), and 70 -99 mass% is more preferable, and 80-98 mass% is still more preferable.

From the viewpoint of peeling strength, the non-fluorine-based polymer (α) is a monomer (VC) of at least one of vinyl chloride and vinylidene chloride (hereinafter, referred to as “A1” component and (A2) component, "(VC) component") is preferably contained as a monomer component.

The component (VC) is preferably vinyl chloride from the viewpoint of maintaining the texture of the textile product.

From the viewpoint of water repellency, durable water repellency and peel strength, the mass of the component (VC) to be blended is 10 parts by mass with respect to a total of 100 masses of the components (A1) and (A2) to be blended. It is preferably at least 20 parts by mass, more preferably at least 20 parts by mass. From the viewpoint of water repellency, durable water repellency and texture, the mass of the (VC) component to be blended is 100 parts by mass or less based on 100 masses of the total of the masses of the (A1) component and the (A2) component to be blended. Is preferable, and more preferably 75 parts by mass or less.

The non-fluorine-based polymer (α) is a component (A1) and a component (A2) in that the non-fluorine-based polymer (α) can improve the emulsion stability of the non-fluorine-based polymer (α) during and after emulsion polymerization or dispersion polymerization. In addition, a compound represented by the following general formula (I-1) in which (B1) HLB is 7 to 18 and a general formula (II-1) in which (B2) HLB is 7 to 18 are represented. At least one reactive emulsifier selected from the group consisting of a compound and (B3) HLB of 7 to 18 and a compound having an alkylene oxide having 2 to 4 carbon atoms added to an oil or fat having a hydroxyl group and a polymerizable unsaturated group. It is preferable to contain (B) (hereinafter, also referred to as “component (B)”) as a monomer component.

［式（Ｉ−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 the formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y ¹ represents an alkyleneoxy group having 2 to 4 carbon atoms. It represents a divalent group containing. ]

［式（ＩＩ−１）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。］

Wherein (II-1), ^{R 4} represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, ^{Y 2} is includes an alkyleneoxy group having 2 to 4 carbon atoms Represents a divalent group. ]

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

Further, “HLB” is an HLB value calculated by the Griffin method by regarding ethyleneoxy groups as hydrophilic groups and all other groups as lipophilic groups.

The HLB of the compounds of (B1) to (B3) used in the present embodiment is 7 to 18, which is obtained during and after emulsion polymerization or dispersion polymerization of the non-fluorine-based polymer (α) of the present embodiment. From the viewpoint of emulsion stability in the composition (hereinafter simply referred to as emulsion stability), 9 to 15 is preferable. Further, in view of storage stability of the water repellent composition, it is more preferable to use two or more kinds of reactive emulsifiers (B) having different HLB within the above range in combination.

In the reactive emulsifier (B1) represented by the general formula (I-1) used in the present embodiment, R ³ is hydrogen or a methyl group, and the component (A1) and/or the component (A2) It is more preferably a methyl group from the viewpoint of copolymerizability. X is a linear or branched alkylene group having 1 to 6 carbon atoms, and from the viewpoint of emulsion stability of the non-fluorine-based polymer (α) of the present embodiment, a linear alkylene group having 2 to 3 carbon atoms is more preferable. .. 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 fall within the above HLB range. When two or more alkyleneoxy groups are used, they can have a block addition structure or a random addition structure.

As the compound represented by the general formula (I-1), a compound represented by the following general formula (I-2) is preferable.

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

In the compound represented by the general formula (I-2), R ³ is hydrogen or a methyl group, and is a methyl group in terms of copolymerizability with the component (A1) and/or the component (A2). More preferable. X is a linear or branched alkylene group having 1 to 6 carbon atoms, and from the viewpoint of emulsion stability of the non-fluorine-based polymer (α) of the present embodiment, a linear alkylene group having 2 to 3 carbon atoms is more preferable. .. 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 fall within the above HLB range. From the viewpoint of emulsion stability of the non-fluorine-based polymer (α) of the present embodiment, 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. Further, when two or more kinds of A ¹ O are used, they can have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the general formula (I-2) can be obtained by a conventionally known method and is not particularly limited. Further, they can be easily obtained from commercial products, and examples thereof include "Latemul PD-420", "Latemuru PD-430", "Latemuru PD-450" manufactured by Kao Corporation.

In the reactive emulsifier (B2) represented by the general formula (II-1) used in the present embodiment, R ⁴ is a monovalent unsaturated carbonization having a polymerizable unsaturated group and having 13 to 17 carbon atoms. Hydrogen group, such as tridecenyl group, tridecadienyl group, tetradecenyl group, tetradienyl group, pentadecenyl group, pentadecadienyl group, pentadecatrienyl group, heptadecenyl group, heptadecadienyl group, heptadecatrienyl group and the like. .. From the viewpoint of the emulsion stability of the non-fluorine-based polymer (α) of the present embodiment, R ⁴ is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

Y ² 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 ² can be appropriately selected so as to fall within the above HLB range. When two or more alkyleneoxy groups are used, they can have a block addition structure or a random addition structure. From the viewpoint of emulsion stability of the non-fluorine-based polymer (α) of the present embodiment, the alkyleneoxy group is more preferably an ethyleneoxy group.

As the compound represented by the general formula (II-1), a compound represented by the following general formula (II-2) is preferable.

［式（ＩＩ−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 the formula (II-2), R ⁴ represents a C 13 to C 17 monovalent unsaturated hydrocarbon group having a polymerizable unsaturated group, and A ² O represents a C ^{2 to} C 4 alkyleneoxy group. , N can be appropriately selected so as to fall within the above HLB range, and specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, n A ² O are the same. May also be different. ]

^{R 4} in the compound represented by the above Formula (II-2) are the same as those for ^{R 4} in the above-mentioned general formula (II-1).

A ² O is an alkyleneoxy group having 2 to 4 carbon atoms. From the viewpoint of the emulsion stability of the non-fluorine-based polymer (α) of the present embodiment, the type and combination of A ² O and the number of n can be appropriately selected so as to fall within the above HLB range. From the viewpoint of emulsion stability of the non-fluorine-based polymer (α) of the present embodiment, A ² O is more preferably an ethyleneoxy group, n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20 and 8 The integer of -14 is more preferable. When n is 2 or more, n A ² O may be the same or different. Further, when two or more kinds of A ² O are used, they can have a block addition structure or a random addition structure.

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

The corresponding phenol having an unsaturated hydrocarbon group includes not only industrially produced pure products or mixtures, but also those present as pure products or mixtures extracted and purified from plants and the like. For example, 3-[8(Z),11(Z),14-pentadecatrienyl]phenol, 3-[8(Z),11(Z), which are extracted from the shells of cashew nuts and are collectively called cardanol. -Pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol, and the like.

The reactive emulsifier (B3) used in the present embodiment is a compound having an HLB of 7 to 18 and an alkylene oxide having 2 to 4 carbon atoms added to an oil or fat having a hydroxyl group and a polymerizable unsaturated group. .. Examples of fats and oils having a hydroxyl group and a polymerizable unsaturated group include hydroxy unsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.). Examples thereof include mono- or diglycerides of fatty acids, and triglycerides of fatty acids containing at least one kind of hydroxy unsaturated fatty acid (ricinoleic acid, ricinoelaidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of emulsion stability of the non-fluorine-based polymer (α) of the present embodiment, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one kind of hydroxy unsaturated fatty acid is preferable, and castor oil (triglyceride of a fatty acid containing ricinoleic acid). 2) C2-C4 alkylene oxide adducts are more preferable, and castor oil ethylene oxide adducts are further preferable. Further, the number of moles of alkylene oxide added can be appropriately selected so as to fall within the above HLB range, and in terms of emulsion stability of the non-fluorine-based polymer (α) of the present embodiment, 20 to 50 moles is preferable. More preferably, it is more preferably 25 to 45 mol. When two or more alkylene oxides are used, they can have a block addition structure or a random addition structure.

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

The composition ratio of the monomer of the component (B) in the non-fluorine-based polymer (α) of the present embodiment is determined by the water repellency of the obtained fiber product, and the non-fluorine-based polymer (α) emulsion polymerization or dispersion of the present embodiment. From the viewpoint that the emulsion stability in the composition during and after the polymerization can be improved, it is 0.5 to 20 mass% with respect to the total amount of the monomer components constituting the non-fluorine-based polymer (α). Is preferable, 1 to 15% by mass is more preferable, and 3 to 10% by mass is further preferable.

The non-fluorine-based polymer (α) contained in the water repellent composition of the present embodiment can improve the durable water repellency of the resulting fiber product, and in addition to the components (A1) and (A2), the following ( C1), (C2), (C3) and at least one second (meth)acrylic acid ester monomer (C) selected from the group consisting of (C4) (hereinafter, also referred to as “C component”) It is preferably contained as a monomer component.

［式（Ｃ−１）中、Ｒ^５は水素又はメチル基を表し、Ｒ^６はヒドロキシル基、アミノ基、カルボキシル基、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。］ (C1) A (meth)acrylic acid ester monomer represented by the following general formula (C-1)

[In the formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ is at least selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth)acryloyloxy group. It represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having one kind of functional group. However, the number of (meth)acryloyloxy groups in the molecule is 2 or less. ]

［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。］ (C2) (Meth)acrylic acid ester monomer represented by the following general formula (C-2)

[In the formula (C-2), R ⁷ represents hydrogen or a methyl group, and R ⁸ represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent. ]

［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。］ (C3) Methacrylic acid ester monomer represented by the following general formula (C-3)

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

［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。］ (C4) (Meth)acrylic acid ester monomer represented by the following general formula (C-4)

[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 polymerizable unsaturated group. Represents a valent organic group. ]

The number of carbon atoms of the monomer (C1) has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth)acryloyloxy group in the ester portion. It is a (meth)acrylic acid ester monomer having a monovalent chain hydrocarbon group of 1 to 11. From the viewpoint of reacting with a crosslinking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms is at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group. It is preferable to have a functional group. When the non-fluorine-containing polymer (α) containing the monomer (C1) having a group capable of reacting with these cross-linking agents is treated with the cross-linking agent into a fiber product, the texture of the resulting fiber product is maintained. As it is, the durable water repellency can be improved. 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 hydrocarbon group or an unsaturated hydrocarbon group. Further, the chain hydrocarbon group may further have a substituent in addition to the above functional group. Above all, in terms of improving the durable water repellency of the obtained fiber product, it is preferably linear and/or saturated hydrocarbon group.

Specific examples of the (C1) monomer include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl. Isocyanate and the like can be mentioned. These monomers may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethylisocyanate are preferable because the durable water repellency of the obtained fiber product can be improved. Further, dimethylaminoethyl (meth)acrylate is preferable from the viewpoint of improving the feel of the obtained fiber product.

From the viewpoint of water repellency, the mass of the component (C1) to be blended is preferably 3 parts by mass or more based on 100 masses of the total mass of the components (A1) and (A2) to be blended, It is more preferably 5 parts by mass or more. From the viewpoint of water repellency, the mass of the component (C1) to be blended is preferably 30 parts by mass or less based on 100 masses of the total mass of the components (A1) and (A2) to be blended, It is more preferably 25 parts by mass or less.

The above-mentioned (C2) monomer is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester portion, and the cyclic hydrocarbon group includes an isobornyl group, Examples thereof include 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. Further, it is preferable that these cyclic hydrocarbon groups are directly bonded to an ester bond from the viewpoint of improving durable water repellency. The cyclic hydrocarbon group may be alicyclic or aromatic, and when it is alicyclic, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specific monomers include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and the like. These monomers may be used alone or in combination of two or more. Among them, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferable, and isobornyl methacrylate is more preferable, from the viewpoint that the durable water repellency of the obtained fiber product can be improved.

From the viewpoint of water repellency, the mass of the component (C2) to be blended is preferably 3 parts by mass or more based on 100 parts by mass of the total mass of the components (A1) and (A2) to be blended. It is more preferably 5 parts by mass or more. From the viewpoint of water repellency, the mass of the component (C2) to be blended is preferably 30 parts by mass or less based on 100 parts by mass of the total mass of the components (A1) and (A2) to be blended. More preferably 25 parts by mass or less.

The above-mentioned monomer (C3) is a methacrylic acid ester monomer in which an unsubstituted monovalent linear 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 straight chain hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group. Specific compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. These monomers may be used alone or in combination of two or more. Of these, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferable, and methyl methacrylate is more preferable, from the viewpoint that the durable water repellency of the obtained fiber product can be improved.

From the viewpoint of water repellency, the mass of the component (C3) to be blended is preferably 3 parts by mass or more based on 100 parts by mass of the total mass of the components (A1) and (A2) to be blended. It is more preferably 5 parts by mass or more. From the viewpoint of water repellency, the mass of the component (C3) to be blended is preferably 30 parts by mass or less based on 100 parts by mass of the total mass of the components (A1) and (A2) to be blended. More preferably 25 parts by mass or less.

The monomer (C4) is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In the present embodiment, T in the general formula (C-4) is a (meth)acryloyloxy group, and a polyfunctional (meth)acrylic acid ester monomer having three or more (meth)acryloyloxy groups in one molecule. A monomer is preferred. In the formula (C-4), p Ts may be the same or different. Specific compounds include, for example, ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Examples thereof include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate. These monomers may be used alone or in combination of two or more. Among them, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferable because the durable water repellency of the obtained fiber product can be improved.

From the viewpoint of water repellency, the mass of the component (C4) to be blended is preferably 3 parts by mass or more based on 100 parts by mass of the total mass of the components (A1) and (A2) to be blended. It is more preferably 5 parts by mass or more. From the viewpoint of water repellency, the mass of the component (C4) to be blended is preferably 30 parts by mass or less based on 100 parts by mass of the total mass of the components (A1) and (A2) to be blended. More preferably 25 parts by mass or less.

From the viewpoint of water repellency and texture of the resulting fiber product, the total composition ratio of the above-mentioned monomer of the component (C) in the non-fluorine-containing polymer (α) of the present embodiment is the same as that of the non-fluorine-containing polymer (α). It is preferably from 1 to 30% by mass, more preferably from 3 to 25% by mass, and further preferably from 5 to 20% by mass, based on the total amount of the constituent monomer components.

From the viewpoint of water repellency, the mass of the component (C) to be blended is preferably 3 parts by mass or more based on 100 parts by mass of the total mass of the components (A1) and (A2) to be blended. It is more preferably 5 parts by mass or more. From the viewpoint of water repellency, the mass of the component (C) to be blended is preferably 30 parts by mass or less based on 100 parts by mass of the total mass of the components (A1) and (A2) to be blended. More preferably 25 parts by mass or less.

The non-fluorine-based polymer (α) contained in the water repellent composition of the present embodiment is, in addition to the component (A1) and the component (A2), a monofunctional monomer (D) (which is copolymerizable with these components). Hereinafter, also referred to as “(D) component”) can be contained in a range that does not impair the effects of the present invention.

Examples of the component (D) include (meth)acryloylmorpholine, (meth)acrylic acid ester having a hydrocarbon group other than the components (A) and (C), (meth)acrylic acid, fumaric acid ester, and maleic acid. Examples thereof include esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, vinyl monomers other than the fluorine-free (VC) component such as ethylene and styrene. The (meth)acrylic acid ester having a hydrocarbon group other than the components (A) and (C) has a hydrocarbon group, a vinyl group, a hydroxyl group, an amino group, an epoxy group and an isocyanate group, a blocked isocyanate group. May have a substituent such as a quaternary ammonium group, may have a substituent other than a group capable of reacting with a crosslinking agent such as a quaternary ammonium group, an ether bond, an ester bond, an amide bond, or a urethane bond Etc. may be included. Examples of the (meth)acrylic acid ester other than the components (A) and (C) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate and the like. Are listed. Among them, (meth)acryloylmorpholine is more preferable because it can improve the peel strength of the obtained fiber product with respect to the coating.

From the viewpoint of water repellency, the mass of the component (D) to be blended is preferably 3 parts by mass or more based on 100 parts by mass of the total mass of the components (A1) and (A2) to be blended. It is more preferably 5 parts by mass or more. From the viewpoint of water repellency, the mass of the above-mentioned (D) monomer to be blended is 40 parts by mass or less based on 100 parts by mass of the total of the mass of the (A1) component and the mass of the (A2) component to be blended. It is preferable that the amount is 35 parts by mass or less.

The non-fluorine-based polymer (α) of the present embodiment has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group, which can react with a crosslinking agent, It is preferable because it improves the durable water repellency of the resulting fiber product. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. In addition, it is preferable that the non-fluorine-based polymer (α) has an amino group because the texture of the resulting fiber product is improved.

The weight average molecular weight of the non-fluorine-based polymer (α) of the present embodiment is preferably 30,000 or more. When the weight average molecular weight is 30,000 or more, the water repellency of the obtained fiber product tends to be further improved. Furthermore, the weight average molecular weight of the non-fluorine-based polymer (α) is more preferably 100,000 or more. In this case, the obtained fiber product can exhibit water repellency more sufficiently. The upper limit of the weight average molecular weight of the non-fluorine-based polymer (α) is preferably about 5,000,000.

The weight average molecular weight of the non-fluorine-based polymer (α) means the eluent under the conditions of a column temperature of 40° C. and a flow rate of 1.0 ml/min by a GPC device (GPC “HLC-8020” manufactured by Tosoh Corporation). It is measured by using tetrahydrofuran and is a value in terms of standard polystyrene. In addition, as the column, one having three connected product names TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation is used.

In the present embodiment, the melt viscosity of the non-fluorine-based polymer (α) at 105° C. is preferably 1000 Pa·s or less. When the melt viscosity at 105° C. is 1000 Pa·s or less, the texture of the obtained fiber product tends to be easily maintained. Further, when the melt viscosity of the non-fluorine-based polymer (α) is 1000 Pa·s or less, when the non-fluorine-based polymer (α) is emulsified or dispersed into a water repellent composition, the non-fluorine-based polymer (α) ) Can be prevented from precipitating or settling, so that the storage stability of the water repellent composition tends to be favorably maintained. The melt viscosity at 105°C is more preferably 500 Pa·s or less. In this case, the obtained textile product or the like is sufficiently water-repellent and also has a better feeling.

“Melt viscosity at 105° C.” means that an elevated flow tester (for example, CFT-500 manufactured by Shimadzu Corporation) is used and 1 g of a non-fluorine-containing polymer is put in a cylinder equipped with a die (length 10 mm, diameter 1 mm). Viscosity when measured at a temperature of 105° C. for 6 minutes with a plunger applied with a load of 100 kg·f/cm ² .

<Silicone resin (β)>
Examples of the silicone resin (β) include silicone resin and silicone oil. The silicone resin is an organopolysiloxane which contains MQ, MDQ, MT, MTQ, MDT or MDTQ as a constituent, is solid at 25° C. and has a three-dimensional structure. Here, M, D, T, and Q represent (R″) ₃ SiO _0.5 unit, (R″) ₂ SiO unit, R″SiO _1.5 unit, and SiO ₂ unit, respectively. R″ represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

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

The silicone resin can also be obtained as a solution prepared by dissolving it in a suitable solvent. Examples of the solvent include relatively low molecular weight methylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and a mixture of these solvents. Etc.

Examples of the silicone resin solution include KF7312J (trimethylsilyl group-containing polysiloxane: decamethylcyclopentasiloxane=50:50 mixture) and KF7312F (trimethylsilyl group-containing polysiloxane: octamethyl) commercially available from Shin-Etsu Chemical Co., Ltd. Cyclotetrasiloxane = 50:50 mixture), KF9021L (trimethylsilyl group-containing polysiloxane: low-viscosity methyl polysiloxane = 50:50 mixture), KF7312L (trimethylsilyl group-containing polysiloxane: low-viscosity methyl polysiloxane = 50:50 mixture), etc. Are listed.

Examples of the silicone resin alone include MQ-1600 solid Resin (trimethylsilyl group-containing polysiloxane) and MQ-1640 Flakes Resin (trimethylsilyl group-containing polysiloxane, polypropylsilsesquioxane), which are commercially available from Toray Dow Corning Co., Ltd. And so on. The above-mentioned commercially available product contains trimethylsilyl group-containing polysiloxane and contains MQ, MDQ, MT, MTQ, MDT or MDTQ.

Silicone oil is a linear organopolysiloxane, and may have an organic group on at least one of the side chain and the terminal of the organopolysiloxane. Examples of such silicone oils include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil; amino-modified silicone oil, epoxy-modified silicone oil, carbinol-modified silicone oil, mercapto-modified silicone oil. , Carboxyl modified silicone oil, polyether modified silicone oil, alkyl modified silicone oil, aralkyl modified silicone oil, alkyl aralkyl modified silicone oil, higher fatty acid ester modified silicone oil, higher aliphatic amide modified silicone oil, with the following general formula (1) Examples thereof include modified silicone oils such as the organo-modified silicone oils represented. In the general formula (1) below, each structural unit may be a block, may be random, or may be arranged alternately.

［式（１）中、Ｒ^２０、Ｒ^２１及びＲ^２２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^２３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^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４及びＲ^３５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、ａは０以上の整数を表し、ｂは１以上の整数を表し、（ａ＋ｂ）は１０〜２００であり、ａが２以上の場合、複数存在するＲ^２０及びＲ^２１はそれぞれ同一であっても異なっていてもよく、ｂが２以上の場合、複数存在するＲ^２２及びＲ^２３はそれぞれ同一であっても異なっていてもよい。］

[In the formula (1), R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, and R ²³ is a carbon atom having an aromatic ring. Represents a hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms, and R ³⁰ , R ³¹ , R ³² , R ³³ , R ^34, and R ³⁵ each independently represent a hydrogen atom, a methyl group, or ethyl. Group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a represents an integer of 0 or more, and b is 1 Represents the above integer, (a+b) is 10 to 200, and when a is 2 or more, a plurality of R ²⁰ and R ²¹ may be the same or different, and when b is 2 or more A plurality of R ²² and R ²³ may be the same or different. ]

Among such silicone resins, silicone oil is preferable from the viewpoint of water repellency and dispersibility of the water repellent composition in an aqueous medium, and methylhydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carbinol. A modified silicone oil, a carboxyl-modified silicone oil, a mercapto-modified silicone oil, and an alkylaralkyl-modified silicone oil are more preferred, and an alkyl-modified silicone is or is obtained because it further improves the water repellency and durable water repellency of the obtained textile product. Amino-modified silicone, methyl hydrogen silicone, and dimethyl silicone are more preferable because they can further improve the texture of the textile product and further reduce the occurrence of chalk marks.

In the organo-modified silicone oil represented by the general formula (1), the alkoxy group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group and the like. It is preferable that R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoint of easy industrial production and easy availability.

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

［式（２）中、Ｒ^４０は、炭素数２〜６のアルキレン基を表し、Ｒ^４１は、単結合又は炭素数１〜４のアルキレン基を表し、ｃは０〜３の整数を表す。ｃが２又は３の場合、複数存在するＲ^４１は同一であっても異なっていてもよい。］

[In the formula (2), R ⁴⁰ represents an alkylene group having 2 to 6 carbon atoms, R ⁴¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and c represents an integer of 0 to 3. When c is 2 or 3, a plurality of R ^{41 s} may be the same or different. ]

The alkylene group may be linear or branched.

［式（３）中、Ｒ^４２は、炭素数２〜６のアルキレン基を表し、Ｒ^４３は、単結合又は炭素数１〜４のアルキレン基を表し、ｄは０〜３の整数を表す。ｄが２又は３の場合、複数存在するＲ^４３は同一であっても異なっていてもよい。］

[In the formula (3), R ⁴² represents an alkylene group having 2 to 6 carbon atoms, R ⁴³ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and d represents an integer of 0 to 3. When d is 2 or 3, a plurality of R ^43's 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 phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, naphthylethyl group and the like. Among them, the phenylethyl group and the phenylpropyl group are preferable because they are industrially easily produced and easily available.

In the group represented by the above general formula (2), R ⁴⁰ is preferably an alkylene group having 2 to 4 carbon atoms, and c is 0 or 1 from the viewpoints of easy industrial production and easy availability. It is preferable that it is, and it is more preferable that it is 0.

In the group represented by the general formula (3), R ⁴² is preferably an alkylene group having 2 to 4 carbon atoms, and d is 0 or 1 from the viewpoint of easy industrial production and easy availability. It is preferable that it is, and it is more preferable that it is 0.

As the above-mentioned hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, the above-mentioned aralkyl group having 8 to 40 carbon atoms and the above general formula ( The group represented by 2) is preferable, and the above aralkyl group having 8 to 40 carbon atoms is more preferable in that the water repellency of the obtained fiber product can be improved.

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 group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, myristyl group, cetyl group, stearyl group and the like. As the alkyl group having 3 to 22 carbon atoms, an alkyl group having 8 to 20 carbon atoms is preferable, and an alkyl group having 12 to 18 carbon atoms is more preferable, from the viewpoint that the water repellency of the obtained fiber product can be improved.

In the organo-modified silicone oil represented by the general formula (1), R ³⁰ , R ³¹ , R ³² , R ³³ , R ^34, and R ³⁵ are each independently a hydrogen atom, a methyl group, an ethyl group, or a carbon number of 1 Is a C4 to C4 alkoxy group, an aromatic ring-containing C8 to C40 hydrocarbon group, or a C3 to C22 alkyl group. R ³⁰ , R ³¹ , R ³² , R ³³ , R ^34, and R ³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group, or a carbon number of 1 in that they are easily industrially produced and easily available. It is preferably an alkoxy group of 4 to 4, and more preferably a methyl group.

In the organo-modified silicone oil represented by the general formula (1), a is an integer of 0 or more. A is preferably 40 or less, and more preferably 30 or less from the viewpoints of easy industrial production, easy availability, and more excellent peel strength of the obtained fiber product with respect to the resin coating.

In the organo-modified silicone oil represented by the general formula (1), (a+b) is 10 to 200. In view of easy industrial production and easy availability, (a+b) is preferably 20 to 100, more preferably 40 to 60. When (a+b) is within the above range, the silicone itself tends to be easily manufactured and handled.

The organo-modified silicone oil represented by the above general formula (1) can be synthesized by a conventionally known method. The organo-modified silicone oil represented by the above general formula (1) can be obtained, for example, by subjecting a silicone having a SiH group to a hydrosilylation reaction of an aromatic compound having a vinyl group and/or an α-olefin.

Examples of the SiH group-containing silicone include methyl hydrogen silicone having a degree of polymerization of 10 to 200, a copolymer of dimethyl siloxane and methyl hydrogen siloxane, and the like. Among these, methylhydrogen silicone is preferable because it is easily manufactured industrially and is easily available.

The aromatic compound having a vinyl group is a compound from which a hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms is derived from R ²³ in the general formula (1). 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-triether. (Phenylethyl)-phenyl ether, allyl-tri(2-phenylpropyl)phenyl ether and the like can be mentioned.

The above α-olefin is a compound from which an alkyl group having 3 to 22 carbon atoms is derived in R ²³ in the general formula (1). Examples of the α-olefin include propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, Examples thereof include α-olefins having 3 to 22 carbon atoms such as 1-hexadecene and 1-octadecene.

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

The amounts of the SiH group-containing silicone, vinyl group-containing aromatic compound and α-olefin used in the hydrosilylation reaction are appropriately selected according to the SiH group equivalent of the SiH group-containing silicone or the number average molecular weight. obtain.

Examples of the catalyst used in the hydrosilylation reaction include compounds such as platinum and palladium, among which platinum compounds are preferable. Examples of the platinum compound include platinum (IV) chloride and the like.

The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C.

Further, the hydrosilylation reaction is preferably performed in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon. Although the reaction proceeds even without solvent, a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate and the like.

Examples of the amino-modified silicone oil include compounds having an organic group containing an amino group and/or an imino group on at least one of a side chain and a terminal of the organopolysiloxane. Examples of such an organic group, the organic group represented by -R-NH _2, and an organic group represented by -R-NH-R'-NH2. Examples of R and R'include a divalent group such as an ethylene group and a propylene group. Part or all of the amino group and/or imino group may be a blocked amino group and/or imino group. The blocked amino group and/or imino group can be obtained, for example, by treating the amino group and/or imino group with a blocking agent. Examples of the blocking agent include fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, acid halides of fatty acids having 2 to 22 carbon atoms, and aliphatic monoisocyanates having 1 to 22 carbon atoms. Can be mentioned.

From the viewpoint of water repellency, the functional group equivalent of the amino-modified silicone oil is preferably 100 to 20000 g/mol, more preferably 150 to 12000 g/mol, and even more preferably 200 to 4000 g/mol.

The amino-modified silicone oil is preferably liquid at 25°C. Kinematic viscosity at 25 ° C. of amino-modified silicone oil is preferably 10~100,000mm ² / s, more preferably 10~30,000mm ² / s, at 10~5,000mm ² / s It is more preferable that there is. When the kinematic viscosity at 25° C. is 100,000 mm ² /s or less, workability tends to be secured easily. The kinematic viscosity at 25° C. means a value measured by the method described in JIS K 2283:2000 (Ubbelohde viscometer).

The amino-modified silicone oil can be easily obtained as a commercial product. Examples of commercially available products include KF8005, KF-868, KF-864, KF-393, KF-8021 (all manufactured by Shin-Etsu Chemical Co., Ltd., trade name), TSF-4709, XF42-B1989 (Momentive. Performance Materials Japan (go), trade name, BY16-872, SF-8417, BY16-853U, BY16-892 (all are trade names, manufactured by Toray Dow Corning Co., Ltd.). ..

Silicone oils other than amino-modified silicone oils can also be easily obtained as commercial products. Examples of commercially available products include KF-101 (produced by Shin-Etsu Chemical Co., Ltd., trade name, epoxy-modified silicone oil), X-22-3701E (produced by Shin-Etsu Chemical Co., Ltd., trade name, carboxyl-modified silicone oil). , SF8428 (Toray Dow Corning Co., Ltd., trade name, carbinol modified silicone oil), KF-9901 (Shin-Etsu Chemical Co., Ltd., trade name, methyl hydrogen silicone oil), X-22-715 ( Shin-Etsu Chemical Co., Ltd., trade name, higher fatty acid ester modified silicone oil), KF-96-3000cp (Shin-Etsu Chemical Co., Ltd., trade name, dimethyl silicone oil), SF8416 (Toray Dow Corning Co., Ltd.) , Trade name, alkyl-modified silicone oil), SH203 (Toray Dow Corning Co., Ltd., trade name, alkyl aralkyl modified silicone oil), SF8410 (Toray Dow Corning Co., Ltd., trade name, polyether modified silicone) Oil).

The silicone resins (β) may be used alone or in combination of two or more.

The content of the non-fluorine-containing polymer (α) and the silicone resin (β) contained in the water repellent composition of the present embodiment is non-fluorine-based in terms of water repellency and texture of the resulting textile product and chalk marks. The ratio (α)/(β) between the mass of the polymer (α) and the mass of the silicone resin (β) is preferably 2.5/97.5 to 97.5/2.5, and 5/ It is more preferably 95 to 95/5, further preferably 10/90 to 90/10, and particularly preferably 15/85 to 85/15.

In the water repellent composition of the present embodiment, silica modified with a hydrophilizing agent and a hydrophobizing agent (silica having a hydrophilic group and a hydrophobic group on the silica surface) can be used in combination. Examples of such silica having a hydrophilic group and a hydrophobic group on the surface of silica include, for example, Reorosil HG-09 (manufactured by Tokuyama Corp., trade name), AEROSIL NA50H, RA200H, RA200HS (above, Nippon Aerosil Co., Ltd. ), product name, etc.

It is also possible to add additives and the like to the water repellent composition of this embodiment, if necessary. Other additives include other water repellents, surfactants, defoamers, pH adjusters, antibacterial agents, antifungal agents, colorants, antioxidants, deodorants, various organic solvents, chelating agents, antistatic agents. Examples include agents, catalysts, cross-linking agents, antibacterial deodorants, flame retardants, softeners, anti-wrinkle agents, and the like.

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

Examples of the defoaming agent include fat and oil defoaming agents such as castor oil, sesame oil, linseed oil, animal and vegetable oil; fatty acid defoaming agents such as stearic acid, oleic acid and palmitic acid; isoamyl stearate and distearyl succinate. , Fatty acid ester-based defoaming agents such as ethylene glycol distearate, butyl stearate; alcohol-based defoaming agents such as polyoxyalkylene monohydric alcohol, di-t-amylphenoxyethanol, 3-heptanol, and 2-ethylhexanol; Ether antifoaming agents such as di-t-amylphenoxyethanol, 3-heptylcellosolve, nonylcellosolve, 3-heptylcarbitol; phosphate antifoaming agents such as tributyl phosphate, tris(butoxyethyl) phosphate; diamylamine and the like. Examples include amine defoaming agents; amide defoaming agents such as polyalkyleneamides and acylate polyamines; sulfuric ester defoaming agents such as sodium lauryl sulfate; mineral oils. The defoaming agents can be used alone or in combination of two or more.

As the pH adjuster, organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, citric acid, malic acid, sulfonic acid, methanesulfonic acid, toluenesulfonic acid; hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Inorganic acids such as boric acid; 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 the organic solvent include aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, hexyl alcohol, and 2-ethylhexyl alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, Ketones such as diacetone alcohol; esters such as ethyl acetate, methyl acetate, butyl acetate, methyl lactate, ethyl lactate; diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tertiary butyl ether, butyl carbyl Ethers such as tall; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, Glycol ethers such as 3-methoxy-3-methyl-1-butanol; glycol esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; formamide, acetamide, benzamide, N,N- Examples thereof include amides such as dimethylformamide and acetanilide. The organic solvent may be used alone or in combination of two or more.

As the antistatic agent, it is preferable to use one that does not easily impair the water repellency. Examples of the antistatic agent include cationic surfactants such as higher alcohol sulfate ester salts, sulfated oils, sulfonates, quaternary ammonium salts, imidazoline type quaternary salts, polyethylene glycol type and polyhydric alcohol ester type. And nonionic surfactants, imidazoline type quaternary salts, alanine type and betaine type amphoteric surfactants, high molecular compound type antistatic polymers, polyalkylamines and the like. The antistatic agent may be used alone or in combination of two or more.

Next, a method for producing the water repellent composition of this embodiment will be described.

The composition containing the non-fluorine-based polymer (α) can be produced by a radical polymerization method. Further, among the radical polymerization methods, it is preferable to polymerize by an emulsion polymerization method or a dispersion polymerization method from the viewpoint of the performance and the environment of the obtained water repellent agent.

For example, the non-fluorine-based polymer (α) can be obtained by emulsion-polymerizing or dispersion-polymerizing the component (A1) and the component (A2) in a medium. More specifically, for example, the component (A1), the component (A2) and, if necessary, the component (B), the component (C) and the component (D), and an emulsification aid or dispersion aid are added. Then, this mixed solution is emulsified or dispersed to obtain an emulsion or dispersion. By adding a polymerization initiator to the obtained emulsion or dispersion, the polymerization reaction is initiated, and the monomer and the reactive emulsifier can be polymerized. As a means for emulsifying or dispersing the above-mentioned mixed liquid, a homomixer, a high-pressure emulsifier, an ultrasonic wave or the like can be mentioned.

Examples of the emulsification auxiliary agent or dispersion auxiliary agent (hereinafter, also referred to as “emulsification auxiliary agent or the like”) include nonionic surfactants other than the reactive emulsifier (B), cationic surfactants, anionic surfactants, and amphoteric One or more selected from surfactants can be used. The content of the emulsification aid and the like is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of all the monomers. Is more preferable. When the content of the emulsification aid or the like is 0.5 parts by mass or more, the dispersion stability of the mixed liquid is further improved as compared with the case where the content of the emulsification aid or the like is less than 0.5 parts by mass. Tend to do. When the content of the emulsification aid or the like is 30 parts by mass or less, the water repellency of the obtained non-fluorine-based polymer tends to be further improved as compared with the case where the content of the emulsification aid or the like exceeds 30 parts by mass. is there.

Examples of the cationic surfactant include monoalkyltrimethylammonium salt having 8 to 24 carbon atoms, dialkyldimethylammonium salt having 8 to 24 carbon atoms, monoalkylamine acetate having 8 to 24 carbon atoms, and dialkylamine having 8 to 24 carbon atoms. Examples thereof include acetate salts and alkyl imidazoline quaternary salts having 8 to 24 carbon atoms. Among these, from the viewpoint of emulsifying property and processing stability, monoalkyltrimethylammonium salt having 12 to 18 carbon atoms and dialkyldimethylammonium salt having 12 to 18 carbon atoms are preferable.

These cationic surfactants may be used alone or in combination of two or more.

Examples of the nonionic surfactant include alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, fats and oils, and propylene oxide adducts of alkylene oxide.

Examples of alcohols include linear or branched C8-24 alcohols or alkenols, and acetylene alcohols represented by the following general formula (AL-1) or general formula (AL-2).

［式中、Ｒ^５１及びＲ^５２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 the formula, R ⁵¹ and R ⁵² each independently represent an alkyl group having a straight chain or branched chain having 1 to 8 carbon atoms or an alkenyl group having a straight chain or branched chain having 2 to 8 carbon atoms. ]

［式中、Ｒ^５３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 the formula, R ⁵³ represents an alkyl group having a linear or branched chain having 1 to 8 carbon atoms or an alkenyl group having a linear or branched chain having 2 to 8 carbon atoms. ]

As the polycyclic phenols, monovalent phenols such as phenol and naphthol which may have a hydrocarbon group having 1 to 12 carbons, or styrenes thereof (styrene, α-methylstyrene, vinyltoluene) addition Compounds or their benzyl chloride reaction products. Examples of amines include linear or branched aliphatic amines having 8 to 44 carbon atoms.

Examples of the amides include straight chain or branched chain fatty acid amides having 8 to 44 carbon atoms.

Examples of the fatty acids include linear or branched fatty acids having 8 to 24 carbon atoms.

Examples of the polyhydric alcohol fatty acid esters include a condensation reaction product of a polyhydric alcohol and a carboxylic acid having 2 to 30 carbon atoms (including carbon of a carboxyl group). Examples of such polyhydric alcohol fatty acid esters include sorbitan esters composed of sorbitan (alcohol) and carboxylic acid having 2 to 30 carbon atoms (including carbon of carboxyl group).

The carboxylic acid constituting the sorbitan ester has 2 to 30 carbon atoms, preferably 5 to 21 carbon atoms. The sorbitan ester may be a monocarboxylic acid ester of sorbitan and one carboxylic acid, a dicarboxylic acid ester of sorbitol and two carboxylic acids, and a tricarboxylic acid ester of sorbitol and three carboxylic acids. Is preferred.

The sorbitan ester may be a compound represented by the following general formula (4) or the following general formula (5).

［式（４）中、Ｒ^６１は炭素数１〜２２のアルキル基又は炭素数２〜２２のアルケニル基を表し、Ｒ^６４、Ｒ^６５及びＲ^６６は水素、−ＣＯ−Ｒ^６１で表される基、又は−（ＣＨ_２ＣＨ_２Ｏ）_ｅ−（Ｒ^６２Ｏ）_ｆ−Ｒ^６３（Ｒ^６２は炭素数３以上のアルキレン基を表し、Ｒ^６３は水素、炭素数１〜２２のアルキル基又は炭素数２〜２２のアルケニル基を表し、ｅは２以上の整数を表し、ｆは０以上の整数を表す。）を表す。］

[In the formula (4), R ⁶¹ represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, and R ⁶⁴ , R ^65, and R ⁶⁶ are represented by hydrogen or —CO—R ^61. group, or ^{_{- (CH 2 CH 2 O)}} e - (R 62 O) f -R 63 (R 62 represents an alkylene group having 3 or more carbon ^{atoms, R 63} is hydrogen, or an alkyl group having 1 to 22 carbon atoms Represents an alkenyl group having 2 to 22 carbon atoms, e represents an integer of 2 or more, and f represents an integer of 0 or more). ]

［式（５）中、Ｒ^６１は炭素数１〜２２のアルキル基又は炭素数２〜２２のアルケニル基を表し、Ｒ^６４、Ｒ^６５及びＲ^６６は水素、−ＣＯ−Ｒ^６１で表される基、又は−（ＣＨ_２ＣＨ_２Ｏ）_ｅ−（Ｒ^６２Ｏ）_ｆ−Ｒ^６３（Ｒ^６２は炭素数３以上のアルキレン基を表し、Ｒ^６３は水素、炭素数１〜２２のアルキル基又は炭素数２〜２２のアルケニル基を表し、ｅは２以上の整数を表し、ｆは０以上の整数を表す。）を表す。］

[In the formula (5), R ⁶¹ represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, and R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are represented by hydrogen or —CO—R ^61. group, or ^{_{- (CH 2 CH 2 O)}} e - (R 62 O) f -R 63 (R 62 represents an alkylene group having 3 or more carbon ^{atoms, R 63} is hydrogen, or an alkyl group having 1 to 22 carbon atoms Represents an alkenyl group having 2 to 22 carbon atoms, e represents an integer of 2 or more, and f represents an integer of 0 or more). ]

Examples of the compound represented by the general formula (4) or (5) include sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquistearate, sorbitan tristearate, and monolaurin. Acid polyoxyethylene sorbitan, monopalmitic acid polyoxyethylene sorbitan, monostearic acid polyoxyethylene sorbitan, monooleic acid polyoxyethylene sorbitan, tristearic acid polyoxyethylene sorbitan, and the like.

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

Among these, from the viewpoints of little influence on water repellency, little influence on light resistance, and good emulsifiability of the copolymer, a linear or branched C8-24 alcohol or alkenol, And, the acetylene alcohol represented by the above general formula (AL-1) or the above general formula (AL-2) is preferable, and a straight or branched chain alcohol having 8 to 24 carbon atoms, and the above general formula (AL- 1) or the acetylene alcohol represented by the general formula (AL-2) is more preferable.

Examples of the alkylene oxide 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 viewpoint of having little influence on water repellency and improving the emulsifying property of the non-fluorine-based polymer (α), the alkylene oxide is preferably ethylene oxide or 1,2-propylene oxide, and more preferably ethylene oxide.

The number of moles of alkylene oxide added is preferably 1 to 200, more preferably 3 to 100, and still more preferably 5 to 50. When the number of added moles of alkylene oxide is within the above range, water repellency and product stability can be easily obtained at a high level.

In the non-fluorine-based polymer (α) according to the present embodiment, when a nonionic surfactant having HLB of 7 to 18 is used as the nonionic surfactant, a better aqueous dispersion is obtained. Here, HLB is based on Griffin's HLB, and the Griffin's formula is changed to the following formula. Here, the hydrophilic group refers to an ethylene oxide group.
HLB=(hydrophilic group×20)/molecular weight

The HLB of the nonionic surfactant used in the present embodiment is 7 to 18, and the non-fluorinated polymer (α) of the present embodiment is used in the composition during and after emulsion polymerization or dispersion polymerization. From the viewpoint of emulsion stability (hereinafter, simply referred to as emulsion stability), 9 to 15 is preferable. Furthermore, in view of storage stability of the water repellent composition, it is more preferable to use two or more kinds of nonionic surfactants having different HLBs within the above range in combination. From the viewpoint of emulsion stability and water repellency, it is preferable to use a cationic surfactant and a nonionic surfactant in combination.

Water is preferable as a medium for emulsion polymerization or dispersion polymerization, and water and an organic solvent may be mixed if necessary. The organic solvent at this time is not particularly limited as long as it is an organic solvent miscible with water, for example, alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, diethyl. Examples thereof include ethers such as ether, and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. The ratio of water to organic solvent is not particularly limited.

As the polymerization initiator, a known polymerization initiator such as an azo type, a peroxide type, or a redox type can be appropriately used. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of all the monomers. When the content of the polymerization initiator is within the above range, the non-fluorine-based polymer (α) having a weight average molecular weight of 30,000 or more can be efficiently produced.

Further, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight. The content of the chain transfer agent is preferably 0.3 part by mass or less, and more preferably 0.1 part by mass or less, based on 100 parts by mass of all the monomers. When the content of the chain transfer agent is 0.3 part by mass or less, it is possible to prevent the molecular weight from decreasing too much, and to efficiently produce the non-fluorine-based polymer (α) having a weight average molecular weight of 30,000 or more. Tends to be easier.

A polymerization inhibitor may be used to adjust the molecular weight. By adding the polymerization inhibitor, the non-fluorine-based polymer (α) having a desired weight average molecular weight can be easily obtained.

The temperature of the polymerization reaction is preferably 20°C to 150°C. When the temperature is 20° C. or higher, it tends to facilitate the polymerization sufficiently as compared with the case where the temperature is lower than 20° C. When the temperature is 150° C. or lower, the reaction heat can be controlled more easily than when the temperature exceeds 150° C.

In the polymerization reaction, the weight average molecular weight of the obtained non-fluorine-based polymer (α) can be adjusted by increasing or decreasing the contents of the above-mentioned polymerization initiator, chain transfer agent, and polymerization inhibitor, and the melt viscosity at 105° C. It can be adjusted by increasing or decreasing the content of the polyfunctional monomer and the content of the polymerization initiator. When it is desired to reduce the melt viscosity at 105° C., the content of the monomer having two or more polymerizable functional groups may be reduced or the content of the polymerization initiator may be increased.

The content of the non-fluorine-containing polymer (α) in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is from the viewpoint of storage stability and handling of the composition, relative to the total amount of the emulsion or dispersion. The amount is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass.

The water repellent composition of the present embodiment can be prepared by mixing the composition containing the non-fluorine-based polymer (α) obtained by the above method with the silicone resin (β). The silicone resin (β) may be a commercially available product or the like.

The water-repellent fiber product of the present embodiment is a fiber product to which the above-mentioned non-fluorine-based polymer (α) of the present embodiment and a silicone resin (β) are attached.

A method for manufacturing the water repellent fiber product of the present embodiment will be described.

The water-repellent textile product of the present embodiment is prepared by treating the textile product with a treatment liquid containing the above-mentioned water repellent composition, whereby the non-fluorine-containing polymer (α) and the silicone resin (β) are added to the textile product. Obtained by attaching. There are no particular restrictions on the material of such fiber products, such as cotton, hemp, silk, natural fibers such as wool, rayon, semi-synthetic fibers such as acetate, synthetic fibers such as nylon, polyester, polyurethane, polypropylene and composite fibers thereof, Examples include mixed fiber. The form of the fiber product may be any form of fiber, yarn, cloth, non-woven fabric, paper and the like.

Examples of the method for treating the textile product with the above-mentioned treatment liquid include processing methods such as dipping, spraying and coating. Further, when the water repellent composition contains water, it is preferable that the water repellent composition is dried in order to remove the water after being attached to the textile product.

The amount of the water repellent composition attached to the textile product can be appropriately adjusted according to the required degree of water repellency. From the viewpoint of water repellency and texture, the water repellent composition is added to 100 g of the textile product. It is preferable to adjust the total amount of non-fluorine-containing polymer (α) and silicone resin (β) contained in the product to be 0.01 to 10 g, and to adjust it to be 0.05 to 5 g. Is more preferable.

In addition, after the non-fluorine-based polymer (α) of the present embodiment and the silicone resin (β) are attached to the textile product, it is preferable to appropriately perform heat treatment. The temperature condition is not particularly limited, but when the water repellent composition of the present embodiment is used, it is possible to cause the fiber product to exhibit sufficiently good water repellency under a mild condition of 100 to 130°C. The temperature condition may be a high temperature treatment of 130° C. or higher (preferably up to 200° C.), but in such a case, the treatment time can be shortened as compared with the conventional case using a fluorine-based water repellent. .. Therefore, according to the water-repellent fiber product of the present embodiment, deterioration of the fiber product due to heat is suppressed, the texture of the fiber product during the water-repellent treatment becomes soft, and under mild heat treatment conditions, that is, under low-temperature curing conditions. Sufficient water repellency can be imparted to textile products.

In particular, if it is desired to improve the durable water repellency, the above-mentioned step of treating the textile with a treatment liquid containing a water repellent composition and one melamine resin, glyoxal resin, isocyanate group or blocked isocyanate group It is preferable that the fiber product is subjected to a water repellent treatment by a method including a step of attaching a crosslinking agent represented by the above-mentioned compounds to the fiber product and heating the same. Furthermore, in order to further improve the durable water repellency, the water repellent composition contains a non-fluorine-containing polymer (α) obtained by copolymerizing a monomer having a functional group capable of reacting with the above-mentioned crosslinking agent. Is preferred.

As the melamine resin, a compound having a melamine skeleton can be used. For example, trimethylolmelamine, polymethylolmelamine such as hexamethylolmelamine; or a part or all of the methylol group of polymethylolmelamine has 1 to 6 carbon atoms. Alkoxymethylmelamine which has become an alkoxymethyl group having an alkyl group; and acyloxymethylmelamine in which a part or all of the methylol group of polymethylolmelamine has become an acyloxymethyl group having an acyl group having 2 to 6 carbon atoms. Can be mentioned. These melamine resins may be either a monomer or a dimer or higher polymer, or a mixture thereof. Furthermore, what co-condensed urea etc. with a part of melamine can also be used. Examples of such a melamine resin include Beckamine APM, Beckamine M-3, Beckamine M-3 (60), Beckamine MA-S, Beckamine J-101, and Beckamine J-101LF manufactured by DIC Corporation, Union Chemical Industry. UNIKA RESIN 380K manufactured by KK, RIKEN RESIN MM series manufactured by Miki Riken Kogyo Co., Ltd. and the like can be mentioned.

As the glyoxal resin, conventionally known resins can be used. Examples of the glyoxal resin include 1,3-dimethylglyoxal urea-based resin, dimethylol dihydroxyethylene urea-based resin, dimethylol dihydroxypropylene urea-based resin, and the like. The functional groups of these resins may be substituted with other functional groups. Examples of such a glyoxal resin include Beckamine N-80, Beckamine NS-11, Beckamine LF-K, Beckamine NS-19, Beckamine LF-55P conc, Beckamine NS-210L, and Beckamine NS-200 manufactured by DIC Corporation. , And Beckamine NF-3, Union Resin GS-20E manufactured by Union Chemical Co., Ltd., Riken Resin RG series manufactured by Miki Riken Kogyo Co., Ltd., and Riken Resin MS series.

A catalyst is preferably used for the melamine resin and the glyoxal resin from the viewpoint of accelerating the reaction. The 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 borofluorite, and neutral metal salt catalysts such as magnesium chloride and magnesium sulfate. An inorganic acid such as phosphoric acid, hydrochloric acid or boric acid. If necessary, these catalysts may be used in combination with an organic acid such as citric acid, tartaric acid, malic acid, maleic acid or lactic acid as a co-catalyst. Examples of such a catalyst include, for example, Catalyst ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3 manufactured by DIC Corporation, and Catalyst NFC-1, Union Chemical Co., Ltd. Unica Catalyst 3-P, and Unica Catalyst MC-109, Miki Riken Co., Ltd. RIKEN FIXER RC series, RIKEN FIXER MX series, and RIKEN FIXER RZ-. 5 and the like.

As the compound having one or more isocyanate groups or blocked isocyanate groups, monofunctional (mono)isocyanate compounds such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate, and polyfunctional isocyanate compounds can be used.

The polyfunctional isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule, and a known polyisocyanate compound 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 alkylenediisocyanate preferably has 1 to 12 carbon atoms.

Examples of the diisocyanate compound 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, dodeca. Methylene 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, 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 may be mentioned.

Examples of the triisocyanate compound include triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, and tris(isocyanatophenyl)-thiophosphate.

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

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

The isocyanate group contained in the polyfunctional isocyanate compound may be as it is or may be a blocked isocyanate group blocked with a blocking agent. 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; phenol, methylphenol, Phenols such as chlorophenol, iso-butylphenol, tert-butylphenol, iso-amylphenol, octylphenol, nonylphenol; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam; malonic acid dimethyl ester, malonic acid diethyl ester , Acetylacetone, methyl acetoacetate, ethyl acetoacetate, and other active methylene compounds; formaldoxime, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, and other oximes; imidazole, 2-methylimidazole And imidazole compounds such as sodium bisulfite and the like. Among these, pyrazoles and oximes are preferable from the viewpoint of water repellency.

As the polyfunctional isocyanate compound, a water-dispersible isocyanate obtained by imparting water dispersibility to the polyisocyanate can be used by introducing a hydrophilic group into the polyisocyanate structure to have a surface active effect. Further, in order to accelerate the reaction, known catalysts such as organic tin and organic zinc can be used together.

The crosslinking agent and the catalyst may be used alone or in combination of two or more.

The cross-linking agent is, for example, by dissolving the cross-linking agent in an organic solvent, or by immersing the object to be treated (fiber product) in a treatment liquid emulsified and dispersed in water, and drying the treatment liquid attached to the object to be treated, It can be attached to the object to be treated. Then, by heating the cross-linking agent attached to the object to be treated, the reaction between the cross-linking agent and the object to be treated and the non-fluorine-based polymer (α) can be advanced. In order to sufficiently advance the reaction of the cross-linking agent and improve the washing durability more effectively, the heating at this time is preferably performed at 110 to 180°C for 1 to 5 minutes. The steps of attaching the cross-linking agent and heating may be performed at the same time as the step of treating with the treatment liquid containing the water repellent composition. When simultaneously performed, for example, a treatment liquid containing a water repellent composition and a cross-linking agent is attached to an object to be treated, water is removed, and then the cross-linking agent attached to the object is further heated. Considering the simplification of the water repellent process, the reduction of the amount of heat, and the economical efficiency, it is preferable to perform it simultaneously with the process of treating the water repellent composition.

Further, excessive use of the crosslinking agent may impair the feeling. The cross-linking agent is preferably used in an amount of 0.1 to 50% by mass, particularly preferably 0.1 to 10% by mass, based on the material to be treated (textile product).

The water-repellent fiber product of the present embodiment thus obtained can sufficiently exhibit water repellency even when used outdoors for a long period of time, and the water-repellent fiber product uses a fluorine-based compound. Because it does not, it can be environmentally friendly.

The water-repellent textile product of the present embodiment can be coated on a predetermined portion. Examples of coating processing include moisture-permeable waterproofing and windproofing for sports and outdoor applications. As a processing method, for example, in the case of moisture-permeable waterproofing, a coating liquid containing a urethane resin, an acrylic resin or the like and a medium may be applied to one surface of a water-repellent treated textile product and dried to perform processing. it can.

Although the preferred embodiment of the present invention has been described above, the present invention is not limited to the above embodiment.

For example, in the case of producing the non-fluorine-containing polymer (α) contained in the water repellent composition of the present invention, in the above-mentioned embodiment, the polymerization reaction is carried out by radical polymerization. The polymerization reaction may be carried out by photopolymerization such as irradiation with ionizing radiation.

Further, in the present invention, the water repellent composition is processed into a fiber product to give a water repellent fiber product, but the product treated with the water repellent composition is not limited to the fiber product use, but may be metal or glass. It may be an article such as a resin.

Further, in such a case, the method of attaching the water repellent composition to the article and the amount of the water repellent attached can be arbitrarily determined according to the type of the object to be treated and the like.

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

<Preparation of polymer dispersion>
A mixed liquid having the composition shown in Tables 1 and 2 (in the table, the numerical value shows (g)) was polymerized by the procedure shown below to obtain a dispersion liquid of a polymer or a hydrophobic compound.

(Synthesis example 1)
In an autoclave, 23.4 g of stearyl acrylate, 0.6 g of diacetone acrylamide, 0.2 g of Neugen XL-100 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7), Neugen XL- 60 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5) 1.3 g, Neugen XL-40 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10) .5) 0.5 g, stearyl trimethylmonmonium sulfate 0.4 g, tripropylene glycol 12.5 g and water 54.9 g were added, and mixed and stirred at 45° C. to obtain a mixed solution. This mixed liquid was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride was added to the mixed solution, and under continuous nitrogen atmosphere, 6 g of vinyl chloride was continuously injected under pressure so that the internal pressure of the autoclave was kept at 0.3 MPa, at 60°C. Radical polymerization was performed for 6 hours to obtain a non-fluorine-containing polymer (α) dispersion containing 30.0 mass% of the non-fluorine-containing polymer (α).

(Synthesis examples 2 to 8)
Polymerization was performed in the same manner as in Synthesis Example 1 except that the materials shown in Table 1 were used to obtain a non-fluorine-containing polymer (α) dispersion containing 30.0 mass% of the non-fluorine-containing polymer (α).

(Comparative Synthesis Examples 1 to 5)
Polymerization was performed in the same manner as in Synthesis Example 1 except that the materials shown in Table 2 were used to obtain other non-fluorine-containing polymer dispersions containing 30.0 mass% of other non-fluorine-containing polymer.

(Comparative Synthesis Example 6)
In a 1000 mL flask, 240.3 g of 1,4-butanediol, 758.5 g of stearic acid and 1.2 g of p-toluenesulfonic acid were put, and dehydration reaction was carried out at 130 to 200° C. for 4 hours under a nitrogen stream to obtain a product. Obtained. As a result of measuring the acid value and the hydroxyl value of the obtained product, the acid value was 0.5 mgKOH/g and the hydroxyl value was 162.1 mgKOH/g. In a separate container, 574.1 g of the above-mentioned product, 270.5 g of hexamethylene diisocyanate, and 0.9 g of a bismuth-based catalyst (Neostan U-600 manufactured by Nitto Kasei Co., Ltd.) were placed and reacted at 80° C. for 3 hours. The reaction was carried out until the NCO% reached 8.0. After the reaction, the temperature was lowered to 40° C., and then 154.6 g of 3,5-dimethylpyrazole was added and the reaction was performed at 40° C. for 1 hour to obtain a hydrophobic compound. In a 500 mL stainless steel container, 40 g of the obtained hydrophobic compound, 50 g of methyl ethyl ketone, 5 g of decagulin 1-L (nonionic surfactant, manufactured by Dai-ichi Kogyo Seiyaku), decagrin 1-SV (nonionic surfactant, Daiichi Kogyo Seiyaku) 5 g) and Arkad T-28 (cationic surfactant, manufactured by Lion Specialty Chemicals), and heated to 50° C. to dissolve. 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 (Nippon Seiki Seisakusho Co., Ltd.). Then, the mixture was cooled to obtain a 10% dispersion liquid of the hydrophobic compound.

Each of the polymers in the polymer dispersions obtained in Synthetic Examples 1 to 8 and Comparative Synthetic Examples 1 to 5 was analyzed by gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation) to find that all the monomers were It was confirmed that 98% or more was polymerized.

Details of the materials shown in Tables 1 and 2 are as follows.
Neugen XL-100 (14.7) (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7)
Neugen XL-60 (12.5) (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5)
Neugen XL-40 (10.5) (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5)

<Preparation of dispersion containing silicone resin>
(Preparation example 1)
20 parts by mass of SF 8416 (alkyl modified silicone, manufactured by Toray Dow Corning Co., Ltd., trade name) as a silicone resin, and SPAN60 (sorbitan nonionic surfactant, HLB=4.7, manufactured by Kao Co., Ltd.) 1 1 part by weight, 1 part by weight of TWEEN 80 (sorbitan nonionic surfactant, HLB=15.0, manufactured by Kao Corporation) and 5 parts by weight of butyldiglycol were mixed. Next, 73.0 parts by mass of water was added to the obtained mixture little by little while mixing to obtain a dispersion liquid containing 20% by mass of the silicone resin (β).

(Preparation Examples 2 to 4)
A silicone resin dispersion liquid containing 20% by mass of the silicone resin was obtained in the same manner as in Preparation Example 1 except that the following resin was used as the silicone resin.
(Preparation Example 2) BY 16-872 (Aminosilicone, manufactured by Toray Dow Corning Co., Ltd., trade name)
(Preparation Example 3) KF-9901 (methyl hydrogen silicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name)
(Preparation Example 4) KF-96-3000cs (dimethyl silicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name)

(Preparation example 5)
KF8005 (amino-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 18.5 parts by mass, formic acid 0.15 parts by mass, ethylene oxide 5 mol adduct 0.5 of branched alcohol having 12 to 14 carbon atoms 0.5 And parts by weight. Next, 80.85 parts by mass of water was added to the obtained mixture little by little while mixing to obtain a dispersion liquid containing 18.5% by mass of amino-modified silicone.

15 parts by mass of dimethyl silicone (6 cs, manufactured by Dow Corning Toray Co., Ltd.) in 15 parts by mass of MQ-1600 (polysiloxane containing trimethylsilyl group of silicone resin, manufactured by Dow Corning Toray Co., Ltd.) Was added and mixed until the silicone resin was dissolved to obtain a mixture. 18.5 parts by mass of the obtained mixture was mixed with 0.5 parts by mass of an ethylene oxide 5 mol adduct of a branched alcohol having 12 to 14 carbon atoms. Next, 81 parts by mass of water was added little by little while mixing to obtain a dispersion liquid containing a total of 18.5% by mass of the silicone resin and dimethyl silicone.

The above amino-modified silicone dispersion and a dispersion containing silicone resin and dimethyl silicone are mixed at a ratio of 100:117, and amino-modified silicone, silicone resin and dimethyl silicone are used as the silicone resin (β) in a mass ratio. A 20% by mass silicone resin dispersion containing 9.2:5.4:5.4 was obtained.

<Preparation of water repellent composition>
(Examples 1 to 15, Comparative Examples 1 to 9)
Non-fluorine-containing polymer (α) dispersion liquid, other non-fluorine-containing polymer dispersion liquid, or hydrophobic compound dispersion liquid so as to have the composition shown in Tables 3 to 5 (in the table, the numerical values indicate (% by mass)). , And the silicone resin (β) dispersion and water were mixed to obtain water repellent compositions.

(Evaluation of water repellency of textile products)
Tests were carried out at a shower water temperature of 20° C. according to the spray method of JIS L 1092 (2009). In this test, a dyed 100% polyester cloth or a polyester (PET)/polyurethane (PU) blended cloth (polyester/polyurethane=80/20) was dipped in the water repellent composition of Examples and Comparative Examples. After that, it was dried at 130° C. for 2 minutes and further heat-treated at 170° C. for 30 seconds to evaluate the water repellency of the obtained cloth. The results were visually evaluated in the following grades. When the characteristics were slightly good, "+" was attached to the grade, and when the characteristics were slightly inferior, "-" was attached to the grade. The results are shown in Tables 3-5.
Water repellency: State 5: No adhesion and wetting on the surface 4: Slight adhesion and wetting on the surface 3: Partial wetting on the surface 2: Wetting on the surface 1: Wetting on the entire surface Thing 0: Both front and back surfaces are completely wet

(Texture evaluation of textile products)
As for the feeling, the dyed 100% polyester cloth was immersed in the treatment liquid for the water repellent compositions of Examples and Comparative Examples, dried at 130° C. for 2 minutes, and further heat treated at 170° C. for 30 seconds. It evaluated using the thing. The results were evaluated by handling in the following 5 grades. The results are shown in Tables 3-5.
1: Hard ~ 5: Soft

(Evaluation of durable water repellency of textile products)
Tests were carried out at a shower water temperature of 20° C. according to the spray method of JIS L 1092 (2009). A blocked isocyanate crosslinking agent (NK Assist NY-50) was added to the water repellent compositions of Examples and Comparative Examples so as to have a concentration of 0.03% by mass to prepare a treatment liquid. Then, a dyed 100% polyester cloth was dipped in the prepared treatment liquid. After the immersion treatment, the cloth (L-0) obtained by drying at 130° C. for 2 minutes and further heat-treating at 170° C. for 60 seconds, and washing by the method 103 of JIS L 0217 (1995) 30 times (L-30) ) The water repellency of the cloth after the evaluation was evaluated in the same manner as the water repellency evaluation method. Also in the case of polyester (PET)/polyurethane (PU) blended fabric (polyester/polyurethane=80/20), the same as the case of 100% polyester fabric except that the heat treatment temperature was changed from 170°C to 160°C. evaluated. The results are shown in Tables 3-5.

(Peel strength against coating of textile products)
The test was conducted according to JIS K 6404-5 (1999). In this test, the dyed 100% nylon cloth was immersed in the water repellent compositions of Examples and Comparative Examples, dried at 130° C. for 2 minutes, and further heat treated at 170° C. for 30 seconds. The obtained product was used as a base fabric. A hot-melt adhesive tape (“MELCO tape” manufactured by Sun Kasei Co., Ltd.) was heat-bonded to the obtained base cloth at 150° C. for 1 minute using a thermocompression bonding apparatus, and the base cloth and the seam tape were separated from each other. The strength was measured with an autograph (AG-IS, manufactured by Shimadzu Corporation). The gripping tool was pulled at a moving speed of 100 mm/min, and the average value of the stress was taken as the peel strength [N/inch]. The results are shown in Tables 3-5.

(Evaluation of repellency of textile products)
A test was conducted at a shower water temperature of 20° C. according to the spray method of JIS L 1092 (2009), and the degree of water repellency at the time of water repellency of the spray was visually confirmed and evaluated according to the following 5 grades. In this test, the dyed polyester/polyurethane blended fabric (polyester/polyurethane=80/20) was immersed in the water repellent compositions of Examples and Comparative Examples, and then dried at 130° C. for 2 minutes, Further, heat treatment was performed at 170° C. for 30 seconds, and the repellency of the obtained cloth was evaluated. When the characteristics were slightly good, "+" was attached to the grade, and when the characteristics were slightly inferior, "-" was attached to the grade. The results are shown in Tables 3-5.
Repellency: State 5: Water in contact with cloth keeps fine droplets and water splashes from cloth surface 4: Water in contact with cloth keeps fine droplets and rolls on cloth surface 3: Cloth The contacted water keeps a large drop of water and rolls down the surface of the cloth. 2: The water in contact with the cloth does not maintain the shape of a drop of water and drops straight down the surface of the cloth. 1: The water in contact with the cloth meanders without maintaining the drop of water. While falling

(Chalk mark evaluation of textile products)
For the chalk mark, a dyed 100% polyester cloth was dipped in the water repellent composition of Examples and Comparative Examples, dried at 130° C. for 2 minutes, and then heat treated at 170° C. for 30 seconds. Evaluated. The surface of the processed cloth was scratched with a nail and visually evaluated according to the following 5 grades. The results are shown in Tables 3-5.
5: Clear scratches are recognized 4: Scratch marks are recognized 3: Slight scratches are recognized 2: Almost no scratches are recognized 1: No scratches are found

Claims (4)

Structural units derived from the (meth)acrylic acid ester monomer (A1) represented by the following general formula (A-1) and compounds derived from the compound (A2) represented by the following general formula (A-2). A non-fluorine-containing polymer (α) containing units,
Silicone resin (β),
A water repellent composition containing:

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. ]

[In the formula (A-2), R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, and W represents -. ^{CO-R 13 (wherein, R 13} is a monovalent hydrocarbon represents a group having 1 to 4 carbon atoms) groups represented by the group represented by -NH-CO-NH _2, or the following formula (a -3) represents a group represented by.

] The water repellent composition according to claim 1, wherein the non-fluorine-based polymer (α) further contains a constituent unit derived from at least one monomer (VC) selected from vinyl chloride and vinylidene chloride. A water repellent fiber product comprising a fiber product to which the water repellent composition according to claim 1 or 2 is attached. A method for producing a water-repellent fiber product, comprising the step of treating the fiber product with a treatment liquid containing the water repellent composition according to claim 1.