JP6883434B2 - Method for manufacturing water repellent composition, water repellent fiber product and water repellent fiber product - Google Patents

Description

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

Conventionally, a fluorine-based water repellent having a fluorine group is known, and a textile product in which water repellency is imparted to the surface of the fiber product or the like by treating the fluorine-based water repellent is known. Such a fluorine-based water repellent is generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group. Although textile products treated with a fluorine-based water repellent exhibit excellent water repellency, it has become clear that monomers having a fluoroalkyl group are concerned about environmental load.

Therefore, in recent years, research has been conducted on non-fluorine-based water repellents that do not contain fluorine. For example, Patent Document 1 below discloses a water repellent made of a specific non-fluoropolymer containing a (meth) acrylic acid ester having 12 or more carbon atoms in the ester portion as a monomer unit. Patent Document 2 below discloses a soft water repellent agent containing an amino-modified silicone and a polyfunctional isocyanate.

Japanese Unexamined Patent Publication No. 2006-328624 Japanese Unexamined Patent Publication No. 2004-59609

By the way, a water-repellent treated textile product or the like may be processed by coating a predetermined portion with a urethane resin, an acrylic resin or the like. In this case, the textile product is required to have sufficient water repellency, but the coating film is not easily peeled off at the portion to be coated.

However, in the water repellent agent described in Patent Document 1 and the soft water repellent agent described in Patent Document 2, the peel strength with respect to the coating has not been sufficiently examined, and the water repellency and the peel strength are at a higher level. There is room for further improvement in order to achieve both.

The present invention has been made in view of the above circumstances, and a water-repellent fiber product having excellent water repellency can be obtained, and the obtained product can also have sufficient peel strength against a coating. , A method for producing a water-repellent fiber product and a water-repellent fiber product.

The present invention is a non-fluorinated polymer containing a structural unit derived from at least one of vinyl chloride and vinylidene chloride (VC), and is a monomer component constituting the non-fluorinated polymer. A non-fluoropolymer (α) having a monomer (VC) content of 50% by mass or more based on the total amount of the above, and a single amount of (meth) acrylic acid ester represented by the following general formula (A-1). A non-fluorinated polymer containing a structural unit derived from the body (A), which contains the (meth) acrylic acid ester monomer (A) based on the total amount of the monomer components constituting the non-fluorinated polymer. Provided is a water repellent composition containing a non-fluoropolymer (β) having a proportion of 50% by mass or more and / or a silicone resin (γ).

［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 a hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. ]

According to the water-repellent composition of the present invention, the specific non-fluoropolymer (α) and the specific non-fluoropolymer (β) and / or silicone resin (γ) are contained in combination. A water-repellent fiber product having excellent water repellency can be obtained, and the obtained product can also have sufficient peeling strength against the coating.

From the viewpoint of water repellency of the obtained textile product and emulsion stability during emulsification polymerization or dispersion polymerization and in the composition after polymerization, the non-fluoropolymer (α) has an (B1) HLB of 7 to 18. A compound represented by the following general formula (I-1), (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18, and (B3) an HLB of 7 to 18. , Further containing a structural unit derived from at least one reactive emulsifier (B) selected from the group consisting of compounds in which an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group. can do.

［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。］

［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。］

[In formula (I-1), R ³ represents a hydrogen or 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. Represents a divalent group containing. ]

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² contains an alkyleneoxy group having 2 to 4 carbon atoms. Represents a divalent group. ]

The water-repellent composition according to the present invention is the non-fluoropolymer (β) from the viewpoint of water repellency of the obtained textile product and emulsion stability during emulsification polymerization or dispersion polymerization and in the composition after polymerization. The non-fluoropolymer (β) is a compound represented by the following general formula (I-1) in which (B1) HLB is 7 to 18, and (B2) is a compound represented by the following general formula (I-1) in which HLB is 7 to 18. From the group consisting of the compound represented by II-1) and the compound (B3) having an HLB of 7 to 18 and having an alkylene oxide having 2 to 4 carbon atoms added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group. It can further contain a structural unit derived from at least one selected reactive emulsifier (B).

［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。］

［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。］

[In formula (I-1), R ³ represents a hydrogen or 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. Represents a divalent group containing. ]

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² contains an alkyleneoxy group having 2 to 4 carbon atoms. Represents a divalent group. ]

From the viewpoint of durable water repellency of the obtained textile product, the non-fluoropolymer (α) is derived from the (meth) acrylic acid ester monomer (A) represented by the general formula (A-1). The unit is further contained, and the (meth) acrylic acid ester monomer (A) in the non-fluoropolymer (α) contains an acrylic acid ester monomer (a1) and a methacrylate ester monomer (a2). The ratio (a1) / (a2) of the mass of the acrylic acid ester monomer (a1) contained in the (meth) acrylic acid ester monomer (A) to the mass of the methacrylic acid ester monomer (a2) is 30. It is preferably / 70 to 90/10.

Further, the water repellent composition according to the present invention contains the non-fluoropolymer (β) from the viewpoint of durable water repellency of the obtained textile product, and the (meth) acrylic acid ester in the non-fluoropolymer (β). The monomer (A) contains an acrylic acid ester monomer (a1) and a methacrylic acid ester monomer (a2), and a single amount of the acrylic acid ester contained in the (meth) acrylic acid ester monomer (A). The ratio (a1) / (a2) of the mass of the body (a1) to the mass of the methacrylic ester monomer (a2) is preferably 30/70 to 90/10.

Further, the water repellent composition according to the present invention contains the above-mentioned silicone resin (γ) from the viewpoint of water repellency and texture of the obtained textile product, and the silicone resin (γ) is amino-modified silicone, silicone resin, dimethyl. It is preferably at least one selected from the group consisting of silicones, methylhydrogen silicones, and alkyl-modified silicones.

The present invention also repels a textile product to which a non-fluorinated polymer (α) and a non-fluorinated polymer (β) and / or a silicone resin (γ) are attached in the water repellent composition according to the present invention. Provide water-based textile products.

The water-repellent fiber product of the present invention can have sufficient water repellency and can have sufficient peel strength against the coating when a predetermined portion is coated with a urethane resin, an acrylic resin or the like.

The present invention also provides a method for producing a water-repellent textile product, which comprises a step of treating the textile 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 has sufficient water repellency and has sufficient peeling strength against the coating when a predetermined portion is coated with a urethane resin, an acrylic resin or the like. Aqueous textile products can be obtained.

According to the present invention, a water-repellent fiber product having excellent water repellency can be obtained, and the obtained product can provide a water-repellent composition which can also have sufficient peel strength against a coating.

According to the water-repellent composition of the present invention, even when the treated base material is coated with a urethane resin, an acrylic resin, or the like, both water repellency and peeling strength against the coating can be achieved at the same time. Further, when the water repellent composition of the present invention contains a silicone resin (γ), a water repellent fiber product having both water repellency and peeling strength against a coating can be obtained while improving the texture of the textile product. ..

Further, the water repellent composition of the present invention is a water repellent composition containing no compound having a fluoroalkyl group or fluorine, but exhibits excellent water repellency, and can be used as a substitute for a fluorine-based water repellent. It is possible to eliminate concerns about the impact on the fluorine supply source and the environment. After the water repellent composition is attached to a textile product or the like, it is usually preferable to heat-treat it. However, since the water repellent composition of the present invention does not use a monomer having a fluoroalkyl group, the temperature is 130 ° C. High water repellency can be exhibited even when heat-treated under the following mild conditions, and when heat-treated at a high temperature exceeding 130 ° C., the heat treatment time is shorter than that of the fluorine-based water-repellent agent. Can be done. Therefore, since deterioration due to heat of the object to be processed is suppressed, the texture becomes flexible, and the amount of heat required for heat treatment can be reduced, which is also excellent in terms of cost.

Furthermore, according to the present invention, as an emulsification / dispersant used for emulsification or dispersion polymerization of a non-fluoropolymer, a water repellent composition is used by using a specific reactive emulsifier instead of a general surfactant. The amount of surfactant contained in can be reduced. As a result, it is possible to suppress a decrease in water repellency of the obtained textile product or the like, and it is possible to realize higher water repellency than the conventional non-fluorine-based water repellent.

The water repellent composition of the present embodiment contains a first non-fluorinated polymer (α) and a second non-fluorinated polymer (β) and / or a silicone resin (γ).

<Non-fluorine polymer (α)>
The non-fluorinated polymer (α) is a non-fluorinated polymer (α) containing a structural unit derived from at least one monomer (VC) of vinyl chloride and vinylidene chloride (hereinafter, also referred to as “(VC) component”). It is a fluorine-based polymer, and the content ratio of the monomer (VC) is 50% by mass or more based on the total amount of the monomer components constituting the non-fluorine-based polymer.

The non-fluorinated polymer (α) is a structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1) (hereinafter, also referred to as “component (A)”). Is contained in a range in which the content ratio of the (meth) acrylic acid ester monomer (A) is less than 0 to 50% by mass based on the total amount of the monomer components constituting the non-fluorine-based polymer (α). Can be done.

［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 a hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. ]

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

Even if the (meth) acrylic acid ester monomer (A) represented by the above general formula (A-1) used in the non-fluorinated polymer (α) of the present embodiment has a substituent. It has a good monovalent hydrocarbon group with 12 to 30 carbon atoms. The 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. Of these, cyclic hydrocarbon groups are preferred. In this case, the peel strength becomes more excellent. When a monovalent hydrocarbon group having 12 to 30 carbon atoms has a substituent, the substituents include 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.

The cyclic hydrocarbon group may have a chain group (eg, a linear or branched chain hydrocarbon group). Examples of the cyclic hydrocarbon group include a monocyclic group, a polycyclic group, a bridging ring group, and the like, which are saturated or unsaturated. The cyclic hydrocarbon group is preferably saturated, more preferably a saturated cyclic aliphatic group. The number of carbon atoms of the cyclic hydrocarbon group is preferably 4 to 30, and more preferably 6 to 20. Further, in terms of peel strength, the number of carbon atoms of the cyclic hydrocarbon group is preferably 15 or less, and more preferably 12 or less.

Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, preferably 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms. Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentenyl group, a dicyclopentenyl group, and an adamantyl group.

Specific examples of the cyclic hydrocarbon group-containing (meth) acrylic acid ester monomer include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopenta. Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) Examples thereof include acrylate and 2-ethyl-2-adamantyl (meth) acrylate.

The component (A) 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 that can react with the cross-linking 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. Further, when the component (A) has an amino group, the texture of the obtained textile product can be further improved.

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

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

As the component (A), it is preferable to use the acrylic acid ester monomer (a1) and the metaacrylic acid ester monomer (a2) in combination in terms of the durable water repellency of the obtained textile product. The ratio (a1) / (a2) of the mass of the component (a1) to the mass of the component (a2) to be blended is preferably 30/70 to 90/10, preferably 40/60 to 85/15. Is more preferable, and 50/50 to 80/20 is even more preferable. When (a1) / (a2) are within the above range, the durable water repellency of the obtained textile product becomes better. When (a1) / (a2) exceeds 90/10 or is less than 30/70, the durable water repellency of the obtained textile product tends to decrease.

At least one monomer (VC) of vinyl chloride and vinylidene chloride used in the present embodiment is contained and obtained as a copolymerization component of the non-fluorinated polymer (α) of the present embodiment. Vinyl chloride is preferable in terms of water repellency of the textile product and peel strength against the coating.

The content ratio of the structural unit derived from the component (A) and the structural unit derived from the component (VC) in the non-fluorine-based polymer (α) of the present embodiment is the peel strength and the production of the non-fluorine-based polymer (α). From the viewpoint of ease of use, the ratio (A) / (VC) of the mass of the component (A) to the mass of the component (VC) to be blended is preferably 40/60 to 0/100, preferably 35/65 to 35. More preferably, it is 10/90.

The total mass of the mass of the component (A) and the mass of the component (VC) to be blended is preferably 80 to 100% by mass with respect to the total amount of the monomer components constituting the non-fluoropolymer (α). , 85-99% by mass, more preferably 90-98% by mass.

When the weight average molecular weights of the non-fluorine-based polymer (α) of the present embodiment are equal, the higher the blending ratio of the non-fluorine-based (meth) acrylic acid ester monomer, the higher the water repellency of the attached textile product. There is a tendency. Further, by copolymerizing a copolymerizable non-fluorine-based monomer, it is possible to improve the performance such as durable water repellency and texture of the attached textile product.

<Non-fluorine polymer (β)>
The non-fluorinated polymer (β) is a non-fluorinated polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the above general formula (A-1), and is the non-fluorinated polymer. The content ratio of the (meth) acrylic acid ester monomer (A) is 50% by mass or more based on the total amount of the monomer components constituting the fluoropolymer.

Even if the (meth) acrylic acid ester monomer (A) represented by the above general formula (A-1) used in the non-fluorinated polymer (β) of the present embodiment has a substituent. It has a good monovalent hydrocarbon group with 12 to 30 carbon atoms. The 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 viewpoint of water repellency and texture, a linear one is preferable, and a linear alkyl group is more preferable. In this case, the water repellency becomes better. When a monovalent hydrocarbon group having 12 to 30 carbon atoms has a substituent, the substituents include 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 the present embodiment, in the above 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.

The number of carbon atoms of the hydrocarbon group is more preferably 12 to 21. When the number of carbon atoms is in this range, the water repellency and texture become particularly excellent. Particularly preferred as the hydrocarbon group is a linear alkyl group having 12 to 18 carbon atoms.

Examples of the component (A) include stearyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, and (meth) acrylic acid. Pentadecyl, heptadecyl (meth) acrylate, nonadecil (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, behenyl (meth) acrylate, ceryl (meth) acrylate, melylyl (meth) acrylate Can be mentioned.

The component (A) 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 that can react with the cross-linking 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. Further, when the component (A) has an amino group, the texture of the obtained textile product can be further improved.

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

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

As the component (A), it is preferable to use the acrylic acid ester monomer (a1) and the metaacrylic acid ester monomer (a2) in combination in terms of the durable water repellency of the obtained textile product. The ratio (a1) / (a2) of the mass of the component (a1) to the mass of the component (a2) to be blended is preferably 30/70 to 90/10, preferably 40/60 to 85/15. Is more preferable, and 50/50 to 80/20 is even more preferable. When (a1) / (a2) are within the above range, the durable water repellency of the obtained textile product becomes better. When (a1) / (a2) exceeds 90/10 or is less than 30/70, the durable water repellency of the obtained textile product tends to decrease.

The non-fluorinated polymer (β) is a structural unit derived from at least one monomer (VC) of vinyl chloride and vinylidene chloride, which is a monomer component constituting the non-fluorinated polymer (β). It can be contained in a range in which the content ratio of the monomer (VC) is less than 0 to 50% by mass based on the total amount.

The content ratio of the structural unit derived from the component (A) and the structural unit derived from the component (VC) in the non-fluorinated polymer (β) of the present embodiment is the emulsion stability of the water repellent composition and the resulting fiber. In terms of peeling strength against the coating of the product, the ratio (A) / (VC) of the mass of the component (A) to the mass of the component (VC) to be blended is preferably 60/40 to 90/10. More preferably, it is 60/40 to 80/20.

The total mass of the mass of the component (A) and the mass of the component (VC) to be blended is preferably 80 to 100% by mass with respect to the total amount of the monomer components constituting the non-fluoropolymer (β). , 85-99% by mass, more preferably 90-98% by mass.

<Non-fluorine polymer (α) and non-fluorine polymer (β)>
The non-fluorinated polymer (α) or (β) of the present embodiment, in particular, the non-fluorinated polymer (α) is the water repellency of the obtained textile product, and the non-fluorinated polymer (α) or (β) of the present embodiment. β), in particular, the component (VC) or the component (A), or (VC) in that the emulsion stability during the emulsion polymerization or dispersion polymerization of the non-fluoropolymer (α) and in the composition after the polymerization can be improved. ) And (A), (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, and (B2) a compound represented by the following general formula (I-1) having an HLB of 7 to 18. It is selected from the compound represented by -1) and the compound in which (B3) an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18. It is preferable that at least one reactive emulsifier (B) (hereinafter, also referred to as “component (B)”) is contained 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 formula (I-1), R ³ represents a hydrogen or 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. 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。］

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² contains an alkyleneoxy group having 2 to 4 carbon atoms. Represents a divalent group. ]

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

The "HLB" is an HLB value calculated by the Griffin method, with the ethyleneoxy group being regarded as a hydrophilic group and all other groups being regarded as lipophilic groups.

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

In the reactive emulsifier (B1) represented by the above general formula (I-1) used in the present embodiment, R ³ is a hydrogen or a methyl group, and is a component (A) and / or a component (VC). It is more preferable that it is a methyl group in terms of copolymerizability. X is a linear or branched alkylene group having 1 to 6 carbon atoms, and in terms of emulsion stability of the non-fluorinated polymer (α) or (β) of the present embodiment, particularly the non-fluorinated polymer (α). , 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 alkyleneoxy groups added in Y ¹ can be appropriately selected so as to be within the above HLB range. Moreover, when there are two or more kinds of alkyleneoxy groups, they can have a block addition structure or a random addition structure.

As the compound represented by the general formula (I-1), the 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 a hydrogen or 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. Can be appropriately selected so that m is within the range of the above HLB. Specifically, an integer of 1 to 80 is preferable, and when m is 2 or more, m A ¹ O are the same. May be different. ]

In the compound represented by the general formula (I-2), R ³ is a hydrogen or a methyl group, and is more preferably a methyl group in terms of copolymerizability with the component (A). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and in terms of emulsion stability of the non-fluorinated polymer (α) or (β) of the present embodiment, particularly the non-fluorinated polymer (α). , 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 be within the above HLB range. In terms of the emulsion stability of the non-fluorinated polymer (α) or (β) of the present embodiment, particularly the non-fluorinated polymer (α), m is preferably an integer of 1 to 80, and is an integer of 1 to 60. Is more preferable. When m is 2 or more, m A ¹ O may be the same or different. Further, ^{when there are two or more types of A 1} O, they can have a block addition structure or a random addition structure.

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

In reactive emulsifier (B2) represented by the above general formula for use in this embodiment (II-1), R ⁴ is a monovalent unsaturated 13 to 17 carbon atoms having a polymerizable unsaturated group hydrocarbon Examples of the hydrogen group include a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group and a heptadecatrienyl group. .. From the viewpoint of emulsion stability of the non-fluorinated polymer 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 alkyleneoxy groups added in Y ² can be appropriately selected so as to be within the above HLB range. Moreover, when there are two or more kinds of alkyleneoxy groups, they can have a block addition structure or a random addition structure. The ethyleneoxy group is more preferable as the alkyleneoxy group in terms of the emulsion stability of the non-fluorinated polymer (α) or (β) of the present embodiment, particularly the non-fluorinated polymer (α).

As the compound represented by the general formula (II-1), the 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 formula (II-2), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and A ² O represents an alkyleneoxy group having 2 to 4 carbon atoms. Represented, n can be appropriately selected so as to be within the above HLB range. 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. Non-fluorine-based polymer of the present embodiment (alpha) or (beta), in particular in terms of emulsion stability of the fluorine-free polymer (alpha), the type and combination of A 2 ^O, and the number of n is, the HLB It can be appropriately selected so as to be within the range of. In terms of emulsion stability of the non-fluorinated polymer (α) or (β) of the present embodiment, particularly the non-fluorinated polymer (α), A ² O is more preferably an ethyleneoxy group, and n is 1 to 50. Integers are preferred, integers of 5 to 20 are more preferred, and integers of 8 to 14 are even more preferred. When n is 2 or more, n A ² O may be the same or different. Further, ^{when there are two or more types of A 2} O, they can have a block addition structure or a random addition structure.

The reactive emulsifier (B2) represented by the above 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 alkaline catalyst such as caustic soda or caustic potassium.

The phenol having the corresponding unsaturated hydrocarbon group includes not only industrially produced pure products or mixtures, but also those existing 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 is extracted from cashew nut shells and is collectively called cardanol. Examples thereof include -pentadecazienyl] phenol, 3- [8 (Z) -pentadecenyl] phenol, and 3- [11 (Z) -pentadecenyl] phenol.

The reactive emulsifier (B3) used in the present embodiment is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18. .. The 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 include mono or diglyceride, which is a good fatty acid, and triglyceride, which is a fatty acid containing at least one hydroxyunsaturated fatty acid (linoleic acid, ricinooleic acid, 2-hydroxytetracosenoic acid, etc.). Addition of alkylene oxide of triglyceride of fatty acid containing at least one hydroxyunsaturated fatty acid in terms of emulsion stability of the non-fluorinated polymer (α) or (β) of the present embodiment, particularly the non-fluorinated polymer (α). The product is preferable, the alkylene oxide adduct having 2 to 4 carbon atoms of castor oil (triglyceride of fatty acid containing ricinoleic acid) is more preferable, and the ethylene oxide adduct of castor oil is further preferable. Further, the number of moles of the alkylene oxide added can be appropriately selected so as to be within the above HLB range, and the non-fluorinated polymer (α) or (β) of the present embodiment, particularly the non-fluorinated polymer (α). ) Is more preferably 20 to 50 mol, further preferably 25 to 45 mol, in terms of emulsion stability. Moreover, when there are two or more kinds of alkylene oxides, they can have a block addition structure or a random addition structure.

The reactive emulsifier (B3) used in the present 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 particularly limited. It's not a thing. For example, it can be synthesized by adding a predetermined amount of alkylene oxide to triglyceride of a fatty acid containing ricinoleic acid, that is, castor oil using an alkaline catalyst such as caustic soda or caustic potassium at 120 to 170 ° C. under pressure. ..

The composition ratio of the monomer of the component (B) in the non-fluoropolymer (α) or (β) of the present embodiment is the water repellency of the obtained textile product and the non-fluoropolymer (α) of the present embodiment. Alternatively, from the viewpoint of improving the emulsion stability during the emulsion polymerization or dispersion polymerization of (β) and in the composition after the polymerization, the total amount of the monomer components constituting the non-fluoropolymer (α) or (β) is used. On the other hand, it is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass.

The non-fluorine-based polymer (α) or (β) contained in the water-repellent composition of the present embodiment, particularly the non-fluorine-based polymer (β), can improve the durable water repellency of the obtained textile product. In addition to the VC) component or the (A) component, or the (VC) component and the (A) component, at least one selected from the group consisting of the following (C1), (C2), (C3) and (C4). It is preferable that the (meth) acrylic acid ester monomer (C) (hereinafter, also referred to as “C component”) of 2 is 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) (Meta) acrylic acid ester monomer represented by the following general formula (C-1)

[In formula (C-1), R ⁵ represents a hydrogen or 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) (Meta) acrylic acid ester monomer represented by the following general formula (C-2)

[In formula (C-2), R ⁷ represents a hydrogen or 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) Methacrylate monomer represented by the following general formula (C-3)

[In 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) (Meta) acrylic acid ester monomer represented by the following general formula (C-4)

[In formula (C-4), R ¹⁰ represents a hydrogen or 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 1 Represents a valent organic group. ]

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 moiety. It is a (meth) acrylic acid ester monomer having 1 to 11 monovalent chain hydrocarbon groups. From the viewpoint of being able to react with a cross-linking 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 preferably has a functional group. A non-fluorinated polymer (α) or (β) containing a monomer of (C1) having a group capable of reacting with these cross-linking agents, particularly a non-fluorinated polymer (β), is added to a textile product together with the cross-linking agent. When treated, the durable water repellency can be improved while maintaining the texture of the obtained textile product. The isocyanate group may be a blocked isocyanate group protected by 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, it is preferable that it is linear and / or is a saturated hydrocarbon group in that the durable water repellency of the obtained textile product can be improved.

Specific examples of the (C1) monomer include 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, and 1,1-bis (acryloyloxymethyl) ethyl. Examples thereof include isocyanate. 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) ethyl isocyanate are preferable because the durable water repellency of the obtained textile product can be improved. Further, dimethylaminoethyl (meth) acrylate is preferable in terms of improving the texture of the obtained textile product.

The composition ratio of the monomer of (C1) in the non-fluorinated polymer (α) or (β) of the present embodiment is the non-fluorinated polymer (α) from the viewpoint of water repellency and texture of the obtained textile product. Alternatively, it is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and further preferably 5 to 20% by mass with respect to the total amount of the monomer components constituting (β). preferable.

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

The composition ratio of the monomer of (C2) in the non-fluorinated polymer (α) or (β) of the present embodiment is the non-fluorinated polymer (α) from the viewpoint of water repellency and texture of the obtained textile product. Alternatively, it is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and further preferably 5 to 20% by mass with respect to the total amount of the monomer components constituting (β). preferable.

The monomer (C3) is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester moiety. As the chain hydrocarbon group having 1 to 4 carbon atoms, a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group and the like. Specific examples of the compound 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. Among them, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferable, and methyl methacrylate is more preferable, because the durable water repellency of the obtained textile product can be improved.

The composition ratio of the monomer of (C3) in the non-fluorinated polymer (α) or (β) of the present embodiment is the non-fluorinated polymer (α) from the viewpoint of water repellency and texture of the obtained textile product. Alternatively, it is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and further preferably 5 to 20% by mass with respect to the total amount of the monomer components constituting (β). preferable.

The monomer (C4) is a (meth) acrylic acid ester monomer having 3 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 simple having 3 or more (meth) acryloyloxy groups in one molecule. A metric is preferred. In formula (C-4), the p Ts may be the same or different. Specific compounds include, for example, ethoxylated isocyanuric acid triacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the like. Examples thereof include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate. These monomers may be used alone or in combination of two or more. Among them, tetramethylolmethanetetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferable in that the durable water repellency of the obtained textile product can be improved.

The composition ratio of the monomer of the above (C4) in the non-fluorinated polymer (α) or (β) of the present embodiment is the non-fluorinated polymer (α) from the viewpoint of water repellency and texture of the obtained textile product. Alternatively, it is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and further preferably 5 to 20% by mass with respect to the total amount of the monomer components constituting (β). preferable.

The total composition ratio of the monomers of the above component (C) in the non-fluorinated polymer (α) or (β) of the present embodiment is the non-fluorinated polymer from the viewpoint of water repellency and texture of the obtained textile product. It is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and 5 to 20% by mass with respect to the total amount of the monomer components constituting (α) or (β). Is even more preferable.

The non-fluorinated polymer (α) or (β) contained in the water repellent composition of the present embodiment includes the component (A), the component (VC), the component (B) and the component (C), as well as these. The copolymerizable monofunctional monomer (D) can be contained within a range that does not impair the effects of the present invention.

Examples of the monomer of (D) include (meth) acryloylmorpholine, (meth) acrylic acid ester having a hydrocarbon group other than the components (A) and (C), (meth) acrylic acid, and fumaric acid. Esters, maleic acid esters, fumaric acid, maleic acid, (meth) acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, styrene and other vinyl-based monomers other than fluorine-free (VC) components, etc. Can be mentioned. The (meth) acrylic acid ester having a hydrocarbon group other than the component (A) and the component (C) has a vinyl group, a hydroxyl group, an amino group, an epoxy group and an isocyanate group, and a blocked isocyanate group in the hydrocarbon group. It may have a substituent other than a group capable of reacting with a cross-linking agent such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond, or a urethane bond. Etc. may be possessed. Examples of the (meth) acrylic acid ester other than the component (A) and the component (C) include methyl acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate and the like. Can be mentioned. Among them, (meth) acryloyl morpholine is more preferable because it can improve the peel strength of the obtained textile product against the coating.

The composition ratio of the monomer of (D) in the non-fluorinated polymer (α) or (β) of the present embodiment is the non-fluorinated polymer (α) from the viewpoint of water repellency and texture of the obtained textile product. Alternatively, it is preferably 10% by mass or less with respect to the total amount of the monomer components constituting (β).

The non-fluoropolymer (α) or (β) of the present embodiment contains 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 capable of reacting with a cross-linking agent. It is preferable to have it because it improves the durable water repellency of the obtained textile product. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Further, it is preferable that the non-fluorine-based polymer (α) or (β) has an amino group because it improves the texture of the obtained textile product.

The weight average molecular weight of the non-fluorinated polymer (α) of the present embodiment is preferably 100,000 or more. If the weight average molecular weight is less than 100,000, the water repellency of the obtained textile product tends to be insufficient. Further, the weight average molecular weight of the non-fluorinated polymer (α) is more preferably 500,000 or more. In this case, the obtained textile product can exhibit more sufficient water repellency. The upper limit of the weight average molecular weight of the non-fluorinated polymer (α) is preferably about 5 million.

The weight average molecular weight of the non-fluorinated polymer (β) of the present embodiment is preferably 100,000 or more. If the weight average molecular weight is less than 100,000, the water repellency of the obtained textile product tends to be insufficient. Further, the weight average molecular weight of the non-fluorinated polymer (β) is more preferably 500,000 or more. In this case, the obtained textile product can exhibit more sufficient water repellency. The upper limit of the weight average molecular weight of the non-fluorinated polymer (β) is preferably about 5 million.

The weight average molecular weight of the non-fluoropolymer is determined by using a GPC device (GPC "HLC-8020" manufactured by Toso Co., Ltd.) under the conditions of a column temperature of 40 ° C. and a flow rate of 1.0 ml / min, using tetrahydrofuran as an eluent. It means the value converted to standard polystyrene. The column used is a column in which three columns of trade names TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation are connected.

In the present embodiment, the melt viscosity of the non-fluorinated polymer (α) at 105 ° C. is preferably 1000 Pa · s or less. When the melt viscosity at 105 ° C. exceeds 1000 Pa · s, the texture of the obtained textile product tends to be coarse and hard. Further, if the melt viscosity of the non-fluorine polymer (α) is too high, the non-fluorine polymer (α) may precipitate when the non-fluorine polymer (α) is emulsified or dispersed to form a water repellent composition. It may settle, and the storage stability of the water repellent composition tends to decrease. The melt viscosity at 105 ° C. is more preferably 500 Pa · s or less. In this case, the obtained textile product or the like exhibits sufficient water repellency and has a better texture.

In the present embodiment, the melt viscosity of the non-fluorinated polymer (β) at 105 ° C. is preferably 1000 Pa · s or less. When the melt viscosity at 105 ° C. exceeds 1000 Pa · s, the texture of the obtained textile product tends to be coarse and hard. Further, if the melt viscosity of the non-fluorine polymer (β) is too high, the non-fluorine polymer (β) may precipitate when the non-fluorine polymer (β) is emulsified or dispersed to form a water repellent composition. It may settle, and the storage stability of the water repellent composition tends to decrease. The melt viscosity at 105 ° C. is more preferably 500 Pa · s or less. In this case, the obtained textile product or the like exhibits sufficient water repellency and has a better texture.

“Melting viscosity at 105 ° C.” means using an elevated flow tester (for example, CFT-500 manufactured by Shimadzu Corporation) and putting 1 g of a non-fluorinated polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm). Viscosity measured by holding at 105 ° C. for 6 minutes and applying ^{a load of 100 kg ・ f / cm 2 with a plunger.}

<Silicone resin (γ)>
Examples of the silicone resin include silicone resin and silicone oil. Silicone resin is an organopolysiloxane containing MQ, MDQ, MT, MTQ, MDT or MDTQ as constituents, solid at 25 ° C. and having 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 referred to as MDQ, MTQ or MDTQ.

Silicone resin can also be obtained as a solution in which it is dissolved 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. And so on.

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 Industry Co., Ltd. Cyclotetrasiloxane), KF9021L (trimethylsilyl group-containing polysiloxane: low-viscosity methylpolysiloxane = 50:50 mixture), KF7312L (trimethylsilyl group-containing polysiloxane: low-viscosity methylpolysiloxane = 50:50 mixture) and the like.

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

The silicone oil is a linear organopolysiloxane, and may have an organic group at at least one of the side chain and the terminal of the organopolysiloxane. As such a silicone oil, the same one as the above-mentioned hydrophobic silicone oil and functionalized silicone oil can be used, and for example, straight silicone such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil can be used. Oils: 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, Examples thereof include modified silicone oils such as higher fatty acid ester-modified silicone oils and higher aliphatic amide-modified silicone oils.

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, and carbinol are preferable. More preferably, modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, and alkyl aralkyl modified silicone oil.

Examples of the amino-modified silicone oil include compounds having an organic group containing an amino group and / or an imino group at at least one of the side chain and the terminal of the organopolysiloxane. Examples of such an organic group include an organic group _{represented by -R-NH 2} and an organic group represented by -R-NH-R'-NH2. Examples of R and R'include divalent groups such as an ethylene group and a propylene group. A part or all of the amino group and / or the imino group may be a sealed amino group and / or the imino group. The sealed amino group and / or imino group can be obtained, for example, by treating the amino group and / or the imino group with a sequestering agent. Examples of the sequestering 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 to have. When the kinematic viscosity at 25 ° C. is ^{larger than 100,000 mm 2} / s, the viscosity tends to be too high and workability tends to deteriorate. The kinematic viscosity at 25 ° C. means a value measured by the method described in JIS K 2283: 2000 (Ubbelohde viscometer).

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

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

The silicone resin may be used alone or in combination of two or more.

The contents of the non-fluorinated polymer (α), the non-fluorinated polymer (β) and the silicone resin (γ) contained in the water repellent composition of the present embodiment are the water repellency of the obtained textile product and the content of the textile product. Ratio (α) / [(β) + (γ) of the mass of the non-fluorinated polymer (α) to the total mass of the non-fluorinated polymer (β) and the silicone resin (γ) in terms of peeling strength against the coating. )] Is preferably 2.5 / 97.5 to 40/60, more preferably 2.5 / 97.5 to 35/65, and preferably 5/95 to 25/75. Even more preferably, it is even more preferably 10/90 to 20/80.

Further, from the viewpoint of further improving the texture of the obtained textile product, the water repellent composition of the present embodiment preferably contains a silicone resin (γ). In this case, the ratio [(α) + (β)] / (γ) of the total mass of the non-fluorinated polymer (α) and the non-fluorinated polymer (β) to the mass of the silicone resin (γ) is 95. It is preferably / 5 to 20/80, more preferably 90/10 to 30/70, even more preferably 80/20 to 40/60, and 80/20 to 50/50. Is even more preferable.

In the water repellent composition of the present embodiment, silica modified by a hydrophilic agent and a hydrophobic agent (silica having a hydrophilic group and a hydrophobic group on the silica surface) can also be used in combination. Examples of silica having a hydrophilic group and a hydrophobic group on the silica surface include Leolosil HG-09 (manufactured by Tokuyama Corporation, trade name), AEROSIL NA50H, RA200H, RA200HS (above, Nippon Aerosil Co., Ltd.). ), Product name), etc.

Additives and the like can be added to the water repellent composition of the present embodiment, if necessary. Additives include other water repellents, surfactants, defoamers, pH regulators, antibacterial agents, fungicides, colorants, antioxidants, deodorants, various organic solvents, chelating agents, antistatic agents. Examples thereof include agents, catalysts, cross-linking agents, antibacterial deodorants, flame retardants, softeners, and anti-wrinkle agents.

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

Examples of the defoaming agent include fat-based defoaming agents such as castor oil, sesame oil, flaxseed oil, and animal and vegetable oils; fatty acid-based defoaming agents such as stearic acid, oleic acid, and palmitic acid; , Ethylene glycol distearate, butyl stearate and other fatty acid ester defoamers; polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3-heptanol, 2-ethylhexanol and other alcohol defoamers; -T-Amilphenoxyethanol 3-heptyl cellosolve nonyl cellosolve 3-ether-based defoamers such as heptyl carbitol; phosphate-based defoamers such as tributyl osphate and tris (butoxyethyl) huosphate; amine-based defoamers such as diamilamine Foaming agents; amide-based defoaming agents such as polyalkyleneamide and acylate polyamine; sulfuric acid ester-based defoaming agents such as sodium lauryl sulfate; mineral oil and the like can be mentioned. The defoaming agent may be used alone or in combination of two or more.

pH adjusters include organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, citric acid, malic acid, sulfonic acid, methanesulfonic acid and toluenesulfonic acid; hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, etc. Inorganic acids such as boric acid; bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolamine, pyridine, morpholin and the like can be mentioned. The pH adjuster may 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, and the like. 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 carbi 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 and diethylene glycol monoethyl ether acetate; formamide, acetamide, benzamide, N, N- Examples thereof include amides such as dimethylformamide and acetanilide. As the organic solvent, one type can be used alone or two or more types can be used in combination.

As the antistatic agent, it is preferable to use an antistatic agent that does not easily impair the water-repellent performance. Antistatic agents include, for example, cationic surfactants such as higher alcohol sulfates, sulfated oils, sulfonates, quaternary ammonium salts, imidazoline type quaternary salts, polyethylene glycol type, polyhydric alcohol ester type. Nonionic surfactants such as, imidazoline type quaternary salts, amphoteric surfactants such as alanine type and betaine type, polymer compound type antistatic polymers, polyalkylamines and the like can be mentioned. The antistatic agent may be used alone or in combination of two or more.

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

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

For example, non-fluorine is obtained by emulsion polymerization or dispersion polymerization of the (meth) acrylic acid ester monomer (A) represented by the general formula (A-1) in the medium in the presence of the (VC) component. The system polymer (α) or (β) can be obtained. More specifically, for example, the component (A), the component (VC), and, if necessary, the component (B), the component (C) and the component (D), and an emulsifying aid or dispersion in the medium. Auxiliary agents are added and the mixture is emulsified or dispersed to give an emulsion or dispersion. By adding a polymerization initiator to the obtained emulsion or dispersion, the polymerization reaction is started, and the monomer and the reactive emulsifier can be polymerized. Examples of the means for emulsifying or dispersing the above-mentioned mixed solution include a homomixer, a high-pressure emulsifier, ultrasonic waves, and the like.

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

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

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

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

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

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

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

[In the formula, R ²¹ and R ²² independently represent 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, respectively. ]

[In the formula, R ²³ 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 polycyclic phenols, monovalent phenols such as phenol and naphthol which may have a hydrocarbon group having 1 to 12 carbon atoms or their styrenes (styrene, α-methylstyrene, vinyltoluene) are added. Products or their benzyl chloride reactants and the like can be mentioned. Examples of amines include aliphatic amines having 8 to 44 carbon atoms in a straight chain or a branched chain.

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

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

Examples of the polyhydric alcohol fatty acid ester include a condensation reaction product of the polyhydric alcohol and a fatty acid having 8 to 24 carbon atoms in a straight chain or a branched chain.

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

Among these, from the viewpoints of having little influence on water and oil repellency, little influence on light resistance, and good emulsifying property of the copolymer, alcohol having 8 to 24 carbon atoms in the straight chain or branched chain or Alkenol, an acetylene alcohol represented by the above general formula (6) is preferable, an alcohol having 8 to 24 carbon atoms in a straight chain or a branched chain, and an acetylene alcohol represented by the above general formula (6) are 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, epichlorohydrin and the like. Ethylene oxide and 1,2-propylene oxide are preferable as the alkylene oxide, and ethylene oxide is more preferable, from the viewpoints that the influence on the water and oil repellency is small and the emulsifying property of the copolymer is improved.

The number of moles of alkylene oxide added is preferably 1 to 200, more preferably 3 to 100, and even more preferably 5 to 50. When the number of moles of alkylene oxide added is within the above range, water repellency and oil repellency and product stability can be easily obtained at a high level. If the number of moles of alkylene oxide added is less than 1 mol, the product stability tends to decrease and the water and oil repellency tends to decrease, and if it exceeds 200 mol, the water and oil repellency tends to decrease.

In the copolymer according to the present embodiment, when a nonionic surfactant having an HLB of 7 to 18 is used as the nonionic surfactant, a better aqueous dispersion can be obtained. Here, the HLB is based on the HLB of Griffin, and the formula of Griffin is changed to the following formula. Here, the hydrophilic group refers to an ethylene oxide group.
HLB = (hydrophilic group x 20) / molecular weight

The HLB of the nonionic surfactant used in the present embodiment is 7 to 18, and the composition of the non-fluoropolymer (α) or (β) of the present embodiment during emulsification polymerization or dispersion polymerization and after polymerization. From the viewpoint of emulsion stability in an object (hereinafter, simply referred to as emulsion stability), 9 to 15 are preferable. Furthermore, it is more preferable to use two or more nonionic surfactants having different HLBs within the above range in combination in terms of storage stability of the water repellent composition. Further, 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 the 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 that can be mixed with water. For example, alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, and diethyl. Examples thereof include ethers such as ether, and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. The ratio of water to the organic solvent is not particularly limited.

As the polymerization initiator, a known polymerization initiator such as an azo-based, peroxide-based, or redox-based polymerization initiator 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 the total monomer. When the content of the polymerization initiator is in the above range, the non-fluorinated polymer (α) or (β) having a weight average molecular weight of 100,000 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 parts by mass or less, and more preferably 0.1 parts by mass or less, based on 100 parts by mass of all the monomers. If the content of the chain transfer agent exceeds 0.1 parts by mass, the molecular weight is lowered, and it is difficult to efficiently produce the non-fluorinated polymer (α) or (β) having a weight average molecular weight of 100,000 or more. It tends to be.

A polymerization inhibitor may be used for adjusting the molecular weight. By adding a polymerization inhibitor, a non-fluorinated polymer having a desired weight average molecular weight can be easily obtained.

The temperature of the polymerization reaction is preferably 20 ° C to 150 ° C. If the temperature is less than 20 ° C, the polymerization tends to be insufficient as compared with the case where the temperature is in the above range, and if the temperature exceeds 150 ° C, it may be difficult to control the heat of reaction. ..

In the polymerization reaction, the weight average molecular weight of the obtained non-fluoropolymer (α) or (β) can be adjusted by increasing or decreasing the contents of the above-mentioned polymerization initiator, chain transfer agent and polymerization inhibitor, and can be adjusted at 105 ° C. The melt viscosity in the above can be adjusted by increasing or decreasing the content of the polyfunctional monomer and the content of the polymerization initiator. If 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-fluoropolymer (α) or (β) in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is the content of the emulsion or dispersion from the viewpoint of storage stability and handleability of the composition. It is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, based on the total amount.

The water repellent composition of the present embodiment includes a composition containing a non-fluorinated polymer (α) obtained by the above method, a composition containing a non-fluorinated polymer (β) obtained by the above method, and a composition containing the non-fluorinated polymer (β) obtained by the above method. / Or can be prepared by mixing with a commercially available silicone resin (γ).

The water-repellent fiber product of the present embodiment comprises the above-mentioned non-fluorine-based polymer (α) of the present embodiment and a fiber product to which the non-fluorine-based polymer (β) and / or silicone resin (γ) is adhered. is there.

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

In the water-repellent textile product of the present embodiment, by treating the textile product with the treatment liquid containing the above-mentioned water-repellent composition, the textile product contains a non-fluorine-based polymer (α) and a non-fluorine-based polymer (β). And / or obtained by adhering to a silicone resin (γ). The material of such textile products is not particularly limited, and natural fibers such as cotton, linen, silk and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as nylon, polyester, polyurethane and polypropylene, and composite fibers thereof, Examples include blended fibers. The form of the textile product may be any form such as fiber, thread, cloth, non-woven fabric, and paper.

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

The amount of the water repellent composition attached to the textile product can be appropriately adjusted according to the required degree of water repellency, but from the viewpoint of water repellency and texture, the water repellent composition is based on 100 g of the textile product. It is preferable to adjust the total adhesion amount of the non-fluoropolymers (α) and (β) and the silicone resin (γ) contained in the product to be 0.01 to 10 g, and to be 0.05 to 5 g. It is more preferable to adjust to.

Further, after adhering the non-fluorinated polymer (α) of the present embodiment, the non-fluorinated polymer (β) and / or the silicone resin (γ) to the textile product, it is preferable to appropriately heat-treat the fiber product. The temperature condition is not particularly limited, but when the water repellent composition of the present embodiment is used, sufficiently good water repellency can be exhibited in the textile product under mild conditions 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 flexible, and under mild heat treatment conditions, that is, low temperature cure conditions. Sufficient water repellency can be imparted to textile products.

In particular, when it is desired to improve durable water repellency, the above-mentioned step of treating a textile product with a treatment liquid containing a water repellent composition and one melamine resin, glioxal resin, isocyanate group or blocked isocyanate group are used. It is preferable to make the textile product water-repellent by a method including a step of attaching a cross-linking agent typified by the above compound to the textile product and heating the cross-linking agent. Further, when it is desired to further improve the durable water repellency, the water repellent composition is a non-fluorinated polymer (α) or (β) in which a monomer having a functional group capable of reacting with the above-mentioned cross-linking agent is copolymerized. ) Is preferably included.

As the melamine resin, a compound having a melamine skeleton can be used. For example, polymethylol melamine such as trimethyl melamine and hexamethylol melamine; a part or all of the methylol groups of polymethylol melamine have 1 to 6 carbon atoms. Amethylmethylmelamine that has become an alkoxymethyl group having an alkyl group; asyloxymethylmelamine in which a part or all of the methylol group of polymethylol melamine has become an acyloxymethyl group having an acyl group having 2 to 6 carbon atoms. Can be mentioned. These melamine resins may be either monomers, dimers or more multimers, or mixtures thereof. Further, a product obtained by copolymerizing a part of melamine with urea or the like can also be used. Examples of such melamine resins include Beccamin APM, Beccamin M-3, Beccamin M-3 (60), Beccamin MA-S, Beccamin J-101, and Beccamin J-101LF manufactured by DIC Corporation. Examples include Unica Resin 380K manufactured by Miki Riken Kogyo Co., Ltd. and Riken Resin MM series manufactured by Miki Riken Kogyo Co., Ltd.

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

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

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 polyisocyanate 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 the polyfunctional isocyanate compound include diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimers or trimers of these diisocyanate compounds. The alkylene diisocyanate 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-phenylenediocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, and dodeca. Methylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, phenylenediocyanate, tolylen 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-diisocyanatecyclohexane, 4,4 '-Methylene-bis (cyclohexamethylene diisocyanate), 3-isocyanate-methyl-3,5,5-trimethylcyclohexylisocyanate, acid-diisocyanate dimerate, ω, ω'-diisocyanate diethylbenzene, ω, ω'-diisocyanate dimethyltoluene, ω, ω'-diisocyanate diethyltoluene, bis (2-isocyanate ethyl) fumarate ester, 1,4-bis (2-isocyanate-prop-2-yl) benzene, and 1,3-bis (2-isocyanate-) Prop-2-yl) benzene can be mentioned.

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

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

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

The isocyanate group contained in the polyfunctional isocyanate compound may be a blocked isocyanate group as it is or may be a blocked isocyanate group blocked by a blocking agent. Blocking agents include pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole, pyrazole; phenol, methylphenol, Phenols such as chlorphenol, iso-butylphenol, tert-butylphenol, iso-amylphenol, octylphenol, nonylphenol; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam; , Acetylacetone, methyl acetoacetate, ethyl acetoacetate and other active methylene compounds; formaldehyde, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime and other oximes; imidazole, 2-methylimidazole Oxime 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 by introducing a hydrophilic group into the polyisocyanate structure to have a surface-active effect can also be used. Further, in order to promote the reaction, a known catalyst such as organic tin or organic zinc can be used in combination.

The cross-linking agent or 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 immersing the object to be treated (textile product) in a treatment liquid emulsified and dispersed in water and drying the treatment liquid adhering to the object to be treated. It can be attached to the object to be treated. Then, by heating the cross-linking agent adhering to the object to be treated, the reaction between the cross-linking agent and the object to be treated and the non-fluorinated polymer (α) or (β) can proceed. In order to sufficiently proceed the reaction of the cross-linking agent and more effectively improve the washing durability, the heating at this time is preferably performed at 110 to 180 ° C. for 1 to 5 minutes. The step of adhering the cross-linking agent and heating may be performed at the same time as the step of treating with the treatment liquid containing the above-mentioned water repellent composition. When performed at the same time, for example, a treatment liquid containing a water repellent composition and a cross-linking agent is attached to the object to be treated, water is removed, and then the cross-linking agent adhering to the object to be treated is further heated. Considering simplification of the water-repellent processing process, reduction of heat quantity, and economy, it is preferable to perform the process at the same time as the treatment process of the water-repellent composition.

In addition, excessive use of the cross-linking agent may impair the texture. 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 object 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 made environmentally friendly.

The water-repellent fiber product of the present embodiment can be coated on a predetermined portion. Examples of the coating process include moisture permeable and waterproof processing and windproof processing for sports and outdoor applications. As a processing method, for example, in the case of moisture permeable and waterproof processing, a coating liquid containing a urethane resin, an acrylic resin or the like and a medium can be applied to one side of a water-repellent treated textile product and dried. 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-fluorinated polymers (α) and (β) contained in the water repellent composition of the present invention, in the above embodiment, the polymerization reaction is carried out by radical polymerization, but ultraviolet rays and electron beams. , The polymerization reaction may be carried out by photopolymerization by irradiating ionizing radiation such as γ-rays.

Further, in the present invention, the water-repellent composition is treated into a textile product to obtain a water-repellent fiber product, but the product treated with the water-repellent composition is not limited to textile products, and is not limited to textile products. , Resin or the like.

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

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited to these Examples.

<Preparation of polymer dispersion>
A mixed solution having the compositions shown in Tables 1 and 2 (in the table, the numerical value indicates (g)) was polymerized by the procedure shown below to obtain a polymer dispersion.

(Synthesis Example 1)
Isobornyl acrylate 2 g, Neugen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7) 0.2 g, Neugen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in an autoclave. , Polyoxyalkylene branched decyl ether, HLB = 12.5) 1.3 g, Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5) 0.5 g, stearyltrimethyl 1 g of ammonium sulfate, 25 g of tripropylene glycol and 144.7 g of water were added, and the mixture was mixed and stirred at 45 ° C. to prepare a mixed solution. The mixed solution was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.3 g of azobis (isobutylamidin) dihydrochloride was added to the mixed solution, and 25 g of vinyl chloride was continuously press-fitted under a nitrogen atmosphere so that the internal pressure of the autoclave was maintained at 0.3 MPa at 60 ° C. Radical polymerization was carried out for 6 hours to obtain a non-fluorine polymer (α) dispersion containing 13.5% by mass of the non-fluorine polymer (α).

(Synthesis Examples 2-11)
Polymerization was carried out in the same manner as in Example 1 except that the materials shown in Table 1 were used to obtain non-fluorinated polymer dispersions containing 13.5% by mass of the non-fluorinated polymer (α).

(Synthesis Examples 12 to 17)
Polymerization was carried out in the same manner as in Example 1 except that the materials shown in Table 2 were used to obtain non-fluorinated polymer dispersions containing 26.7% by mass of non-fluorinated polymer (β).

In each polymer in the polymer dispersions obtained in Synthesis Examples 1 to 17, 98% or more of all the monomers were polymerized by a gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation). It was confirmed that there was.

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) (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5)

<Preparation of dispersion liquid containing silicone resin>
(Preparation Example 1)
As a silicone resin, 20 parts by mass of TSF-4709 (amino-modified silicone oil, manufactured by Momentive Performance Materials Japan LLC, trade name), 0.3 parts by mass of glycolic acid, and branched alcohol having 12 to 14 carbon atoms. 4 parts by mass of 5 mol of ethylene oxide adduct and 5 parts by mass of butyl diglycol were mixed. Then, 70.7 parts by mass of water was added to the obtained mixture while mixing little by little to obtain a dispersion liquid containing 20% by mass of a silicone resin.

(Preparation Examples 2-5)
A silicone resin dispersion 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 (Amino Silicone, manufactured by Toray Dow Corning Co., Ltd., trade name)
(Preparation Example 3) KF-9901 (Methylhydrogen 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) SF 8416 (alkyl silicone, manufactured by Toray Dow Corning Co., Ltd., trade name)

(Preparation Example 6)
KF8005 (amino-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 18.5 parts by mass, 0.15 parts by mass of formic acid, and 0.5 mol adduct of ethylene oxide of branched alcohol having 12 to 14 carbon atoms. The parts by mass were mixed. Then, 80.85 parts by mass of water was added to the obtained mixture while mixing little by little to obtain a dispersion liquid containing 18.5% by mass of amino-modified silicone.

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

The amino-modified silicone dispersion and the 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 mixed as silicone resin (γ) in terms of mass ratio. A 20 mass% silicone resin dispersion containing 9.2: 5.4: 5.4 was obtained.

(Preparation Example 7)
Leoloseal HG-09 (silica having an amino group and a trimethylsilyl group, manufactured by Tokuyama Co., Ltd.) as silica modified by a hydrophilic agent and a hydrophobic agent (silica having a hydrophilic group and a hydrophobic group on the silica surface) ) 10 parts by mass, 1 part by mass of 90% acetic acid as an acid component, and 89 parts by mass of water were mixed. Then, using an ultrasonic emulsifier US-600E (Nissei Tokyo Office Co., Ltd.), the mixture was dispersed for 10 minutes while maintaining 60 ° C. After that, it was cooled to obtain a dispersion liquid containing 10% by mass of Leoloseal HG-09.

<Preparation of water repellent composition>
(Examples 1 to 29 and Comparative Examples 1 to 4)
The non-fluorinated polymer (α) dispersion, the non-fluorine polymer (β) dispersion, and the silicone resin dispersion are mixed at the ratios shown in Tables 3 to 7 (in the table, the numerical values indicate (parts by mass)). , Water repellent compositions were obtained respectively.

<Evaluation of water repellent composition>
The water repellent composition obtained above was evaluated as follows.

(Evaluation of water repellency of textile products)
The test was conducted with the shower water temperature set to 20 ° C. according to the spray method of JIS L 1092 (2009). In this test, the dyed 100% polyester cloth or 100% nylon cloth was used, and the water repellent compositions of Examples and Comparative Examples were used as a non-fluorinated polymer (α), a non-fluorinated polymer (β), and a silicone resin. After immersion treatment (pickup rate 60% by mass) in a treatment liquid diluted with water so that the total content of the above is 3% by mass, it is dried at 130 ° C. for 2 minutes, and further heat-treated at 170 ° C. for 30 seconds. Then, the water repellency of the obtained cloth was evaluated. The results were visually evaluated according to the following grades. When the characteristics were slightly good, a "+" was added to the grade, and when the characteristics were slightly inferior, a "-" was added to the grade. The results are shown in Tables 3-7.
Water repellency: Condition 5: No wetness adhered to the surface 4: Slightly adhered to the surface Wetness 3: Partial wetness on the surface 2: Wetness on the surface 1: Wetness on the entire surface Item 0: Both front and back sides are completely moist.

(Evaluation of texture of textile products)
As for the texture, the dyed 100% polyester cloth was used, and the water repellent compositions of Examples and Comparative Examples had a total content of non-fluorine polymer (α), non-fluorine polymer (β) and silicone resin. The evaluation was made using a product which was immersed in a treatment liquid diluted with water so as to have a concentration of 3% by mass (pickup rate 60% by mass), dried at 130 ° C. for 2 minutes, and further heat-treated at 170 ° C. for 30 seconds. The results were evaluated by handling on the following five stages. The results are shown in Tables 3-7.
1: Hard ~ 5: Soft

(Evaluation of durable water repellency of textile products)
The test was conducted with the shower water temperature set to 20 ° C. according to the spray method of JIS L 1092 (2009). In this test, the dyed 100% polyester cloth was used as a blocked isocyanate-based cross-linking agent having a total content of 3% by mass of the non-fluorinated polymer (α), the non-fluorinated polymer (β) and the silicone resin. The water repellency of Examples and Comparative Examples is 1% by mass of NK Assist NY-50, 1% by mass of Textport BG-290 as a penetrant, and 0.5% by mass of Nice Pole FE-26 as an antistatic agent. A cloth (L) obtained by immersing the agent composition and each of the above agents in a treatment liquid diluted with water (pickup rate 60% by mass), drying at 130 ° C. for 2 minutes, and further heat-treating at 170 ° C. for 60 seconds. The water repellency of the cloth after washing by the 103 method of -0) and JIS L 0217 (1995) 10 times (L-10) was evaluated in the same manner as in the above water repellency evaluation method. Further, the case of the 100% nylon cloth was evaluated in the same manner as the case of the 100% polyester cloth except that the heat treatment temperature was changed from 170 ° C. to 160 ° C. The results are shown in Tables 3-7.

(Peeling strength against coating of textile products)
The test was conducted in accordance with JIS K 6404-5 (1999). In this test, the dyed 100% nylon cloth was used as the water repellent composition of Examples and Comparative Examples, and the total content of the non-fluorinated polymer (α), the non-fluorinated polymer (β) and the silicone resin was used. After dipping treatment (pickup rate 60% by mass) in a treatment liquid diluted with water so that the content is 3% by mass, drying at 130 ° C. for 2 minutes, and further heat-treating at 170 ° C. for 30 seconds, the obtained product is obtained. It was used as a base cloth. 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 device, and the layers between the base cloth and the seam tape were peeled off. The strength was measured by an autograph (AG-IS, manufactured by Shimadzu Corporation). The moving speed of the gripper was pulled at 100 mm / min, and the average value of stress was defined as the peel strength [N / inch]. The results are shown in Tables 3-7.

The textile products treated with the water repellent compositions of Examples 1 to 29 exhibited sufficient water repellency and durable water repellency, but did not contain the non-fluorinated polymer (α). It was confirmed that the peel strength against the coating was superior to that when the agent composition was used.

The textile product treated with the water repellent composition of Comparative Example 1 containing no non-fluorinated polymer (β) and silicone resin (γ) was shown to be inferior in water repellency and durable water repellency.

Claims (8)

A non-fluorinated polymer containing a structural unit derived from at least one of vinyl chloride and vinylidene chloride monomer (VC), based on the total amount of the monomer components constituting the non-fluorinated polymer. As a non-fluoropolymer (α) having a content ratio of the monomer (VC) of 50% by mass or more,
A non-fluorine-based polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1), and a monomer constituting the non-fluorine-based polymer. A non-fluorinated polymer (β) having a content of the (meth) acrylic acid ester monomer (A) of 50% by mass or more based on the total amount of the components, and / or a silicone resin (γ).
A water repellent composition for textile products , including.

[In the formula (A-1), R ¹ represents a hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. ] The non-fluoropolymer (α) is a compound represented by the following general formula (I-1) in which (B1) HLB is 7 to 18, and the following general formula (II-) in which (B2) HLB is 7 to 18. It is selected from the group consisting of the compound represented by 1) and the compound in which (B3) an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18. The water repellent composition for textile products according to claim 1, further containing a structural unit derived from at least one reactive emulsifier (B).

[In formula (I-1), R ³ represents a hydrogen or 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. Represents a divalent group containing. ]

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² contains an alkyleneoxy group having 2 to 4 carbon atoms. Represents a divalent group. ] The water repellent composition comprises the non-fluorinated polymer (β).
The non-fluoropolymer (β) is a compound represented by the following general formula (I-1) in which (B1) HLB is 7 to 18, and the following general formula (II-) in which (B2) HLB is 7 to 18. It is selected from the group consisting of the compound represented by 1) and the compound in which (B3) an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18. The water repellent composition for textile products according to claim 1 or 2, further containing a structural unit derived from at least one reactive emulsifier (B).

[In formula (I-1), R ³ represents a hydrogen or 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. Represents a divalent group containing. ]

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² contains an alkyleneoxy group having 2 to 4 carbon atoms. Represents a divalent group. ] The non-fluorinated polymer (α) further contains a structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the general formula (A-1).
The (meth) acrylic acid ester monomer (A) in the non-fluoropolymer (α) contains an acrylic acid ester monomer (a1) and a methacrylic acid ester monomer (a2), and the (meth) The ratio (a1) / (a2) of the mass of the acrylic acid ester monomer (a1) contained in the acrylic acid ester monomer (A) to the mass of the methacrylic acid ester monomer (a2) is 30 /. The water repellent composition for textile products according to any one of claims 1 to 3, which is 70 to 90/10. The water repellent composition comprises the non-fluorinated polymer (β).
The (meth) acrylic acid ester monomer (A) in the non-fluoropolymer (β) contains an acrylic acid ester monomer (a1) and a methacrylic acid ester monomer (a2), and the (meth) The ratio (a1) / (a2) of the mass of the acrylic acid ester monomer (a1) contained in the acrylic acid ester monomer (A) to the mass of the methacrylic acid ester monomer (a2) is 30 /. The water repellent composition for a textile product according to any one of claims 1 to 4, which is 70 to 90/10. The water repellent composition contains the silicone resin (γ).
Any one of claims 1 to 5, wherein the silicone resin (γ) is at least one selected from the group consisting of amino-modified silicone, silicone resin, dimethyl silicone, methylhydrogen silicone, and alkyl-modified silicone. The water repellent composition for textile products according to. The non-fluorinated polymer (α) and the non-fluorinated polymer (β) and / or the silicone resin (γ) in the water repellent composition according to any one of claims 1 to 6 adhere to each other. Water-repellent textile products made of silicone products. A method for producing a water-repellent textile product, comprising a step of treating the textile product with a treatment liquid containing the water-repellent composition according to any one of claims 1 to 6.