KR102153279B1 - Water repellent agent composition, water repellent fiber product and method for producing water repellent fiber product - Google Patents

Abstract

Constituent units derived from the (meth)acrylic acid ester monomer (A) having a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent, and compounds (B1) to (B3) having a HLB of 7 to 18 and containing a polymerizable unsaturated group ), a water repellent composition comprising a non-fluorine-based polymer containing a structural unit derived from at least one reactive emulsifier (B) selected from.

Description

A water-repellent composition, a water-repellent fiber product, and a method of manufacturing a water-repellent fiber product TECHNICAL FIELD [WATER REPELLENT AGENT COMPOSITION, WATER REPELLENT FIBER PRODUCT AND METHOD FOR PRODUCING 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.

Conventionally, a fluorine-based water repellent having a fluorine-containing group has been known, and a fiber product having water repellency imparted to its surface by treating such a fluorine-based water repellent with a fiber product or the like is known. These fluorine-based water repellents are generally prepared by polymerizing or copolymerizing a monomer having a fluoroalkyl group.

Fiber products treated with a fluorine-based water repellent exhibit excellent water repellency, but in order to exhibit water repellency, it is necessary to adjust the orientation of the fluoroalkyl group. After attaching the fluorine-based water repellent to the fiber product, heat treatment is performed at a temperature exceeding 130°C. Should be. However, the heat treatment at high temperature requires high energy, and there is a problem in the flow of international energy saving.

Further, since the monomer having a fluoroalkyl group is expensive, it is not satisfactory in terms of economy, and since the monomer having a fluoroalkyl group is hardly decomposable, there is also a problem in the environment.

On the other hand, in the field of water-repellent processing of textile products, in order to stabilize quality and reduce cost, a water repellent capable of imparting excellent water repellency to textile products even at a low concentration or a low heat treatment temperature is desired.

Therefore, in recent years, research is being conducted on a non-fluorine-based water repellent that does not contain fluorine. For example, Non-Patent Document 1 discloses a water repellent 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 obtained by emulsifying and dispersing a specific non-fluorine-based polymer for the purpose of imparting water repellency comparable to that of a conventional fluorine-based water repellent.

Patent Document 1: Japanese Unexamined Patent Application Publication No. 2006-328624

Non-Patent Literature 1: "Super water repellent processing, conversion of processing agents and new trends in moisture-permeable waterproof materials", published by Osaka Chemical Marketing Center, 1996, p.7 to 9

However, with the non-fluorine-based water repellent agent described in Non-Patent Document 1, it is difficult to obtain a fiber product having the same water repellency as in the case of treatment with a conventional fluorine-based water repellent agent. In addition, the treated fiber product tends to become hard, and it cannot be said that it is sufficient for the touch.

In the case of the non-fluorine-based water repellent described in Patent Document 1, if a surfactant in an amount in which the non-fluorine-based polymer is sufficiently emulsified and dispersed in order to secure storage stability is blended, the water repellency of the obtained fiber product tends to decrease, so storage stability and water repellency It is difficult to promote the compatibility of

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

The present invention provides a structural unit derived from a (meth)acrylic acid ester monomer (A) represented by the following formula (A-1), and a compound represented by the following formula (I-1), wherein (B1) HLB is 7 to 18. , (B2) a compound represented by the following formula (II-1) having an HLB of 7 to 18, and (B3) having a hydroxyl group and a polymerizable unsaturated group having a HLB of 7 to 18, having 2 to It provides a water repellent composition comprising a non-fluorine-based polymer containing a structural unit derived from at least one reactive emulsifier (B) selected from compounds to which the alkylene oxide of 4 is added.

Formula (A-1)

[In 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]

Formula (I-1)

[In Formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. Represents a group]

Formula (II-1)

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

In the non-fluorine-based polymer, 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) and (C4) is added. It may contain as.

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

Formula (C-1)

[In Formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group. It represents a C1-C11 monovalent chain hydrocarbon group which has a functional group of. However, the number of (meth)acryloyloxy groups in the molecule is 2 or less]

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

Formula (C-2)

[In 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) Methacrylic acid ester monomer represented by the following formula (C-3)

Formula (C-3)

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

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

Formula (C-4)

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

In the present invention, the (meth)acrylic acid ester monomer (A) represented by the above formula (A-1), (B1) a compound represented by the above formula (I-1) having an HLB of 7 to 18, (B2 ) A compound represented by the above formula (II-1) having an HLB of 7 to 18, and (B3) an alkylene oxide having 2 to 4 carbon atoms in a fat or oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18 It provides a water repellent composition comprising a non-fluorine-based polymer obtained by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing at least one reactive emulsifier (B) selected from the added compounds.

The emulsion or the dispersion further comprises at least one second (meth)acrylic acid ester monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4), You may have it.

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

In the present invention, the structural unit derived from the (meth)acrylic acid ester monomer (A) represented by the formula (A-1), and (B1) the HLB represented by the formula (I-1) is 7 to 18 Compound, (B2) a compound represented by the above formula (II-1) having an HLB of 7 to 18, and (B3) an HLB of 7 to 18, having a hydroxyl group and a polymerizable unsaturated group having 2 to 4 carbon atoms It provides a water-repellent fiber product comprising a fiber product to which a non-fluorine-based polymer containing structural units derived from at least one reactive emulsifier (B) selected from compounds to which an alkylene oxide is added is attached.

The non-fluorine-based polymer further comprises a structural unit derived from at least one second (meth)acrylic acid ester monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4). It may contain.

In the present invention, the (meth)acrylic acid ester monomer (A) represented by the above formula (A-1), (B1) a compound represented by the above formula (I-1) having an HLB of 7 to 18, (B2 ) A compound represented by the above formula (II-1) having an HLB of 7 to 18, and (B3) an alkylene oxide having 2 to 4 carbon atoms in a fat or oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18 It provides a water-repellent fiber product comprising a fiber product to which a non-fluorine-based polymer is attached, which is obtained by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing at least one reactive emulsifier (B) selected from the added compounds.

The emulsion or the dispersion further comprises at least one second (meth)acrylic acid ester monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4), You may have it.

The water-repellent fiber product of the present invention can sufficiently maintain the touch and water repellency even when used outdoors for a long period of time.

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

According to the method of manufacturing a water-repellent fiber product of the present invention, the water-repellent composition is excellent in touch and water repellency by using the water repellent composition according to the present invention, which has excellent storage stability and can impart sufficient water repellency to fiber products even when heat treatment is not performed. Textile products can be stably manufactured. In addition, since the manufacturing method of the water-repellent fiber product of the present invention does not require heat treatment at a high temperature, energy saving can be achieved and at the same time, since a non-fluorine-based water repellent is used, the load on the environment can be reduced. I can.

Advantageous Effects of Invention According to the present invention, it is possible to provide a water-repellent composition capable of providing a fiber product with excellent storage stability and sufficient water repellency even when heat treatment is not performed, and a water-repellent fiber product having excellent touch and water repellency.

The water repellent composition of the present invention is a water repellent composition that does not contain a fluoroalkyl group or a fluorine-containing compound, yet exhibits excellent water repellency, and can be used as a substitute for a fluorine-based water repellent, thereby eliminating concerns about influences on a fluorine source or environment. can do. In addition, after attaching the water repellent composition to textile products, it is generally preferable to heat treatment. However, since the water repellent composition of the present invention does not use a monomer having a fluoroalkyl group, it is high even when heat treated under mild conditions of 130°C or lower. Water repellency can be exhibited, and in the case of heat treatment at a high temperature exceeding 130°C, the heat treatment time can be made shorter than in the case of a fluorine-based water repellent. Accordingly, since it is possible to suppress deterioration due to heat of the object to be treated, the touch becomes flexible, and it is excellent in terms of cost, such as reducing the amount of heat required for heat treatment.

In addition, according to the present invention, as an emulsifying and dispersing agent used in the emulsion or dispersion polymerization of a non-fluorine-based polymer, it is possible to reduce the amount of surfactant contained in the water repellent composition by using a specific reactive emulsifier instead of a general surfactant. As a result, it is possible to suppress a decrease in water repellency of the obtained fiber product and the like, and realize higher water repellency than conventional non-fluorine-based water repellent agents. In addition, since the water repellent composition according to the present invention can improve the emulsion dispersibility of the non-fluorine-based polymer itself, it is easy to maintain a stable emulsified state even when added to a processing bath, and it is possible to cope with various fiber processing. It becomes.

The water repellent composition of this embodiment is a structural unit derived from a (meth)acrylic acid ester monomer (A) represented by the following formula (A-1) (hereinafter, also referred to as ``component (A)''), and (B1) HLB Is 7 to 18, a compound represented by the following formula (I-1), (B2) an HLB is 7 to 18, a compound represented by the following formula (II-1), and (B3) HLB is 7 to 18, a hide Composition derived from at least one reactive emulsifier (B) selected from compounds in which alkylene oxides having 2 to 4 carbon atoms are added to fats and oils having a hydroxyl group and a polymerizable unsaturated group (hereinafter also referred to as ``component (B)'') It includes a non-fluorine-based polymer containing a unit.

Formula (A-1)

[In 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]

Formula (I-1)

[In Formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. Represents a group]

Formula (II-1)

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

Here, "(meth)acrylic acid ester" refers to "acrylic acid ester" or a corresponding "methacrylic acid ester", and has the same meaning also in "(meth)acrylic acid" and "(meth)acrylamide".

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

In addition, "HLB" refers to the HLB value calculated by the Griffin method, considering the ethyleneoxy group as a hydrophilic group and all others as a lipophilic group.

The (meth)acrylic acid ester monomer (A) represented by the general formula (A-1) used in the present embodiment has a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent. This hydrocarbon group may be linear or branched, a saturated hydrocarbon group or an unsaturated hydrocarbon group may be used, and further, may have an alicyclic or aromatic ring. Among these, a linear one is preferable, and it is more preferable that it is a linear alkyl group. In this case, the water repellency becomes more excellent. When a monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, examples of the substituent include one or more of 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 general formula (A-1), R ² is preferably an unsubstituted hydrocarbon group.

The hydrocarbon group preferably has 12 to 24 carbon atoms. If the number of carbon atoms is less than 12, sufficient water repellency cannot be exhibited when a non-fluorine-based polymer is attached to a fiber product or the like. On the other hand, when the carbon number exceeds 24, compared with the case where the carbon number is in the above range, when a non-fluorine-based polymer is attached to a fiber product or the like, the texture of the fiber product tends to be rough and hard.

It is more preferable that the hydrocarbon group has 12 to 21 carbon atoms. When the number of carbon atoms is within this range, the water repellency and touch are particularly excellent. Particularly preferred as the hydrocarbon group is a linear alkyl group having 12 to 18 carbon atoms.

As the component (A), for example, stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, penta (meth)acrylate Decyl, Heptadecyl (meth)acrylate, Nonadecyl (meth)acrylate, Eicosyl (meth)acrylate, Heicosyl (meth)acrylate, Behenyl (meth)acrylate, Seryl (meth)acrylate, Melicyl (meth)acrylate Can be mentioned.

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, the durable water repellency of the obtained fiber product can be further improved. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Further, when the component (A) has an amino group, it is possible to further improve the feel of the fiber product obtained.

It is preferable that the said (A) component is a monofunctional (meth)acrylic acid ester monomer which has one polymerizable unsaturated group in 1 molecule.

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

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

In the reactive emulsifier (B1) represented by the formula (I-1) used in the present embodiment, R ³ is hydrogen or a methyl group, and from the viewpoint of copolymerization with the component (A), it is more preferably a methyl group. X is a linear or branched alkylene group having 1 to 6 carbon atoms, and from the viewpoint of the emulsion stability of the non-fluorine-based polymer of the present embodiment, a linear alkylene group having 2 to 3 carbon atoms is more preferable. Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The kind, combination, and number of additions of the alkyleneoxy group in Y ¹ can be appropriately selected so as to fall within the range of HLB. In addition, when the alkyleneoxy groups are two or more, they may have a block addition structure or a random addition structure.

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

Formula (I-2)

[In Formula (I-2), R ³ represents hydrogen or a methyl group, X represents a straight chain or branched alkylene group having 1 to 6 carbon atoms, A ¹ O represents an alkyleneoxy group having 2 to 4 carbon atoms, and m May be appropriately selected so as to fall within the range of 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 C1-C6 linear or branched alkylene group, and a C2-C3 linear alkylene group is more preferable from the viewpoint of the emulsion stability of the non-fluorine-based polymer of this embodiment. A ¹ O is an alkyleneoxy group having 2 to 4 carbon atoms. The type and combination of A ¹ O and the number of m can be appropriately selected so as to fall within the range of the HLB. In terms of the emulsion stability of the non-fluorine-based polymer of the present embodiment, m is preferably an integer of 1 to 80, and more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ O may be the same or different. In addition, when A ¹ O is two or more, 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. In addition, it can be obtained more easily than a commercial item, and examples include "LATEMUL PD-420", "LATEMUL PD-430", "LATEMUL PAD-450" manufactured by Kao Corporation.

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

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

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

Formula (II-2)

[In Formula (II-2), 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 is the range of the HLB It can be appropriately selected so that it may be, and 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) may be the same as R ⁴ in the above formula (II-1).

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

The reactive emulsifier (B2) represented by the general formula (II-2) used in this 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 specifically limited. It is not. For example, it can be synthesized by adding a predetermined amount of alkylene oxide at 120 to 170°C under pressure using an alkali catalyst such as caustic soda or caustic potassium.

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

The reactive emulsifier (B3) used in this embodiment is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to fats and oils having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18. The fats and oils having a hydroxyl group and a polymerizable unsaturated group may contain hydroxy unsaturated fatty acids (palmitraic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.). And triglycerides of fatty acids containing mono or diglycerides of fatty acids, and at least one hydroxy unsaturated fatty acid (ricinolic acid, ricinoeloidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of the emulsion stability of the non-fluorine-based polymer of the present embodiment, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one hydroxy unsaturated fatty acid is preferable, and castor oil (trigly of a fatty acid containing ricinoleic acid Ceride) is more preferably an alkylene oxide adduct having 2 to 4 carbon atoms, and an ethylene oxide adduct of castor oil is still more preferable. In addition, the number of added moles of the alkylene oxide can be appropriately selected so as to fall within the range of the HLB, and from the viewpoint of the emulsion stability of the non-fluorine-based polymer of the present embodiment, 20 to 50 moles are more preferable, and 25 to 45 moles are still more preferable. . In addition, when there are two or more kinds of alkylene oxides, they may have a block addition structure or a random addition structure.

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

The content ratio of the structural unit derived from the component (A) and the structural unit derived from the component (B) in the non-fluorine-based polymer of this embodiment is determined by the water repellency of the resulting fiber product and the emulsion stability of the non-fluorine-based polymer of this embodiment. From the point of view, the ratio (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, and 90/10 to 97/3. More preferable. When (A)/(B) is less than 85/15, the water repellency of the fiber product obtained tends to be insufficient. When (A)/(B) exceeds 99/1, the emulsion stability of the non-fluorine-based polymer of the present embodiment tends to be insufficient.

In addition, the total mass of the mass of the component (A) and the mass of the component (B) to be blended is preferably 80 to 100% by mass, and 85 to 99% by mass based on the total amount of the monomer components constituting the non-fluorine-based polymer. It is more preferable and 90-98 mass% is still more preferable.

It is preferable that the weight average molecular weight of the non-fluorine-based polymer of this embodiment is 100,000 or more. When the weight average molecular weight is less than 100,000, the water repellency of the fiber product obtained tends to be insufficient. Moreover, it is more preferable that the weight average molecular weight of a non-fluorine-type polymer is 500,000 or more. In this case, the obtained fibrous product can exhibit more sufficiently water repellency. The upper limit of the weight average molecular weight of the non-fluorine-based polymer is preferably about 5 million.

In this embodiment, the melt viscosity at 105°C of the non-fluorine-based polymer is preferably 1000 Pa·s or less. When the melt viscosity at 105° C. exceeds 1000 Pa·s, the texture of the resulting fiber product tends to become coarse and hard. In addition, if the melt viscosity of the non-fluorine-based polymer is too high, when the non-fluorine-based polymer is emulsified or dispersed to form a water repellent composition, the non-fluorine-based polymer may precipitate or settle, and the storage stability of the water-repellent composition tends to be lowered. . Further, the melt viscosity at 105°C is more preferably 500 Pa·s or less. In this case, the obtained fiber product or the like sufficiently exhibits water repellency and is more excellent in touch.

"Melt viscosity at 105°C" refers to the ratio in a cylinder with a die (10 mm in length and 1 mm in diameter) using a high-value flow tester (for example, CFT-500 manufactured by Shimadzu Corporation). It refers to the viscosity when 1 g of a fluorine-based polymer is put, maintained at 105°C for 6 minutes, and measured by applying a load of 100 kg·f/cm 2 with a plunger.

When the weight average molecular weight of the non-fluorine-based polymer of this embodiment is the same, the higher the blending ratio of the non-fluorine-based (meth)acrylic acid ester monomer, the higher the water repellency of the attached fiber product tends to be. Further, by copolymerizing a copolymerizable non-fluorine-based monomer, it is possible to improve the performance such as durable water repellency and touch of the attached fiber product.

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

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

Formula (C-1)

[In Formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group. It represents a C1-C11 monovalent chain hydrocarbon group which has a functional group of. However, the number of (meth)acryloyloxy groups in the molecule is 2 or less]

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

Formula (C-2)

[In 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) Methacrylic acid ester monomer represented by the following formula (C-3)

Formula (C-3)

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

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

Formula (C-4)

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

In the non-fluorine-based polymer of this embodiment, the content ratio of the structural unit derived from the component (A), the structural unit derived from the component (B), and the structural unit derived from the component (C) is The ratio (A) + (B) / (C) of the sum of the mass of the mass and the mass of the component (B) and the mass of the component (C) is preferably 70/30 to 99.9/0.1, and 75/25 to 99/ It is more preferable that it is 1.

The monomer of (C1) is 1 having 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. It is a (meth)acrylic acid ester monomer having a valent chain hydrocarbon group. From the viewpoint of being capable of reacting with a crosslinking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group. When the non-fluorine-based polymer containing the monomer of (C1) having a group capable of reacting with these crosslinking agents is treated to a fiber product together with a crosslinking agent, the durability and water repellency can be improved while maintaining the feel of the fiber product obtained. The isocyanate group may be a blocked 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. Moreover, the chain hydrocarbon group may further have a substituent other than the said functional group. Among them, a linear one and/or a saturated hydrocarbon group is preferable from the viewpoint of improving the durable water repellency of the resulting fiber product.

Specific monomers of (C1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, etc. Can be lifted. These monomers may be used singly or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are used in that the durability and water repellency of the obtained fiber product can be improved. desirable. Further, dimethylaminoethyl (meth)acrylate is preferred from the viewpoint of improving the feel of the fiber product obtained.

The composition ratio of the monomer of (C1) is preferably 0.1 to 30% by mass, and 1 to 25% by mass, based on the total amount of the monomer components constituting the non-fluorine-based polymer from the viewpoint of the water repellency and touch of the fiber product obtained. It is more preferable that it is, and it is still more preferable that it is 5-20 mass %.

The monomer of (C2) is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester portion, and examples of the cyclic hydrocarbon group include isobornyl group, cyclohexyl group, dicyclopentanyl group, and the like. I can. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group in which the total number of carbon atoms of the substituent and the cyclic hydrocarbon group is 11 or less is selected. In addition, it is preferable from the viewpoint of improving durable water repellency that these cyclic hydrocarbon groups are directly bonded to the ester bond. The cyclic hydrocarbon group may be alicyclic or aromatic, and in the case of alicyclic, saturated hydrocarbon group or unsaturated hydrocarbon group may be used. As a specific monomer, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc. are mentioned. These monomers may be used singly or in combination of two or more. Among them, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferable, and isobornyl methacrylate is more preferable from the viewpoint of being able to improve the durable water repellency of the obtained fiber product.

The composition ratio of the monomer of (C2) is preferably 0.1 to 30% by mass, and 1 to 25% by mass with respect to the total amount of the monomer components constituting the non-fluorine-based polymer from the viewpoint of water repellency and touch of the fiber product obtained It is more preferable that it is, and it is still more preferable that it is 5-20 mass %.

The monomer of (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 C1-C4 chain hydrocarbon group, a C1-C2 linear hydrocarbon group and a C3-C4 branched hydrocarbon group are preferable. As a C1-C4 chain hydrocarbon group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, etc. are mentioned, for example. 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. Among them, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferable, and methyl methacrylate is more preferable from the viewpoint of improving the durable water repellency of the obtained fiber product.

The constitution ratio of the monomer of (C3) is preferably 0.1 to 30% by mass, and 1 to 25% by mass, based on the total amount of the monomer components constituting the non-fluorine-based polymer, from the viewpoint of the water repellency and touch of the fiber product to be obtained. It is more preferable that it is %, and it is still more preferable that it is 5-20 mass %.

The monomer of the above (C4) is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In this embodiment, a polyfunctional (meth)acrylic acid ester monomer having three or more (meth)acryloyloxy groups in one molecule, wherein T in the formula (C-4) is a (meth)acryloyloxy group is preferred. . In formula (C-4), p number of Ts may be the same or different. As a specific compound, for example, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol Trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are mentioned. These monomers may be used singly or in combination of two or more. Among them, tetramethylolmethane tetraacrylate is more preferable from the viewpoint of improving the durable water repellency of the resulting fiber product.

It is preferable that the constitutional ratio of the monomer of the above (C4) is 0.1 to 5% by mass with respect to the total amount of the monomer components constituting the non-fluorine-based polymer from the viewpoint of the water repellency and touch of the fiber product obtained.

The non-fluorine-based polymer contained in the water repellent composition of the present embodiment, in addition to the component (A), the component (B), and the component (C), contains a monofunctional monomer (D) that can be copolymerized with these components without impairing the effects of the present invention. It can be contained within a range not included.

As the monomer of the above (D), for example, (meth)acrylic acid ester, (meth)acrylic acid, fumaric acid ester, maleic acid ester, fumaric acid, maleic acid, ( And fluorine-free vinyl monomers such as meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, vinyl chloride, vinylidene chloride, ethylene, and styrene. In addition, the (meth)acrylic acid ester having a hydrocarbon group other than component (A) and component (C) may have a substituent such as a vinyl group, a hydroxyl group, an amino group, an epoxy group and an isocyanate group, and a block isocyanate group. It may have a substituent other than a group capable of reacting with a crosslinking agent such as a quaternary ammonium group or the like, and may have an ether bond, an ester bond, an amide bond, or a urethane bond. Examples of (meth)acrylic acid esters other than component (A) and component (C) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, etc. Can be lifted.

It is preferable that the constitutional ratio of the monomer of the above (D) is 10% by mass or less with respect to the total amount of the monomer components constituting the non-fluorine-based polymer from the viewpoint of the water repellency and touch of the resulting fiber product.

The non-fluorine-based polymer contained in the water repellent composition of this embodiment has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group capable of reacting with the crosslinking agent. It is preferable from the viewpoint of improving water repellency. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Further, it is preferable that the non-fluorine-based polymer has an amino group because it also improves the feel of the resulting fiber product.

It is also possible to add additives etc. to the water repellent composition of this embodiment as needed. Examples of the additives include water repellents, crosslinking agents, antibacterial deodorants, flame retardants, antistatic agents, softeners, anti-wrinkle agents, and the like.

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

A water repellent composition containing a non-fluorine-based polymer can be prepared by a radical polymerization method. In addition, among these radical polymerization methods, it is preferable to perform polymerization by emulsion polymerization or dispersion polymerization from the viewpoint of the performance and environment of the water repellent to be obtained.

For example, in the medium, in the presence of at least one reactive emulsifier (B) selected from the compounds of (B1) to (B3), the (meth)acrylic acid ester monomer represented by the formula (A-1) ( A) can be obtained by emulsion polymerization or dispersion polymerization to obtain a non-fluorine-based polymer. More specifically, for example, a component (A), a component (B), and, if necessary, an emulsifying aid or a dispersion aid are added to the medium, and the mixture is emulsified or dispersed to obtain an emulsion or dispersion. By adding a polymerization initiator to the obtained emulsion or dispersion, a polymerization reaction is initiated, and a monomer and a reactive emulsifier can be polymerized. In addition, as a means for emulsifying or dispersing the above-described liquid mixture, a homomixer, a high pressure emulsifier, or ultrasonic waves may be mentioned.

As the emulsification aid or dispersion aid (hereinafter, also referred to as ``emulsification aid, etc.''), one selected from nonionic surfactants other than the reactive emulsifier (B), cationic surfactants, anionic surfactants, and amphoteric surfactants You can use the above. 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 still more preferably 1 to 10 parts by mass based on 100 parts by mass of all monomers. When the content of the emulsifying aid or the like is less than 0.5 parts by mass, the dispersion stability of the mixed solution tends to decrease as compared with the case where the content of the emulsifying aid or the like is in the above range, and when the content of the emulsifying aid or the like exceeds 30 parts by mass , The water repellency of the resulting non-fluorine-based polymer tends to decrease as compared with the case where the content of the emulsifying aid or the like is in the above range.

Water is preferable as a medium for emulsion polymerization or dispersion polymerization, and water and an organic solvent may be mixed as necessary. The organic solvent at this time is not particularly limited as long as it is an organic solvent that can be miscible with water. For example, alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, And glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol, such as ethers such as ethyl ether. In addition, the ratio of water and an organic solvent is not specifically limited.

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

Further, in the polymerization reaction, for the purpose of adjusting the molecular weight, a chain transfer agent such as dodecyl mercaptan and t-butyl alcohol may be used. It is preferable that it is 0.3 mass part or less, and, as for content of a chain transfer agent, it is more preferable that it is 0.1 mass part or less with respect to 100 mass parts of all monomers. When the content of the chain transfer agent exceeds 0.1 parts by mass, the molecular weight decreases, and it tends to be difficult to efficiently produce a non-fluorine-based polymer having a weight average molecular weight of 100,000 or more.

Moreover, you may use a polymerization inhibitor for molecular weight adjustment. By adding a polymerization inhibitor, a non-fluorine-based polymer having a desired weight average molecular weight can be easily obtained.

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

In the polymerization reaction, the weight average molecular weight of the resulting non-fluorine-based polymer can be adjusted by increasing or decreasing the content of the polymerization initiator, chain transfer agent, and polymerization inhibitor described above, and the melt viscosity at 105°C is the content of the polyfunctional monomer. , And it can be adjusted by increasing or decreasing the content of the polymerization initiator. In addition, when it is desired to decrease the melt viscosity at 105°C, the content of the monomer having two or more polymerizable functional groups may be reduced, or the content of the polymerization initiator may be increased.

The content of the non-fluorine-based polymer in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is preferably 10 to 50 mass% with respect to the total amount of the emulsion or dispersion from the viewpoint of storage stability and handling properties of the composition, It is more preferable to set it as 20-40 mass %.

The water-repellent fiber product of this embodiment is made of the fiber product to which the non-fluorine-based polymer of the present embodiment is adhered.

The manufacturing method of the water-repellent fiber product of this embodiment is demonstrated.

The water-repellent fiber product of the present embodiment is obtained by treating the fiber product with a treatment liquid containing the water repellent composition described above, thereby adhering a non-fluorine-based polymer to the fiber product. There is no particular limitation on the material of these textile products, and natural fibers such as cotton, hemp, silk, wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as nylon, polyester, polyurethane, polypropylene, and composite fibers thereof And blended fibers. The form of the fiber product may be any form such as fiber, thread, cloth, nonwoven fabric, or paper.

As a method of treating a fiber product with the treatment liquid, for example, a processing method such as immersion, spraying, or coating may be mentioned. In addition, when the water repellent composition contains water, it is preferable to dry it to remove water after adhering to the fiber product.

The adhesion amount of the water repellent composition to the fiber product can be appropriately adjusted according to the degree of water repellency required, but it is preferable to adjust the adhesion amount of the non-fluorine-based polymer contained in the water repellent composition to 0.01 to 10 g per 100 g of the fiber product, It is more preferable to adjust so as to be 0.05 to 5 g. When the adhesion amount of the non-fluorine-based polymer is less than 0.01 g, compared with the case where the adhesion amount of the non-fluorine-based polymer is in the above range, there is a tendency that the fiber product cannot exhibit sufficient water repellency, and when it exceeds 10 g, the adhesion amount of the non-fluorine-based polymer Compared to the case in the above range, the texture of the textile product tends to be rough and hard.

In addition, after attaching the non-fluorine-based polymer of the present embodiment to the fiber product, it is preferable to perform appropriate heat treatment. Although the temperature conditions are not particularly limited, if the water repellent composition of the present embodiment is used, a sufficiently good water repellency can be expressed in a fiber product under mild conditions of 100 to 130°C. The temperature condition may be a high temperature treatment of 130°C or higher (preferably up to 200°C), but in this case, it is possible to shorten the treatment time compared to the conventional case using a fluorine-based water repellent. Therefore, according to the water repellent fiber product of the present embodiment, deterioration of the fiber product due to heat is suppressed, the texture of the fiber product at the time of the water repellent treatment is flexible, and in addition, the fiber product has sufficient water repellency under mild heat treatment conditions, that is, low temperature curing conditions. Can be given.

In particular, in the case of wanting to improve the durable water repellency, a crosslinking agent represented by a compound having at least one methylol melamine, an isocyanate group, or a block isocyanate group, and the above-described process of treating the fiber product with a treatment liquid containing a water repellent composition, It is preferable to water-repellent the fiber product by a method including attaching it to the fiber product and heating it. In addition, when it is desired to further improve the durable water repellency, it is preferable that the water repellent composition contains a non-fluorine-based polymer copolymerized with the aforementioned crosslinking agent and a monomer having a reactive functional group.

Examples of the compound having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate, tylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like. Diisocyanates, trimers and trimethylolpropane adducts which are these isocyanurate rings. Further, examples of the compound having one or more blocked isocyanate groups include compounds obtained by protecting the isocyanate group from the compound having the above isocyanate group with a blocking agent. Examples of the blocking agent used at this time include organic blocking agents such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, and lactams, and bisulfite salts such as sodium bisulfite and potassium bisulfite. The above-mentioned crosslinking agent may be used individually by 1 type, and multiple types may be combined.

The crosslinking agent can be avoided by, for example, dissolving the crosslinking agent in an organic solvent or immersing the object to be treated (textile product) in a treatment liquid emulsified and dispersed in water, and drying the treatment liquid adhered to the object. Can be attached to the treatment. In addition, by heating the crosslinking agent attached to the object to be treated, the reaction between the crosslinking agent and the object to be treated and the non-fluorine-based polymer can proceed. In order to sufficiently advance the reaction of the crosslinking agent to more effectively improve the washing durability, heating at this time is preferably performed at 110 to 180°C for 1 to 5 minutes. The step of attaching the crosslinking agent and heating may be performed simultaneously with the step of treating with a treatment liquid containing the water repellent composition described above. When performing at the same time, for example, a treatment liquid containing a water repellent composition and a crosslinking agent is attached to an object to be treated, water is removed, and then the crosslinking agent adhered to the object to be treated is heated. When simplification of the water-repellent processing step, reduction of calories, and economical efficiency are considered, it is preferable to perform simultaneously with the treatment step of the water-repellent composition.

In addition, excessive use of the crosslinking agent may damage the touch. The crosslinking agent is preferably used in an amount of 0.1 to 50% by mass, and particularly preferably 0.1 to 10% by mass, based on the object to be treated (fiber product).

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

As mentioned above, although preferred embodiment of this invention was demonstrated, this invention is not limited to the said embodiment.

For example, in the case of producing the non-fluorine-based polymer contained in the water repellent composition of the present invention, in the above embodiment, the polymerization reaction is carried out by radical polymerization, but ionizing properties such as ultraviolet rays, electron beams, and γ rays The polymerization reaction may be carried out by photopolymerization irradiated with radiation or the like.

Further, in the present invention, the water repellent composition is treated on a fiber product to obtain a water repellent fiber product, but the product treated with the water repellent composition is not limited to the use of fiber products, and may be articles such as metal, glass, and resin.

Further, in this case, the method of attaching the water repellent composition to the article or the amount of the water repellent to be applied may be arbitrarily determined according to the type of the object to be treated.

Example

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

<Adjustment of polymer dispersion>

A mixed liquid having the composition described in Tables 1 to 5 (in the table, the numerical value indicates (g)) was polymerized by the procedure shown below to obtain a polymer dispersion.

(Example 1)

In a 500 mL flask, 60 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and water 162.75 g were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 2)

In a 500 mL flask, 55 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, acrylic acid 2-hydroxyethyl 5 g, stearyldimethylamine hydrochloride 3 g, dodecyl mercaptan 0.15 g, tripropylene glycol 20 g, and water 162.6 g were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 3)

To a 500 mL flask, 55 g of stearyl methacrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alcohol) Kenyl ether, HLB = 14.4) 2 g, acrylic acid 2-hydroxyethyl 5 g, stearyldimethylamine hydrochloride 3 g, dodecyl mercaptan 0.05 g, tripropylene glycol 20 g, and water 162.7 g were added, mixed and stirred at 45°C to obtain a mixed solution. . All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 4)

In a 500 mL flask, 55 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, acrylic acid 2-hydroxyethyl 5 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and water 162.75 g were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 5)

In a 500 mL flask, cetyl acrylate 55 g, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 14.4) 2 g, acrylic acid 2-hydroxyethyl 5 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and water 162.75 g were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 6)

To a 500 mL flask, 55 g of lauryl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, acrylic acid 2-hydroxyethyl 5 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and water 162.75 g were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 7)

In a 500 mL flask, 55 g of stearyl acrylate, 12.5 mol of cardanol ethylene oxide 12.5 mol addition product (HLB = 12.9, in the table, described as ``cardanol 12.5EO'') 2 g, 8.3 mol of cardanol ethylene oxide addition product (HLB = 11.0, in the table, described as "cardanol 8.3EO") 2g, acrylic acid 2-hydroxyethyl 5g, stearyldimethylamine hydrochloride 3g, tripropylene glycol 20g, and water 162.75g were added, mixed and stirred at 45°C, and the mixture was stirred. I did it. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 8)

In a 500 mL flask, 55 g of stearyl acrylate, 42 mol of ethylene oxide adduct of castor oil (HLB = 13.3, in the table, described as ``castor oil 42EO'') 2 g, ethylene oxide 30 mol adduct of castor oil (HLB = 11.7, table In the above, 2 g of "castor oil 30EO", 5 g of 2-hydroxyethyl acrylic acid, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 9)

To a 500 mL flask, 57 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, tetramethylolmethane tetraacrylate 3 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and water 162.75 g were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 10)

In a 500 mL flask, 55 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, dimethylamino ethyl methacrylate 5 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 11)

In a 500 mL flask, 55 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, glycidyl methacrylate 5 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and water 162.75 g were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 12)

In a 500 mL flask, 55 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, 5 g of methyl ethyl ketone oxime blocked product of 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol, and 162.75 g of water were added, and 45° C. Mixing and stirring was carried out to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 13)

To a 500 mL flask, 51 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 4 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 4g, acrylic acid 2-hydroxyethyl 5g, stearyldimethylamine hydrochloride 3g, tripropylene glycol 20g, and water 162.75g were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 14)

To a 500 mL flask, 56 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 0.5 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl) Ether, HLB = 14.4) 0.5 g, polyoxyethylene (10 mol) lauryl ether 2 g, acrylic acid 2-hydroxyethyl 5 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and water 162.75 g were added thereto at 45°C. The mixture was stirred to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 15)

To a 500 mL flask, 45 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, acrylic acid 2-hydroxyethyl 5 g, acrylic acid isobornyl 10 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and water 162.75 g were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 16)

To a 500 mL flask, 45 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, 2-hydroxyethyl acrylic acid 5 g, isobornyl methacrylate 10 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and 162.75 g water were added, followed by mixing and stirring at 45°C to obtain a mixed solution. . All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 17)

To a 500 mL flask, 45 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, 2-hydroxyethyl acrylic acid 5 g, cyclohexyl methacrylate 10 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g, and 162.75 g water were added, followed by mixing and stirring at 45° C. to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Example 18)

To a 500 mL flask, 45 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) , HLB = 14.4) 2 g, acrylic acid 2-hydroxyethyl 5 g, methyl methacrylate 10 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g were added, followed by mixing and stirring at 45°C to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 26% by mass.

(Comparative Example 1)

In a 500 mL flask the following formula (III):

Formula (III)

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

(Comparative Example 2)

In a 500 mL flask, 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 added thereto at 45°C. The mixture was stirred to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 24% by mass.

(Comparative Example 3)

In a 500 mL flask, 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 added thereto at 45°C. The mixture was stirred to obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 24% by mass.

(Comparative Example 4)

In a 500 mL flask, 55 g of stearyl acrylate, Neugen XL-100 (manufactured by Daiichi Kogyo Seyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7) 2 g, Neugen XL-60 (Daiichi Kogyo Seyaku) Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5) 2 g, acrylic acid 2-hydroxyethyl 5 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g were added, and mixed and stirred at 45°C. To obtain a mixed solution. All monomers were emulsified and dispersed by irradiating the mixture with ultrasonic waves. Subsequently, 0.25 g of azobis(isobutylamidine) dihydrochloride was added to the mixture, followed by radical polymerization at 60°C for 6 hours in a nitrogen atmosphere to obtain a non-fluorine-based polymer dispersion having a polymer concentration of 24% by mass.

In addition, each of the polymers in the polymer dispersions obtained in Examples 1 to 18 and Comparative Examples 1 to 4 were 98% of all monomers by a gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation). It was confirmed that the abnormality was polymerization.

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

(Evaluation of physical properties of non-fluorine-based polymer)

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

(1) Melt viscosity measurement method

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

(2) Measurement method of weight average molecular weight

For the polymers of Examples 1 to 18 and Comparative Examples 2 to 4 obtained above, by a GPC apparatus (GPC "HLC-8020" manufactured by Tosoh Corporation), the conditions of a column temperature of 40°C and a flow rate of 1.0 ml/min Below, it was measured using tetrahydrofuran as an eluent, and the weight average molecular weight was measured in terms of standard polystyrene. In addition, the column was attached by connecting three of the brand names TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation.

(Evaluation of storage stability of water repellent composition)

The stability when the polymer dispersions obtained in Examples 1 to 18 or Comparative Examples 1 to 4 were stored at 45° C. for 2 weeks were evaluated according to the following criteria. The results are shown in Tables 6 to 9.

A: No change in appearance

B: Oily matter near the liquid surface and very little polymer precipitates on the container wall

C: Polymer sedimentation, separation, and gelation are observed

(Evaluation of water repellency of textile products)

In accordance with the spray method of JIS L 1092 (1998), the test was conducted with the shower water temperature set to 27°C. In this test, the dyed 100% polyester fabric or 100% nylon fabric is immersed in a treatment solution diluted with water so that the polymer dispersion of Examples 1 to 18 or Comparative Examples 1 to 4 is 3% by mass. After (pickup rate 60 mass%), it dried at 130 degreeC for 2 minutes, and it heat-processed under the conditions as shown in Tables 6-9, and evaluated the water repellency of the obtained cloth. The results were evaluated by the following grades visually. In addition, when the characteristic is very slightly good, "+" is added to the grade, and when the characteristic is very little, "-" is added to the grade. The results are shown in Tables 6 to 9.

Water repellency: state

5: There is no wet adhesion to the surface

4: To show very little adhesion wetting to the surface

3: showing partial wetting on the surface

2: showing wetting on the surface

1: showing wetting over the entire surface

0: The front and back sides completely show wetness

(Tactile evaluation of textile products)

To the touch, the dyed 100% polyester fabric was immersed in a treatment 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% by mass (pickup rate 60% by mass). ), dried at 130° C. for 2 minutes, and further heat-treated at 170° C. for 30 seconds to evaluate. 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 and water repellency of textile products)

In accordance with the spray method of JIS L 1092 (1998), the test was conducted with the shower water temperature set to 27°C. In this test, the dyed 100% polyester fabric had a polymer content of 3% by mass, a content of UNIKA RESIN 380-K (crosslinking agent, trimethylol melamine resin manufactured by Union Chemical Industries, Ltd.) of 0.3% by mass, and The polymer dispersion of Examples 1 to 18 or Comparative Examples 1 to 4 and each of the above agents so that the content of UNIKA CATALYST 3-P (surfactant, amino alcohol hydrochloride, manufactured by Union Chemical Co., Ltd.) is 0.2% by mass. Was immersed in a treatment solution diluted with water (pickup rate 60% by mass), dried at 130° C. for 2 minutes, and further heat treated at 170° C. for 60 seconds (L-0), and JIS L 0217 ( The water repellency of the fabric after washing by the 103 method of 1995) was performed 10 times (L-10) in the same manner as in the above water repellency evaluation method. In addition, in the case of the 100% nylon fabric, the evaluation was performed in the same manner as in the case of the 100% polyester fabric, except that the heat treatment temperature was changed from 170°C to 160°C. The results are shown in Tables 6 to 9.

The fiber product treated with the water repellent composition of Examples 1 to 18 exhibits water repellency and durable water repellency equal to or higher than that of the case of using a conventional fluorine-based water repellent (Comparative Example 1), even without heat treatment, and has a good touch. Confirmed. In addition, it was confirmed that the storage stability of the composition was also good.

Comparing Example 2 and Example 4, it was confirmed that even if the composition of the non-fluorine-based polymer is close, when the weight average molecular weight of the polymer is different, the larger the weight average molecular weight is, the better the water repellency is.

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

The water repellent composition of Comparative Example 3, compared with Comparative Example 2, for the purpose of improving the storage stability of the composition, by increasing the amount of emulsifying aid (general surfactant), the water repellency of the fiber product treated with the composition is lowered. There was a tendency.

The water repellent composition of Comparative Example 4 was subjected to emulsion polymerization in combination with a general surfactant having HLB within the preferred range of the present invention instead of a reactive emulsifier, and it was confirmed that the water repellency of the treated fiber product was lowered.

From the above, according to the present invention, it is possible to provide a water repellent composition that has excellent storage stability and can impart sufficient water repellency to fiber products and the like even when heat treatment is not performed, and obtain a water repellent fiber product having excellent touch and water repellency. It was confirmed that there is.

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 textile products, after treating the fiber product with the water repellent composition, heat treatment at a low temperature can exhibit sufficiently excellent water repellency, so that even special fibers or natural fibers that are vulnerable to heat can exhibit sufficient water repellency. I can. Further, by using a crosslinking agent together or copolymerizing a reactive monomer, the durable water repellency and touch can be improved. Further, since the water repellent composition of the present invention does not contain a fluorine-containing group, it is inexpensive and is useful as a water repellent composition with little adverse effect on the human body or environment. In addition, compared to the conventional water repellent, the amount of surfactant used can be reduced, and it is possible to cope with various fiber processing.

Claims (9)

A structural unit derived from a (meth)acrylic acid ester monomer (A) represented by the following formula (A-1), and
(B1) a compound represented by the following formula (I-1) in which HLB is 7 to 18, (B2) a compound represented by the following formula (II-1) in which HLB is 7 to 18, and (B3) HLB is from 7 to Constituent units derived from at least one reactive emulsifier (B) selected from compounds in which alkylene oxides having 2 to 4 carbon atoms are added to fats and oils having a hydroxyl group and a polymerizable unsaturated group of 18
A water repellent composition containing a non-fluorine-based polymer containing.
Formula (A-1)

[In 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]
Formula (I-1)

[In Formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. Represents a group]
Formula (II-1)

[In Formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms] The method of claim 1, wherein the non-fluorine-based polymer is added to at least one second (meth)acrylic acid ester monomer (C) selected from the group consisting of the following (C1), (C2), (C3) and (C4). A water repellent composition further containing a derived structural unit.
(C1) (meth)acrylic acid ester monomer represented by the following formula (C-1)
Formula (C-1)

[In Formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group. It represents a C1-C11 monovalent chain hydrocarbon group which has a functional group of. However, the number of (meth)acryloyloxy groups in the molecule is 2 or less]
(C2) (meth)acrylic acid ester monomer represented by the following formula (C-2)
Formula (C-2)

[In 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) Methacrylic acid ester monomer represented by the following formula (C-3)
Formula (C-3)

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

[In formula (C-4), R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents a (p+1) valent organic group, and T represents a 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) in which HLB is 7 to 18, (B2) a compound represented by the following formula (II-1) in which HLB is 7 to 18, and (B3) HLB is from 7 to At least one reactive emulsifier (B) selected from compounds in which alkylene oxides having 2 to 4 carbon atoms are added to fats and oils having 18 phosphorus, hydroxyl groups and polymerizable unsaturated groups
A water repellent composition comprising a non-fluorine-based polymer obtained by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing a.
Formula (A-1)

[In 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]
Formula (I-1)

[In Formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. Represents a group]
Formula (II-1)

[In Formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms] The method of claim 3, wherein the emulsion or the dispersion is at least one second (meth)acrylic acid ester monomer selected from the group consisting of the following (C1), (C2), (C3) and (C4) ) Further comprising a water repellent composition.
(C1) (meth)acrylic acid ester monomer represented by the following formula (C-1)
Formula (C-1)

[In Formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group. It represents a C1-C11 monovalent chain hydrocarbon group which has a functional group of. However, the number of (meth)acryloyloxy groups in the molecule is 2 or less]
(C2) (meth)acrylic acid ester monomer represented by the following formula (C-2)
Formula (C-2)

[In 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) Methacrylic acid ester monomer represented by the following formula (C-3)
Formula (C-3)

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

[In formula (C-4), R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents a (p+1) valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group. ] A structural unit derived from a (meth)acrylic acid ester monomer (A) represented by the following formula (A-1), and
(B1) a compound represented by the following formula (I-1) in which HLB is 7 to 18, (B2) a compound represented by the following formula (II-1) in which HLB is 7 to 18, and (B3) HLB is from 7 to Constituent units derived from at least one reactive emulsifier (B) selected from compounds in which alkylene oxides having 2 to 4 carbon atoms are added to fats and oils having a hydroxyl group and a polymerizable unsaturated group of 18
A water-repellent fiber product consisting of a fiber product to which a non-fluorine-based polymer is attached.
Formula (A-1)

[In 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]
Formula (I-1)

[In Formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. Represents a group]
Formula (II-1)

[In Formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms] The method of claim 5, wherein the non-fluorine-based polymer is added to at least one second (meth)acrylic acid ester monomer (C) selected from the group consisting of the following (C1), (C2), (C3) and (C4). A water-repellent fiber product further containing the derived structural unit.
(C1) (meth)acrylic acid ester monomer represented by the following formula (C-1)
Formula (C-1)

[In Formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group. It represents a C1-C11 monovalent chain hydrocarbon group which has a functional group of. However, the number of (meth)acryloyloxy groups in the molecule is 2 or less]
(C2) (meth)acrylic acid ester monomer represented by the following formula (C-2)
Formula (C-2)

[In 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) Methacrylic acid ester monomer represented by the following formula (C-3)
Formula (C-3)

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

[In formula (C-4), R ¹⁰ represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents a (p+1) valent organic group, and T represents a 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) in which HLB is 7 to 18, (B2) a compound represented by the following formula (II-1) in which HLB is 7 to 18, and (B3) HLB is from 7 to At least one reactive emulsifier (B) selected from compounds in which alkylene oxides having 2 to 4 carbon atoms are added to fats and oils having 18 phosphorus, hydroxyl groups and polymerizable unsaturated groups
A water-repellent fiber product consisting of a fiber product to which a non-fluorine-based polymer is attached, which is made by emulsion polymerization or dispersion polymerization of an emulsion or dispersion comprising a.
Formula (A-1)

[In 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]
Formula (I-1)

[In Formula (I-1), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. Represents a group]
Formula (II-1)

[In Formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms] The method of claim 7, wherein the emulsion or the dispersion is at least one second (meth)acrylic acid ester monomer selected from the group consisting of the following (C1), (C2), (C3) and (C4) ), a water-repellent fiber product further comprising.
(C1) (meth)acrylic acid ester monomer represented by the following formula (C-1)
Formula (C-1)

[In Formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group. It represents a C1-C11 monovalent chain hydrocarbon group which has a functional group of. However, the number of (meth)acryloyloxy groups in the molecule is 2 or less]
(C2) (meth)acrylic acid ester monomer represented by the following formula (C-2)
Formula (C-2)

[In 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) Methacrylic acid ester monomer represented by the following formula (C-3)
Formula (C-3)

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

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