KR20160110947A - Water repellent agent composition, water repellent fiber product and method for producing water repellent fiber product - Google Patents

Abstract

(B1) to (B3) having an HLB of 7 to 18 and containing a polymerizable unsaturated group, a structural unit derived from a (meth) acrylic acid ester monomer (A) having a monovalent hydrocarbon group which may have a substituent, And a structural unit derived from at least one reactive emulsifier (B) selected from the group consisting of a water-soluble polymer and a water-soluble polymer.

Description

TECHNICAL FIELD [0001] The present invention relates to a water repellent composition, a water repellent fiber product, and a method for producing a water repellent fiber product,

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

BACKGROUND ART Conventionally, a fluorine-based water repellent agent having a fluorine-containing group is known, and a fiber product whose surface is imparted with water repellency by treating such a fluorine-based water repellent agent with a fiber product or the like is known. Such a fluorine-based water repellent agent is generally prepared by polymerizing, or copolymerizing, a monomer having a fluoroalkyl group.

A fiber product treated with a fluorine-based water repellent agent exhibits excellent water repellency. However, since it is necessary to adjust the orientation property of a fluoroalkyl group in order to exhibit water repellency, a fluorine-based water repellent agent is attached to the fiber product and then heat treatment is performed at a temperature exceeding 130 캜 Should be. However, heat treatment at a high temperature requires a high energy, and there is a problem in the flow of international energy saving.

Further, monomers having a fluoroalkyl group are not satisfactory from an economic point of view because they are expensive, and monomers having a fluoroalkyl group are also poorly degradable, which is also problematic in terms of the environment.

On the other hand, in the field of water-repellent processing of textile products, there is a demand for a water-repellent agent capable of imparting excellent water repellency to a fiber product even at a low concentration or a low heat treatment temperature for stabilization of quality and cost reduction.

Therefore, in recent years, studies have been made on non-fluorine-based water repellent agents that do not contain fluorine. For example, Non-Patent Document 1 discloses a water repellent agent obtained by emulsifying and dispersing a hydrocarbon compound such as paraffin or wax, a fatty acid metal salt or an alkyl urea.

In addition, Patent Document 1 proposes a water repellent agent in which specific non-fluorinated polymers are emulsified and dispersed for the purpose of imparting water repellency that is inferior to that of conventional fluorinated water repellents.

Patent Document 1: JP-A-2006-328624

Non-Patent Document 1: "New water-repellent and water-repellent material for exclusive use of super water-repellent processing, processing agent", published by Osaka Chemical Marketing Center, 1996, p.7 to 9

However, it is difficult to obtain a fiber product having the same water repellency as in the case of treating with a conventional fluorine-based water repellent agent in the non-fluorine-based water repellent agent described in Non-Patent Document 1. In addition, the processed fiber product tends to be hardened, so that it can not be said that the tactile feeling is sufficient.

In the case of the non-fluorine-based water repellent agent described in Patent Document 1, the water repellency of the obtained fiber product tends to be lowered when a surfactant in an amount such that the non-fluorinated polymer is emulsified and dispersed sufficiently to ensure storage stability tends to decrease, It is difficult to plan for compatibility.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a water repellent agent composition capable of imparting sufficient water repellency to a textile product even when the heat treatment is not performed and obtaining a water repellent fiber product excellent in touch and water repellency , A water-repellent fiber product using the same, and a method for producing a water-repellent fiber product.

The present invention relates to a resin composition comprising a structural unit derived from a (meth) acrylic acid ester monomer (A) represented by the following formula (A-1) and a structural unit derived from a compound represented by the following formula (B1) (B2) a compound represented by the following general formula (II-1) in which the HLB is 7 to 18, and (B3) a compound having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18, And at least one reactive emulsifier (B) selected from the group consisting of alkylene oxide adducts and alkylene oxide adducts.

(A-1)

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

The compound of formula (I-1)

Wherein R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y ¹ represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms, Lt; / RTI >

The compound of formula (II-1)

Wherein R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group and Y ² represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms,

The non-fluorine-based polymer is obtained by adding a structural unit derived from at least one second (meth) acrylic acid ester monomer (C) selected from the group consisting of the following (C1), (C2), (C3) .

(C1) a (meth) acrylic acid ester monomer represented by the following formula (C-1)

The compound of formula (C-1)

Wherein R ⁵ represents hydrogen or a methyl group and R ⁶ represents at least one member 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, Represents a monovalent straight chain hydrocarbon group having 1 to 11 carbon atoms and having a functional group of the following formula Provided that the number of (meth) acryloyloxy groups in the molecule is 2 or less.

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

The compound of formula (C-2)

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

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

The compound of formula (C-3)

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

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

The compound of formula (C-4)

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

(B) a compound represented by the above formula (I-1) wherein the HLB is 7 to 18, (B2) a compound represented by the above formula (I) ) A compound represented by the above formula (II-1) wherein the HLB is 7 to 18, and (B3) an alkylene oxide having 2 to 4 carbon atoms in the oil having a hydroxyl group and a polymerizable unsaturated group, And a non-fluorinated polymer formed by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing at least one reactive emulsifier (B) selected from the compounds added.

The emulsion or the dispersion further contains at least one second (meth) acrylic acid ester monomer (C) selected from the group consisting of (C1), (C2), (C3) There may be.

According to the water repellent composition of the present invention, it is possible to provide a water repellent fiber product having excellent storage stability and imparting sufficient water repellency to a fiber product even when the heat treatment is not performed, and having excellent tactile feeling and water repellency.

The present invention also relates to a resin composition comprising a structural unit derived from a (meth) acrylic acid ester monomer (A) represented by the above formula (A-1) (B2) a compound represented by the above formula (II-1) wherein the HLB is 7 to 18, and (B3) a compound having an HLB of 7 to 18, wherein the oil having a hydroxyl group and a polymerizable unsaturated group has 2 to 4 (B) having at least one reactive emulsifier (B) selected from the group consisting of an alkylene oxide adducted with an alkylene oxide.

The non-fluorinated polymer preferably contains a structural unit derived from at least one second (meth) acrylic acid ester monomer (C) selected from the group consisting of (C1), (C2), (C3) .

(B) a compound represented by the above formula (I-1) wherein the HLB is 7 to 18, (B2) a compound represented by the above formula (I) ) A compound represented by the above formula (II-1) wherein the HLB is 7 to 18, and (B3) an alkylene oxide having 2 to 4 carbon atoms in the oil having a hydroxyl group and a polymerizable unsaturated group, And a non-fluorine polymer-adhered fiber product obtained by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing at least one reactive emulsifier (B) selected from the compounds added thereto.

The emulsion or the dispersion further contains at least one second (meth) acrylic acid ester monomer (C) selected from the group consisting of (C1), (C2), (C3) There may be.

The water repellent fiber product of the present invention can sufficiently maintain tactile feeling and water repellency even when it is used outdoors for a long time.

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

According to the method for producing a water repellent fiber product of the present invention, by using the water repellent composition according to the present invention which is excellent in storage stability and can impart sufficient water repellency to a textile product even when heat treatment is not performed, The fiber product can be stably produced. In addition, since the method of producing a water-repellent fiber product of the present invention does not require heat treatment at a high temperature, energy saving can be achieved, and a non-fluorine-based water repellent agent is used. .

According to the present invention, it is possible to provide a water repellent composition which is excellent in storage stability, can impart sufficient water repellency to a fiber product even when heat treatment is not performed, and can obtain a water repellent fiber product excellent in touch and water repellency.

The water repellent composition of the present invention exhibits excellent water repellency even in the case of a water repellent composition that does not contain a fluoroalkyl group or a compound having fluorine and can be used as a substitute for a fluorinated water repellent agent to solve the problem of influences on a fluorine source or environment can do. The water repellent composition of the present invention does not use a monomer having a fluoroalkyl group. Therefore, even when the water repellent composition is subjected to a heat treatment under a mild condition of 130 DEG C or less, Water repellency can be exhibited, and when the heat treatment is performed at a high temperature exceeding 130 캜, the heat treatment time can be made shorter than that of the fluorine-based water repellent agent. Therefore, deterioration due to heat of the object to be treated can be suppressed, so that the feel is flexible, and the amount of heat required for the heat treatment can be reduced, which is also excellent in cost.

Furthermore, according to the present invention, the amount of the surfactant contained in the water repellent composition can be reduced by using a specific reactive emulsifier instead of a general surfactant as the emulsifying dispersant used in the emulsion or dispersion polymerization of the non-fluorinated polymer. As a result, deterioration of the water repellency of the obtained fiber product or the like can be suppressed, and water repellency higher than that of the conventional non-fluorine-based water repellent agent can be realized. Further, the water repellent composition according to the present invention can improve the emulsion dispersibility of the non-fluorinated polymer itself, so that it is easy to maintain a stable emulsified state even when it is added to a processing bath, It becomes.

The water repellent composition of the present embodiment contains a constitutional unit derived from a (meth) acrylic acid ester monomer (A) (hereinafter also referred to as "component (A)") represented by the following formula (A- (B2) a compound represented by the following formula (II-1) wherein the HLB is 7 to 18, and (B3) a compound represented by the formula (I- Derived from at least one reactive emulsifier (B) (hereinafter also referred to as " component (B) ") selected from compounds having a carboxyl group, a carboxyl group, a hydroxyl group, Units based on the total weight of the non-fluorinated polymer.

(A-1)

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

The compound of formula (I-1)

Wherein R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y ¹ represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms, Lt; / RTI >

The compound of formula (II-1)

Wherein R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group and Y ² represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms,

Here, the term "(meth) acrylic acid ester" refers to "acrylic acid ester" or "methacrylic acid ester" corresponding thereto, and "(meth) acrylic acid", "(meth) acrylamide"

The term " reactive emulsifier " refers to an emulsifying dispersant having radical reactivity, that is, a surfactant having at least one polymerizable unsaturated group in the molecule, and can be copolymerized with a monomer such as a (meth) acrylic acid ester.

The term " HLB " refers to an HLB value calculated by the Griffin method, in which the ethyleneoxy group is regarded as a hydrophilic group and all others are regarded as a lipophilic group.

The (meth) acrylic acid ester monomer (A) represented by the above formula (A-1) used in the present embodiment has a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent. The hydrocarbon group may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may further have an alicyclic or aromatic cyclic structure. Of these, straight-chain alkyl groups are preferable, and straight-chain alkyl groups are more preferable. In this case, water repellency is more excellent. When the monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, examples of the substituent include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a block isocyanate group and a (meth) acryloyloxy group. In the present embodiment, in the above formula (A-1), R ² is preferably an unsubstituted hydrocarbon group.

The hydrocarbon group preferably has 12 to 24 carbon atoms. When the carbon number is less than 12, sufficient water repellency can not be exhibited when the non-fluorinated polymer is adhered to a textile product or the like. On the other hand, when the number of carbon atoms is more than 24, when the non-fluorinated polymer is adhered to a fiber product or the like as compared with the case where the number of carbon atoms is within the above range, the feel of the fiber product tends to be rough and rough.

And the carbon number of the hydrocarbon group is more preferably 12 to 21. When the carbon number is in this range, the water repellency and the feel are particularly excellent. Particularly preferable hydrocarbon groups are straight chain alkyl groups 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, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, hemeocosyl .

The component (A) may 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 capable of reacting with a crosslinking agent. In this case, durability and water repellency of the obtained fiber product can be further improved. The isocyanate group may form a blocked isocyanate group protected with a blocking agent. Further, when the component (A) has an amino group, it is possible to further improve the feel of the obtained fiber product.

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

The above component (A) may be used singly or in combination of two or more.

The HLB of the compounds (B1) to (B3) used in the present embodiment is 7 to 18 and the HLB of the non-fluorinated polymer (hereinafter referred to as the non-fluorinated polymer of the present embodiment) contained in the water repellent composition of this embodiment Is preferably from 9 to 15 in terms of emulsion stability during emulsion polymerization or dispersion polymerization and in emulsion stability in a composition after polymerization (hereinafter simply referred to as emulsion stability). In addition, from the viewpoint of storage stability of the water repellent composition, it is more preferable to use two or more reactive emulsifiers (B) having different HLB within the above range.

In the reactive emulsifier (B1) represented by the above formula (I-1) used in the present embodiment, R ³ is hydrogen or a methyl group, and more preferably a methyl group from the viewpoint of copolymerization with the component (A). X is a straight chain or branched alkylene group having 1 to 6 carbon atoms, and from the viewpoint of emulsion stability of the non-fluorinated polymer of the present embodiment, a straight chain 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 kind, combination and addition number of the alkyleneoxy group in Y ¹ can be appropriately selected so as to be within the HLB range described above. When two or more kinds of alkyleneoxy groups are present, they may have a block addition structure or a random addition structure.

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

The compound of formula (I-2)

Wherein R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, A ¹ O represents an alkyleneoxy group having 2 to 4 carbon atoms, m May be appropriately selected so as to be in the range of the HLB, specifically, an integer of 1 to 80 is preferable, and when m is 2 or more, m A ¹ O may be the same or different)

In the compound represented by the above formula (I-2), R ³ is hydrogen or a methyl group, and more preferably a methyl group from the viewpoint of copolymerization with the component (A). X is a straight chain or branched alkylene group having 1 to 6 carbon atoms and more preferably a straight chain alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of the non-fluorinated polymer of the present embodiment. A ¹ O is an alkyleneoxy group having 2 to 4 carbon atoms. The kind and combination of A ¹ O and the number of m can be appropriately selected to be within the HLB range. In view of the emulsion stability of the non-fluorinated polymer of the present embodiment, m is preferably an integer of 1 to 80, more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ O may be the same or different. When two or more A < ¹ > O's are present, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the above formula (I-2) can be obtained by a conventionally known method and is not particularly limited. LATEMUL PD-420 "," LATEMUL PD-430 "and" LATEMUL PAD-450 "manufactured by Kao Corporation can be exemplified.

In the reactive emulsifier (B2) represented by the above formula (II-1) used in the present embodiment, R ⁴ is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, A decanediyl group, a decadienyl 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 . R ⁴ is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms from the viewpoint of emulsion stability of the non-fluorinated polymer of the present embodiment.

Y ² is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The kind, combination and addition number of the alkyleneoxy group in Y ² can be appropriately selected so as to be within the HLB range described above. When two or more kinds of alkyleneoxy groups are present, they may have a block addition structure or a random addition structure. In view of the emulsion stability of the non-fluorinated polymer of the present embodiment, the alkyleneoxy group is more preferably an ethyleneoxy group.

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

The compound of formula (II-2)

Wherein R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, A ² O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n represents a range of the HLB Specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, n A ² O may be the same or different)

R ⁴ in the compound represented by the above formula (II-2), there may be mentioned the same as R ⁴ in the above-described formula (II-1).

A ² O is an alkyleneoxy group having 2 to 4 carbon atoms. From the viewpoint of the emulsion stability of the non-fluorinated polymer of the present embodiment, the kind and combination of A ² O and the number of n can be appropriately selected so as to be within the HLB range described above. In view of the emulsion stability of the non-fluorinated polymer of the present embodiment, A ² O is more preferably an ethyleneoxy group, and n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, An integer is more preferable. When n is 2 or more, n A ² O may be the same or different. When two or more kinds of A ² O are present, they may have a block addition structure or a random addition structure.

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

The phenol having the corresponding unsaturated hydrocarbon group includes not only pure products or mixtures manufactured industrially, but also pure products or mixtures extracted or purified from plants and the like. For example, 3- [8 (Z), 11 (Z), 14-pentadecatetrienyl] phenol, 3- [8 (Z), 11 (Z) -pentadecadienyl] phenol, 3- [8 (Z) -pentadecenyl] phenol and 3- [11 (Z) -pentadecenyl] phenol.

The reactive emulsifier (B3) used in the present embodiment is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a hydrocarbon group having an HLB of 7 to 18 and a polymerizable unsaturated group-containing oil. Examples of the fat-and-oil having a hydroxyl group and a polymerizable unsaturated group may include a hydroxy unsaturated fatty acid (palmitoleic acid, oleic acid, linoleic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosa-pentaenoic acid, etc.) Triglycerides of fatty acids including mono- or diglycerides of fatty acids, and at least one hydroxy-unsaturated fatty acid (ricinolic acid, ricinoleic acid, 2-hydroxytetracosic acid, etc.). From the viewpoint of emulsion stability of the non-fluorinated polymer of the present embodiment, an alkylene oxide adduct of triglyceride of a fatty acid containing at least one hydroxy unsaturated fatty acid is preferable, and an alkylene oxide adduct of a castor oil (triglyceride of a fatty acid including ricinoleic acid Alkylene oxide adducts having 2 to 4 carbon atoms in the alkylene oxide adducts are more preferred, and ethylene oxide adducts with castor oil are more preferred. The number of moles of the alkylene oxide to be added can be appropriately selected so as to be in the range of the above HLB and is preferably 20 to 50 moles, more preferably 25 to 45 moles, from the viewpoint of emulsion stability of the non-fluorinated polymer of the present embodiment . When two or more kinds of alkylene oxides are used, they may 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 hydroxyl group and a fat having a polymerizable unsaturated group by a conventionally known method, and is not particularly limited. For example, it is possible to synthesize triglycerides of fatty acids containing ricinoleic acid, that is, an alkali catalyst such as castor oil sodium hydroxide, caustic potassium and the like, and adding a predetermined amount of alkylene oxide at 120 to 170 ° C under pressure .

The content ratio of the constitutional unit derived from the component (A) and the constitutional unit derived from the component (B) in the non-fluorinated polymer of the present embodiment is such that the water repellency of the obtained fiber product and the emulsion stability (A) / (B) of the mass of the component (A) and the mass of the component (B) to be blended is preferably 85/15 to 99/1, more preferably 90/10 to 97/3 More preferable. When the ratio (A) / (B) is less than 85/15, the water repellency of the resulting fiber product tends to be insufficient. (A) / (B) exceeds 99/1, the emulsion stability of the non-fluorinated polymer of this embodiment tends to become insufficient.

The total mass of the mass of the component (A) and the mass of the component (B) to be blended is preferably from 80 to 100 mass%, more preferably from 85 to 99 mass%, based on the total amount of the monomer components constituting the non- , And more preferably 90 to 98 mass%.

The weight average molecular weight of the non-fluorinated polymer 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 resulting fiber product tends to become insufficient. Further, the weight average molecular weight of the non-fluorinated polymer is more preferably 500,000 or more. In this case, the obtained fiber product can exhibit water repellency more sufficiently. The upper limit of the weight average molecular weight of the non-fluorinated polymer is preferably about 5,000,000.

In the present embodiment, the non-fluorinated polymer preferably has a melt viscosity at 105 캜 of 1000 Pa · s or less. If the melt viscosity at 105 ° C exceeds 1000 Pa · s, the resulting textile product tends to be rough and hard. If the non-fluorinated polymer has a too high melt viscosity, if the non-fluorinated polymer is emulsified or dispersed to form a water repellent composition, the non-fluorinated polymer may precipitate or precipitate, and the storage stability of the water repellent composition tends to decrease . It is more preferable that the melt viscosity at 105 ° C is 500 Pa · s or less. In this case, the obtained fiber products and the like exhibit sufficient water repellency and superior tactility.

The " melt viscosity at 105 캜 " refers to a viscosity in a cylinder equipped with a die (10 mm in length and 1 mm in diameter) using a high-temperature flow tester (for example, CFT-500 manufactured by Shimadzu Corporation) Refers to the viscosity measured by adding 1 g of the fluorine-containing polymer, maintaining the temperature at 105 ° C for 6 minutes, and applying a load of 100 kg · f / cm 2 by means of a plunger.

When the non-fluorinated polymer of the present embodiment has the same weight average molecular weight, the water-repellent property of the attached fiber product tends to be higher as the blending ratio of the non-fluorinated (meth) acrylic acid ester monomer is higher. Further, copolymerization of a copolymerizable non-fluorine-based monomer can improve the durability and water repellency of the attached fiber product.

The non-fluorinated polymer contained in the water repellent composition of the present embodiment is preferably a fluorinated polymer obtained by the following (C1), (C2), or the like in addition to the components (A) and (B) , At least one second (meth) acrylic acid ester monomer (C) (hereinafter also referred to as " component C ") selected from the group consisting of (C3) and (C4)

(C1) a (meth) acrylic acid ester monomer represented by the following formula (C-1)

The compound of formula (C-1)

Wherein R ⁵ represents hydrogen or a methyl group and R ⁶ represents at least one member 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, Represents a monovalent straight chain hydrocarbon group having 1 to 11 carbon atoms and having a functional group of the following formula Provided that the number of (meth) acryloyloxy groups in the molecule is 2 or less.

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

The compound of formula (C-2)

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

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

The compound of formula (C-3)

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

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

The compound of formula (C-4)

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

The content ratio of the constitutional unit derived from the component (A), the constitutional unit derived from the component (B) and the constitutional unit derived from the component (C) in the non-fluorinated polymer of the present embodiment, (A) + (B) / (C) of the mass of the component (A) and the mass of the component (B) is preferably 70/30 to 99.9 / 1 is more preferable.

The monomer of (C1) has 1 to 11 carbon atoms having 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. (Meth) acrylic acid ester monomer having a straight chain hydrocarbon group. The monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group in that it can react with a crosslinking agent. When the non-fluorine-containing polymer containing the monomer (C1) having a group capable of reacting with these crosslinking agents is treated with a crosslinking agent in a fiber product, durability and water repellency can be improved while maintaining the tactile sensation of the obtained fiber product. The isocyanate group may be a block isocyanate protected with a blocking agent.

The chain hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The chain hydrocarbon group may further have a substituent in addition to the functional group. Among them, it is preferably a linear hydrocarbon group and / or a saturated hydrocarbon group in that the durability of the fiber product obtained can be improved.

Specific examples of the monomer (C1) include 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate and 1,1- . These monomers may be used singly or in combination of two or more kinds. Among them, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate and 1,1-bis (acryloyloxymethyl) ethyl isocyanate are preferable because they can improve the durability of water- desirable. In addition, dimethylaminoethyl (meth) acrylate is preferred in view of improving the feel of the obtained fiber product.

The constituent ratio of the monomer (C1) is preferably from 0.1 to 30% by mass, more preferably from 1 to 25% by mass with respect to the total amount of the monomer components constituting the non-fluorine polymer from the viewpoints of water repellency and touch of the obtained fiber product. , And more preferably from 5 to 20 mass%.

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 moiety. Examples of the cyclic hydrocarbon group include an isobornyl group, a cyclohexyl group and a dicyclopentanyl group. . These cyclic hydrocarbon groups may have a substituent such as an alkyl group. When the substituent is a hydrocarbon group, a hydrocarbon group in which the total number of carbon atoms of the substituent and the cyclic hydrocarbon group is 11 or less is selected. These cyclic hydrocarbon groups are preferably bonded directly to the ester bond from the viewpoint of improving durability of water repellency. The cyclic hydrocarbon group may be an alicyclic group or an aromatic group, and when it is an alicyclic group, a saturated hydrocarbon group or an unsaturated hydrocarbon group may be used. Specific examples of the monomer include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. These monomers may be used singly or in combination of two or more kinds. Among them, isobornyl (meth) acrylate and cyclohexyl methacrylate are preferable, and isobornyl methacrylate is more preferable in that the fiber product obtained can be improved in water repellency.

The constituent ratio of the monomer (C2) is preferably from 0.1 to 30% by mass, more preferably from 1 to 25% by mass with respect to the total amount of the monomer components constituting the non-fluorine polymer from the viewpoints of water- , And more preferably from 5 to 20 mass%.

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 straight chain hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group. Specific 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 singly or in combination of two or more kinds. Of these, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferable, and methyl methacrylate is more preferable because it is possible to improve the durability of water repellency of the obtained fiber product.

The constituent ratio of the monomer (C3) is preferably from 0.1 to 30% by mass, more preferably from 1 to 25% by mass with respect to the total amount of the monomer components constituting the non-fluorine polymer from the viewpoints of water repellency and touch of the obtained fiber product , More preferably from 5 to 20 mass%.

The monomer (C4) is a (meth) acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In the present embodiment, a multifunctional (meth) acrylic acid ester monomer having three or more (meth) acryloyloxy groups in one molecule, wherein T in the above formula (C-4) is a (meth) acryloyloxy group, . In formula (C-4), p T may be the same or different. Specific examples of the compound include tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol Trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexa methacrylate, and the like. These monomers may be used singly or in combination of two or more kinds. Of these, tetramethylolmethane tetraacrylate is more preferable in that it can improve the durability of water repellency of a fiber product obtained.

The constituent ratio of the monomer (C4) is preferably 0.1 to 5% by mass with respect to the total amount of the monomer components constituting the non-fluorinated polymer, from the viewpoint of water repellency and tactile property of the obtained fiber product.

The non-fluorine-based polymer contained in the water repellent composition of the present embodiment can be obtained by copolymerizing monofunctional monomers (D) copolymerizable with the components (A), (B) and And the like.

Examples of the monomer (D) include (meth) acrylic acid esters, (meth) acrylic acid, fumaric acid esters, maleic acid esters, fumaric acid, maleic acid, (meth) acrylic acid esters having a hydrocarbon group other than the components (A) Vinyl monomers not containing fluorine such as vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, and styrene, and the like can be given. The (meth) acrylic acid ester having a hydrocarbon group other than the component (A) and the component (C) may have a substituent such as a vinyl group, a hydroxyl group, an amino group, an epoxy group and an isocyanate group or a block isocyanate group in a hydrocarbon group , A quaternary ammonium group, and the like, and may have an ether bond, an ester bond, an amide bond, a urethane bond, or the like. 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) .

The constituent ratio of the monomer (D) is preferably 10% by mass or less with respect to the total amount of the monomer components constituting the non-fluorinated polymer from the viewpoints of water repellency and tactility of the obtained fiber product.

The non-fluorinated polymer contained in the water repellent composition of the present embodiment is preferably a fluoropolymer having at least one functional group selected from the group consisting of a hydroxyl group, amino group, carboxyl group, epoxy group and isocyanate group capable of reacting with a crosslinking agent. It is preferable from the viewpoint of improving water repellency. The isocyanate group may form a blocked isocyanate group protected with a blocking agent. Further, the non-fluorine-containing polymer has an amino group because it improves the tactile sensation of the resulting fiber product.

Additives and the like may be added to the water repellent composition of the present embodiment as required. Examples of the additive include other water repellent agents, crosslinking agents, antibacterial deodorants, flame retardants, antistatic agents, softening agents and anti-wrinkle agents.

Next, a method for producing the water repellent composition comprising the non-fluorinated polymer of the present embodiment will be described.

The water repellent composition containing a non-fluorinated polymer can be produced by a radical polymerization method. Among these radical polymerization methods, polymerization is preferably carried out by emulsion polymerization or dispersion polymerization in terms of performance and environment of the obtained water repellent agent.

(Meth) acrylic acid ester monomer (A) represented by the above formula (A-1) in the presence of at least one reactive emulsifier (B) selected from the compounds (B1) A) can be emulsion-polymerized or dispersion-polymerized to obtain a non-fluorinated polymer. More specifically, for example, an emulsion or dispersion is obtained by adding the component (A), the component (B) and, if necessary, an emulsifying or dispersing aid into the medium and emulsifying or dispersing the mixture. By adding the polymerization initiator to the obtained emulsion or dispersion, the polymerization reaction is initiated, and the monomer and the reactive emulsifier can be polymerized. Examples of means for emulsifying or dispersing the above-mentioned mixed liquid include a homomixer, a high-pressure emulsifier, and an ultrasonic wave.

Examples of the emulsifying or dispersing agent (hereinafter also referred to as "emulsifying assistant") include a nonionic surfactant other than the reactive emulsifier (B), a cationic surfactant, an anionic surfactant, and a positive surfactant Or more can be used. The content of the emulsifying aid or the like is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and further preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total monomer. If the content of the emulsifying aid or the like is less than 0.5 part by mass, the dispersion stability of the mixed solution tends to be lowered as compared with the case where the content of the emulsifying aid or the like is in the above range. When the content of the emulsifying aid exceeds 30 parts by mass , The emulsifying aid, and the like are within the above-mentioned range, the water repellency of the obtained non-fluorinated polymer tends to be lowered.

As a medium for emulsion polymerization or dispersion polymerization, water is preferable, and water and an organic solvent may be mixed as necessary. The organic solvent is not particularly limited as long as it is an organic solvent capable of being mixed with water. Examples of the organic solvent include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, Ethers such as ethyl ether; and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. The ratio of water to organic solvent is not particularly limited.

As the polymerization initiator, known polymerization initiators such as azo-based, peroxide-based, or redox-based can be suitably used. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass of the polymerization initiator based on 100 parts by mass of the total monomer. When the content of the polymerization initiator is within the above range, a non-fluorinated polymer having a weight average molecular weight of 100,000 or more can be efficiently produced.

In the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight. The content of the chain transfer agent is preferably 0.3 part by mass or less, more preferably 0.1 part by mass or less, based on 100 parts by mass of the total monomer. When the content of the chain transfer agent exceeds 0.1 part by mass, the molecular weight is lowered, and it becomes difficult to efficiently produce a non-fluorinated polymer having a weight average molecular weight of 100,000 or more.

A polymerization inhibitor may be used for adjusting the molecular weight. By adding the 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 占 폚 to 150 占 폚. If the temperature is less than 20 占 폚, polymerization tends to become insufficient as compared with the case where the temperature is in the above range, and when the temperature exceeds 150 占 폚, control of the reaction heat may become difficult.

In the polymerization reaction, the weight average molecular weight of the obtained non-fluorinated polymer can be adjusted by increasing or decreasing the content of the above-mentioned polymerization initiator, chain transfer agent and polymerization inhibitor, and the melt viscosity at 105 ° C , And the content of the polymerization initiator. When it is desired to lower the melt viscosity at 105 占 폚, 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-fluorinated polymer in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is preferably from 10 to 50 mass% with respect to the total amount of the emulsion or dispersion from the viewpoints of storage stability and handleability of the composition, More preferably 20 to 40% by mass.

The water repellent fiber product of the present embodiment is made of a fiber product to which the non-fluorinated polymer of the present embodiment described above is adhered.

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

The water repellent fiber product of the present embodiment is obtained by adhering a non-fluorinated polymer to a fiber product by treating the fiber product with a treatment liquid containing the above-described water repellent composition. The material of such a fiber product is not particularly limited and natural fibers such as cotton, hemp, dog, wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as nylon, polyester, polyurethane, polypropylene, , Blend fibers, and the like. The form of the fiber product may be any of fiber, yarn, cloth, nonwoven fabric, paper and the like.

As a method of treating the fiber product with the treatment liquid, for example, a processing method such as dipping, spraying, or coating may be mentioned. When the water repellent composition contains water, it is preferable that the water repellent composition is dried to remove water after adhering to the fiber product.

The amount of the water repellent composition to be adhered to the fiber product can be appropriately adjusted in accordance with the required degree of water repellency. It is preferable to adjust the adhesion amount of the non-fluorinated polymer contained in the water repellent composition to 0.01 to 10 g with respect to 100 g of the fiber product, More preferably 0.05 to 5 g. If the adhesion amount of the non-fluorinated polymer is less than 0.01 g, the fiber product tends not to exhibit sufficient water repellency as compared with the case where the adhesion amount of the non-fluorinated polymer falls within the above range. If the adhesion amount exceeds 10 g, Compared with the case where the content is in the above range, the feel of the fiber product tends to become rough and hard.

Further, after the non-fluorinated polymer of the present embodiment is attached to the fiber product, it is preferable that heat treatment is appropriately performed. The temperature condition is not particularly limited, but when the water repellent composition of the present embodiment is used, it is possible to exhibit sufficiently good water repellency in a fiber product under a mild condition of 100 to 130 캜. The temperature condition may be a high-temperature treatment of 130 ° C or higher (preferably up to 200 ° C). In this case, the treatment time can be shortened in comparison with the conventional case using a fluorine-based water repellent. Therefore, according to the water repellent fiber product of the present embodiment, the deterioration of the fiber product due to heat is suppressed, the feel of the fiber product during the water repellent treatment becomes flexible, and the water repellency of the fiber product is satisfactory under mild heat treatment conditions, .

Particularly, when it is desired to improve the durability of water repellency, the above-described step of treating the fiber product with the treatment liquid containing the water repellent composition and the above-mentioned step of treating the fiber product with a crosslinking agent represented by a compound having at least one methylolmelamine, isocyanate group, or block isocyanate group, It is preferable that the fiber product is subjected to water-repellent processing by a method including a step of adhering to a fiber product and heating it. When it is desired to further improve the durability of water repellency, it is preferable that the water repellent composition includes a non-fluorinated polymer obtained by copolymerizing a monomer having a functional group capable of reacting with the above-mentioned crosslinking agent.

Examples of the compound having at least one isocyanate group include monoisocyanates such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate and naphthalene isocyanate, such as triphenyl diisocyanate, diphenyl methane diisocyanate, tetramethyl xylene diisocyanate, hydrogenated diphenyl methane diisocyanate Diisocyanates of isocyanurates of these, and trimethylolpropane adducts thereof. Examples of the compound having at least one block isocyanate group include compounds in which the isocyanate group is protected with a blocking agent as a compound having an isocyanate group. Examples of the blocking agent used herein include organic blockers such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, and lactams; and bisulfates such as sodium bisulfate and potassium bisulfite. The above-mentioned cross-linking agent may be used singly or in combination of plural kinds.

The cross-linking agent can be obtained by, for example, dissolving a cross-linking agent in an organic solvent, or immersing a to-be-treated product (fiber product) in a treatment solution in which the cross-linking agent is emulsified and dispersed in water, and drying the treatment solution adhered to the to- It can be attached to the treated product. By heating the cross-linking agent attached to the object to be treated, the reaction between the cross-linking agent and the substance to be treated and the non-fluorine-based polymer can proceed. In order to improve the washing durability more effectively by sufficiently accelerating the reaction of the crosslinking agent, the heating at this time is preferably performed at 110 to 180 DEG C for 1 to 5 minutes. The step of adhering and heating the crosslinking agent may be carried out simultaneously with the step of treating with the treatment liquid containing the above-mentioned water repellent composition. In the case of simultaneous execution, for example, the treatment liquid containing the water repellent composition and the cross-linking agent is attached to the object to be treated, water is removed, and then the cross-linking agent attached to the object is further heated. In consideration of simplification of the water-repellent processing step, reduction of the heat amount, and economical efficiency, it is preferable to carry out simultaneously with the step of processing the water repellent composition.

In addition, excessive use of a cross-linking agent may deteriorate tactile sensation. The crosslinking agent is preferably used in an amount of 0.1 to 50 mass%, particularly preferably 0.1 to 10 mass%, based on the product to be treated (fiber product).

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

While the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

For example, in the case of producing a non-fluorinated polymer contained in the water repellent composition of the present invention, the polymerization reaction is carried out by radical polymerization in the above-mentioned embodiment. However, in the case of electrolytic polymerization such as ultraviolet ray, electron beam, The polymerization reaction may be carried out by photopolymerization which irradiates radiation.

In the present invention, the water repellent composition is treated with a fiber product to form a water repellent fiber product. However, the product treated with the water repellent composition is not limited to a textile product, and may be an article such as metal, glass, or resin.

In this case, the method of adhering the water repellent composition to the article or the amount of the water repellent to be adhered may be arbitrarily determined depending on the type of the object to be treated and the like.

Example

Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited by these examples at all.

≪ Adjustment of polymer dispersion >

A mixture solution having the compositions (indicated in the table, (g)) shown in Tables 1 to 5 was polymerized by the following procedure to obtain a polymer dispersion.

(Example 1)

60 g of stearyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corp.), and 2 g of LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylenealkenyl ether , HLB = 14.4), 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were placed and mixed and stirred at 45 ° C to prepare a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 2)

55 g of stearyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylenealkenyl ether , HLB = 14.4), 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 0.15 g of dodecylmercaptan, 20 g of tripropylene glycol and 162.6 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 3)

55 g of stearyl methacrylate, 2 g of LATEMUL PD-420 (polyoxyalkylenealkenyl ether, manufactured by Kao Corporation, HLB = 12.6), LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene 2 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 0.05 g of dodecylmercaptan, 20 g of tripropylene glycol and 162.7 g of water were placed and mixed and stirred at 45 DEG C to obtain a mixed solution . Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 4)

55 g of stearyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylenealkenyl ether , HLB = 14.4), 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 5)

55 g of cetyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylenealkenyl ether, HLB = 14.4), 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were placed and mixed and stirred at 45 캜 to prepare a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 6)

55 g of lauryl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylenealkenyl ether , HLB = 14.4), 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 7)

55 g of stearyl acrylate, 2 g of adduct of 12.5 moles of ethylene oxide of cardanol (HLB = 12.9, referred to as "cardanol 12.5 EO" in the table) and 8.3 molar addition of cardanol ethylene oxide (HLB = 11.0, "CARDANOL 8.3EO" in the table), 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C. to obtain a mixture Respectively. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 8)

55 g of stearyl acrylate, 2 g of ethylene oxide 42 mol adduct (HLB = 13.3, indicated as "castor oil 42EO" in the table) and 30 mol of adduct of castor oil (HLB = 11.7, 2 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were placed and mixed and stirred at 45 DEG C to prepare a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 9)

57 g of stearyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corp.), 2 g of LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylenealkenyl ether , HLB = 14.4), 3 g of tetramethylolmethane tetraacrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 10)

55 g of stearyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylenealkenyl ether , HLB = 14.4), 5 g of dimethylaminoethyl methacrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 11)

55 g of stearyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylenealkenyl ether , HLB = 14.4), 5 g of glycidyl methacrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 12)

55 g of stearyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylenealkenyl ether , HLB = 14.4), 5 g of methyl ethyl ketone oxime block of 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were charged, Were mixed and stirred to prepare a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 13)

51 g of stearyl acrylate, 4 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), 4 g of LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylenealkenyl ether , HLB = 14.4), 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 14)

56 g of stearyl acrylate, 0.5 g of LATEMUL PD-420 (polyoxyalkylenealkenyl ether, HLB = 12.6, manufactured by Kao Corp.), and LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylenealkenyl Ether, HLB = 14.4), 2 g of polyoxyethylene (10 mol) lauryl ether, 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water, And the mixture was stirred to prepare a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 15)

45 g of stearyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), LATEMUL PD-430 (manufactured by Kao Corp., polyoxyalkylenealkenyl ether , HLB = 14.4), 5 g of 2-hydroxyethyl acrylate, 10 g of isobornyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 16)

45 g of stearyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), LATEMUL PD-430 (manufactured by Kao Corp., polyoxyalkylenealkenyl ether , HLB = 14.4), 5 g of 2-hydroxyethyl acrylate, 10 g of isobornyl methacrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution . Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 17)

45 g of stearyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), LATEMUL PD-430 (manufactured by Kao Corp., polyoxyalkylenealkenyl ether , HLB = 14.4), 5 g of 2-hydroxyethyl acrylate, 10 g of cyclohexyl methacrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Example 18)

45 g of stearyl acrylate, 2 g of LATEMUL PD-420 (polyoxyalkylene alkenyl ether, HLB = 12.6, manufactured by Kao Corporation), LATEMUL PD-430 (manufactured by Kao Corp., polyoxyalkylenealkenyl ether , HLB = 14.4), 5 g of 2-hydroxyethyl acrylate, 10 g of methyl methacrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were mixed and stirred at 45 ° C to obtain a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 ° C for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 26% by mass.

(Comparative Example 1)

A 500 mL flask was charged with the following formula (III):

(III)

, 60 g of a mixture in which the average value of n is 8 (the compound in which n is 6, 8, 10, 12 and 14 are mixed), 3 g of stearyldimethylamine hydrochloride, 10 g of polyoxyethylene Mol), 7 g of lauryl ether, 20 g of tripropylene glycol and 158.5 g of water were placed and mixed and stirred at 45 ° C to prepare a mixed solution. The mixture was emulsified and dispersed by irradiating ultrasonic waves to the mixed solution. Subsequently, 1.5 g of azobis (isobutylamidine) dihydrochloride was added to the mixture, and the mixture was subjected to radical polymerization at 60 DEG C for 6 hours in a nitrogen atmosphere to obtain a fluoropolymer dispersion having a polymer concentration of 24 mass%.

(Comparative Example 2)

55 g of stearyl acrylate, 4 g of polyoxyethylene (10 mol) lauryl ether, 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were placed in a 500 mL flask, And the mixture was stirred to prepare a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 占 폚 for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 24 mass%.

(Comparative Example 3)

55 g of stearyl acrylate, 4 g of polyoxyethylene (10 mol) lauryl ether, 5 g of 2-hydroxyethyl acrylate, 7 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 158.75 g of water were placed in a 500 mL flask, And the mixture was stirred to prepare a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 占 폚 for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 24 mass%.

(Comparative Example 4)

55 g of stearyl acrylate, 2 g of NOIGEN XL-100 (polyoxyalkylene branched decyl ether, manufactured by Daiichi Kyoe Sake Co., Ltd., HLB = 14.7) and 2 g of Neigen XL-60 2 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were placed, and the mixture was stirred at 45 DEG C with stirring, To prepare a mixed solution. Ultrasonic waves were applied to this mixed solution to emulsify and disperse the whole monomer. Subsequently, 0.25 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, followed by radical polymerization at 60 占 폚 for 6 hours in a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 24 mass%.

Each of the polymers in the polymer dispersions obtained in Examples 1 to 18 and Comparative Examples 1 to 4 was analyzed by a gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation) at a ratio of 98% Was polymerized.

The polymer dispersion thus obtained and the polymer obtained by the method described below were evaluated.

(Evaluation of physical properties of non-fluorinated polymer)

The polymer and the emulsifier were separated by adding 500 mL of acetone to 50 g of the polymer dispersion obtained in Examples 1 to 18 and Comparative Examples 1 to 4, the polymer was filtered off, and the polymer was dried under reduced pressure at 25 DEG C for 24 hours . The obtained polymer was evaluated as follows. The results are shown in Tables 6 to 9.

(1) Method of measuring melt viscosity

A die (length 10 mm, diameter 1 mm) was used for the polymers of Examples 1 to 18 and Comparative Examples 2 to 4 obtained above by using a high-price flotester CFT-500 (manufactured by Shimadzu Corporation) 1 g of the polymer was put in the mounted cylinder, held at 105 ° C for 6 minutes, and subjected to a load of 100 kg · f / cm 2 by a plunger to measure the melt viscosity at 105 ° C.

(2) Method of measuring weight average molecular weight

The polymers obtained in Examples 1 to 18 and Comparative Examples 2 to 4 obtained above were subjected to measurement under the conditions of a column temperature of 40 占 폚 and a flow rate of 1.0 ml / min using a GPC apparatus (GPC "HLC-8020" manufactured by Tosoh Corporation) , Tetrahydrofuran was used as the eluent, and the weight average molecular weight was measured in terms of standard polystyrene. The column was connected by connecting three TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation.

(Evaluation of storage stability of water repellent composition)

The stability of the polymer dispersions obtained in Examples 1 to 18 or Comparative Examples 1 to 4 at 45 占 폚 for 2 weeks was evaluated based on the following criteria. The results are shown in Tables 6 to 9.

A: No appearance change

B: Oil matters near the liquid surface, and polymer precipitates on the wall surface of the container are slightly observed.

C: Confirmation of sediment, separation and gelation of polymer

(Evaluation of water repellency of textile products)

The test was carried out at a shower water temperature of 27 ° C in accordance with the spray method of JIS L 1092 (1998). In this test, 100% polyester or 100% nylon cloth subjected to dyeing was dipped in a treating solution obtained by diluting the polymer dispersion of Examples 1 to 18 or Comparative Examples 1 to 4 with water so that the content of the polymer was 3 mass% (Pickup ratio 60% by mass), dried at 130 ° C for 2 minutes, and further heat-treated under the conditions described in Tables 6 to 9, and the water repellency of the obtained cloth was evaluated. The results were visually evaluated in the following grades. In addition, when the characteristics are slightly better, "+" is added to the grade, and when the characteristics are slightly lowered, "-" is added to the grade. The results are shown in Tables 6 to 9.

Water repellency: State

5: without wetting on the surface

4: Very little adhesion wetting on the surface

3: Partial wetting on the surface

2: wetting on the surface

1: showing wetting on the entire surface

0: Both sides show complete wetting

(Tactile evaluation of textile products)

The tactile sensation was evaluated by immersing 100% polyester in a dyeing solution in which the polymer dispersion of Examples 1 to 18 or Comparative Examples 1 to 4 was diluted with water so that the content of the polymer was 3 mass% ), Dried at 130 ° C for 2 minutes, and further heat-treated at 170 ° C for 30 seconds. The results were evaluated in five steps shown below by handling. The results are shown in Tables 6 to 9.

1: Hard ~ 5: Soft

(Evaluation of durability of textile products)

The test was carried out at a shower water temperature of 27 ° C in accordance with the spray method of JIS L 1092 (1998). In the present test, 100% of polyester subjected to dyeing was mixed with 3% by mass of a polymer, 0.3% by mass of UNIKA RESIN 380-K (a crosslinking agent, trimethylol melamine resin manufactured by Union Carbide Corporation) The polymer dispersion of Examples 1 to 18 or Comparative Examples 1 to 4 and each of the above-mentioned medicaments (1) to (4) were mixed so that the content of UNIKA CATALYST 3-P (surfactant, amino alcohol hydrochloride produced by Union Kagakuko K.K.) (L-0) and JIS L 0217 (L-0) obtained by immersing treatment (picking rate 60% by mass) in the treatment solution diluted with water, drying at 130 캜 for 2 minutes and further heat treatment at 170 캜 for 60 seconds 1995), the water repellency of the fabric after 10 times (L-10) was evaluated in the same manner as the above water repellency evaluation method. The nylon 100% cloth was evaluated in the same manner as in the case of the 100% polyester cloth, except that the heat treatment temperature was changed from 170 캜 to 160 캜. The results are shown in Tables 6 to 9.

The fiber products treated with the water repellent composition of Examples 1 to 18 exhibited water repellency and durability water repellency equal to or higher than those of the conventional fluorine-based water repellent agent (Comparative Example 1) even when heat treatment was not performed, . Further, it was confirmed that the storage stability of the composition was also good.

Comparing Example 2 and Example 4, it was confirmed that even when the composition of the non-fluorinated polymer is close to that of the polymer, when the weight average molecular weight of the polymer is different, the polymer having a larger weight average molecular weight is excellent in water repellency.

The water repellent composition of Comparative Example 2 used a general surfactant that was not a reactive emulsifier and it was confirmed that the storage stability of the composition deteriorated at the same amount of surfactant as that of Example 4 using a reactive emulsifier.

The water repellent composition of Comparative Example 3 had an increased amount of emulsifying aid (general surfactant) for the purpose of improving the storage stability of the composition as compared with Comparative Example 2, and the water repellency of the fiber product treated with the composition was decreased There was a tendency.

It was confirmed that the water repellent composition of Comparative Example 4 was subjected to emulsion polymerization using a common surfactant having HLB within the preferred range of the present invention in place of the reactive emulsifier to lower the water repellency of the treated fiber product.

As described above, according to the present invention, it is possible to provide a water repellent composition which is excellent in storage stability, can impart sufficient water repellency to a fiber product even when heat treatment is not performed, and can obtain a water repellent fiber product excellent in touch and water repellency .

The water repellent composition of the present invention is particularly effective for use in textile products. When the water repellent composition of the present invention is used for a textile product, since the fiber product is treated with the water repellent composition and then heat-treated at a low temperature, the water repellent property can be sufficiently exhibited. . Further, by using a crosslinking agent in combination or by copolymerizing a reactive monomer, durability and water repellency can be improved. Further, the water repellent composition of the present invention is useful as a water repellent composition which is low in cost because it does not contain a fluorine-containing group and has a small adverse effect on the human body and the environment. Further, the amount of the surfactant used can be reduced as compared with the conventional water repellent agent, and it is possible to cope with various fiber processing.

Claims (9)

(Meth) acrylic acid ester monomer (A) represented by the following general formula (A-1) and a structural unit derived from
(B1) a compound represented by the following formula (I-1) wherein the HLB is 7 to 18, (B2) a compound represented by the following formula (II-1) wherein the HLB is 7 to 18, and (B3) (B) derived from at least one reactive emulsifier (B) selected from the group consisting of a hydroxyl group and a polymer having a polymerizable unsaturated group and an alkylene oxide having 2 to 4 carbon atoms added to a fat and oil having a polymerizable unsaturated group
Wherein the water-repellent agent comprises a non-fluorine-containing polymer.
(A-1)

(In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms, which may have a substituent.
The compound of formula (I-1)

Wherein R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y ¹ represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms, Lt; / RTI >
The compound of formula (II-1)

Wherein R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group and Y ² represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms, The non-fluorinated polymer according to claim 1, wherein the non-fluorinated polymer is at least one kind of second (meth) acrylic acid ester monomer (C) selected from the group consisting of the following (C1), (C2), (C3) Wherein the water-repellent agent further comprises a derived constituent unit.
(C1) a (meth) acrylic acid ester monomer represented by the following formula (C-1)
The compound of formula (C-1)

Wherein R ⁵ represents hydrogen or a methyl group and R ⁶ represents at least one member 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, Represents a monovalent straight chain hydrocarbon group having 1 to 11 carbon atoms and having a functional group of the following formula Provided that the number of (meth) acryloyloxy groups in the molecule is 2 or less.
(C2) a (meth) acrylic acid ester monomer represented by the following formula (C-2)
The compound of formula (C-2)

[In the formula (C-2), R ⁷ represents hydrogen or a methyl group, and R ⁸ represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent]
(C3) a methacrylic acid ester monomer represented by the following formula (C-3)
The compound of formula (C-3)

[In the formula (C-3), R ⁹ represents an unsubstituted monovalent straight chain hydrocarbon group having 1 to 4 carbon atoms]
(C4) a (meth) acrylic acid ester monomer represented by the following formula (C-4)
The compound of formula (C-4)

Wherein R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents a (p + 1) -valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group ] (Meth) acrylic acid ester monomer (A) represented by the following formula (A-1)
(B1) a compound represented by the above formula (I-1) wherein the HLB is 7 to 18, (B2) a compound represented by the above formula (II-1) wherein the HLB is 7 to 18, and (B3) (B) at least one reactive emulsifier selected from compounds having a hydroxyl group and a compound having a polymerizable unsaturated group and an alkylene oxide having 2 to 4 carbon atoms added to the oil,
And a non-fluorinated polymer formed by emulsion polymerization or dispersion polymerization of an emulsion or a dispersion containing the emulsion or dispersion.
(A-1)

(In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms, which may have a substituent.
The compound of formula (I-1)

Wherein R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y ¹ represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms, Lt; / RTI >
The compound of formula (II-1)

Wherein R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group and Y ² represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms, 4. The composition according to claim 3, wherein the emulsion or the dispersion contains at least one second (meth) acrylic acid ester monomer selected from the group consisting of (C1), (C2), (C3) ). ≪ / RTI >
(C1) a (meth) acrylic acid ester monomer represented by the following formula (C-1)
The compound of formula (C-1)

Wherein R ⁵ represents hydrogen or a methyl group and R ⁶ represents at least one member 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, Represents a monovalent straight chain hydrocarbon group having 1 to 11 carbon atoms and having a functional group of the following formula Provided that the number of (meth) acryloyloxy groups in the molecule is 2 or less.
(C2) a (meth) acrylic acid ester monomer represented by the following formula (C-2)
The compound of formula (C-2)

[In the formula (C-2), R ⁷ represents hydrogen or a methyl group, and R ⁸ represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent]
(C3) a methacrylic acid ester monomer represented by the following formula (C-3)
The compound of formula (C-3)

[In the formula (C-3), R ⁹ represents an unsubstituted monovalent straight chain hydrocarbon group having 1 to 4 carbon atoms]
(C4) a (meth) acrylic acid ester monomer represented by the following formula (C-4)
The compound of formula (C-4)

Wherein R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents a (p + 1) -valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group ] (Meth) acrylic acid ester monomer (A) represented by the following general formula (A-1) and a structural unit derived from
(B1) a compound represented by the following formula (I-1) wherein the HLB is 7 to 18, (B2) a compound represented by the following formula (II-1) wherein the HLB is 7 to 18, and (B3) (B) derived from at least one reactive emulsifier (B) selected from the group consisting of a hydroxyl group and a compound having a polymerizable unsaturated group and an alkylene oxide having 2 to 4 carbon atoms added thereto,
Wherein the water-repellent fiber product comprises a non-fluorinated polymer-containing fiber product.
(A-1)

(In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms, which may have a substituent.
The compound of formula (I-1)

Wherein R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y ¹ represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms, Lt; / RTI >
The compound of formula (II-1)

Wherein R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group and Y ² represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms, The non-fluorine-containing polymer according to claim 5, wherein the non-fluorine-based polymer is at least one kind of second (meth) acrylic ester monomer (C) selected from the group consisting of the following (C1), (C2), (C3) Water-repellent < / RTI > fiber product.
(C1) a (meth) acrylic acid ester monomer represented by the following formula (C-1)
The compound of formula (C-1)

Wherein R ⁵ represents hydrogen or a methyl group and R ⁶ represents at least one member 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, Represents a monovalent straight chain hydrocarbon group having 1 to 11 carbon atoms and having a functional group of the following formula Provided that the number of (meth) acryloyloxy groups in the molecule is 2 or less.
(C2) a (meth) acrylic acid ester monomer represented by the following formula (C-2)
The compound of formula (C-2)

[In the formula (C-2), R ⁷ represents hydrogen or a methyl group, and R ⁸ represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent]
(C3) a methacrylic acid ester monomer represented by the following formula (C-3)
The compound of formula (C-3)

[In the formula (C-3), R ⁹ represents an unsubstituted monovalent straight chain hydrocarbon group having 1 to 4 carbon atoms]
(C4) a (meth) acrylic acid ester monomer represented by the following formula (C-4)
The compound of formula (C-4)

Wherein R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents a (p + 1) -valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group ] (Meth) acrylic acid ester monomer (A) represented by the following formula (A-1)
(B1) a compound represented by the following formula (I-1) wherein the HLB is 7 to 18, (B2) a compound represented by the following formula (II-1) wherein the HLB is 7 to 18, and (B3) (B) at least one reactive emulsifier selected from compounds having a hydroxyl group and a compound having a polymerizable unsaturated group and an alkylene oxide having 2 to 4 carbon atoms added to the oil,
And a non-fluorine-based polymer formed by emulsion polymerization or dispersion polymerization of the emulsion or dispersion.
(A-1)

(In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms, which may have a substituent.
The compound of formula (I-1)

Wherein R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y ¹ represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms, Lt; / RTI >
The compound of formula (II-1)

Wherein R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group and Y ² represents a divalent group including an alkyleneoxy group having 2 to 4 carbon atoms, The method according to claim 7, wherein the emulsion or the dispersion contains at least one second (meth) acrylic acid ester monomer selected from the group consisting of (C1), (C2), (C3) ). ≪ / RTI >
(C1) a (meth) acrylic acid ester monomer represented by the following formula (C-1)
The compound of formula (C-1)

Wherein R ⁵ represents hydrogen or a methyl group and R ⁶ represents at least one member 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, Represents a monovalent straight chain hydrocarbon group having 1 to 11 carbon atoms and having a functional group of the following formula Provided that the number of (meth) acryloyloxy groups in the molecule is 2 or less.
(C2) a (meth) acrylic acid ester monomer represented by the following formula (C-2)
The compound of formula (C-2)

[In the formula (C-2), R ⁷ represents hydrogen or a methyl group, and R ⁸ represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent]
(C3) a methacrylic acid ester monomer represented by the following formula (C-3)
The compound of formula (C-3)

[In the formula (C-3), R ⁹ represents an unsubstituted monovalent straight chain hydrocarbon group having 1 to 4 carbon atoms]
(C4) a (meth) acrylic acid ester monomer represented by the following formula (C-4)
The compound of formula (C-4)

Wherein R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents a (p + 1) -valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group ] A process for producing a water repellent fiber product, which comprises a step of treating a fiber product with a treatment liquid containing the water repellent composition according to any one of claims 1 to 4.