WO2020054401A1

WO2020054401A1 - Water-repellent agent composition for fibers, water-repellent textile product, and production method for water-repellent textile product

Info

Publication number: WO2020054401A1
Application number: PCT/JP2019/033580
Authority: WO
Inventors: 高輔前田; 弓子漆崎; 好揮柘植
Original assignee: 日華化学株式会社
Priority date: 2018-09-14
Filing date: 2019-08-27
Publication date: 2020-03-19
Also published as: TW202018058A; KR20210049171A; JP2020045586A; JP7469845B2; TWI734187B; KR102538168B1; CN112673128A

Abstract

This water-repellent agent composition contains: an acrylic resin having a constituent unit derived from a (meth)acrylic acid ester monomer (A) represented by general formula (A-1) and/or a urethane resin having a structural unit derived from a polyfunctional compound represented by general formula (I-1) and a structural unit derived from an isocyanate compound represented by general formula (II-1); an organo-modified silicone represented by general formula (L-1); and a wax. [In formula (A-1), R¹ represents hydrogen or a methyl group, R² represents an optionally substituted monovalent hydrocarbon group having 12 or more carbon atoms.] (I-1): R³¹[-W¹-R³²]_d[-V¹]_e [In formula (I-1), d represents an integer of one or more, e represents an integer of two or more, (d+e) is 3-6, R³¹ represents a (d+e)-valent organic group, W¹ represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group, R³² represents a straight-chain or branched monovalent hydrocarbon group having 8-24 carbon atoms, and V¹ represents a hydroxyl group, an amino group, or a carboxy group. Note that two or more among the e-number of V¹'s are a hydroxyl group and/or an amino group.] (II-1): R³³[-NCO]_f [In formula (II-1), R³³ represents an f-valent organic group, and f represents an integer of 2-7.] [In formula (L-1), R²²⁰, R²²¹, and R²²² each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1-4 carbon atoms, R²²³ represents a hydrocarbon group having an aromatic ring and having 8-40 carbon atoms, or an alkyl group having 3-22 carbon atoms, R²³⁰, R²³¹, R²³², R²³³, R²³⁴, and R²³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1-4 carbon atoms, a hydrocarbon group having an aromatic ring and having 8-40 carbon atoms, or an alkyl group having 3-22 carbon atoms, a1 represents an integer of zero or more, a2 represents an integer of one or more, (a1 + a2) is 10-200, in the case where a1 is two or more, respective R²²⁰'s and respective R²²¹'s may be the same or different from each other, and in the case where a2 is two or more, respective R²²²'s and respective R²²³'s may be the same or different from each other.]

Description

Water repellent composition for fiber, water repellent fiber product, and method for producing water repellent fiber product

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

Conventionally, a fluorine-based water repellent having a fluoroalkyl group has been known as a water-repellent used for water-repellent processing and the like, and water repellency is imparted by treating such a fluorine-based water repellent on the fiber surface. The resulting fibrous product is obtained. However, although textiles treated with a fluorine-based water repellent exhibit excellent water repellency, concerns about the environmental impact of the long-chain fluoroalkyl compounds used have become apparent, and they do not contain any fluorine-based compounds at all. Non-fluorine-based water repellents that exhibit high-performance water-repellent properties comparable to those of fluorine-based ones have been required internationally.

Therefore, in recent years, research on a non-fluorine-based water repellent containing no fluorine has been advanced. For example, Patent Document 1 listed below discloses a fiber processing agent containing at least one of a silicon compound, a wax compound, and a wax-zirconium compound. Patent Literature 2 below proposes a flexible water repellent containing an amino-modified silicone and a polyfunctional isocyanate. Further, Patent Document 3 listed below proposes a water repellent comprising a specific non-fluorinated polymer containing a (meth) acrylic acid ester having 12 or more carbon atoms in the ester portion as a monomer unit.

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

However, conventional non-fluorine-based water repellents show the initial water-repellent effect in the spray method of JIS L # 1092 (2009), which is one of the general water repellency evaluation tests, but the practical use and actual application of textile products In some cases, sufficient results were not obtained in evaluation tests that assumed For practical use, durable water repellency, which is unlikely to decrease in water repellency even after repeated washing, is required. For actual attachment, it is required that water immersion can be prevented for a long time. If the water immersion prevention property is insufficient, when water droplets stay on the fiber surface for a certain period of time, a part of the water droplets may penetrate into the fiber over time, leading to wetting of the opposite surface. Conventional non-fluorine-based water repellents are still insufficient in performance in practical use and actual mounting surface as compared with fluorine-based water-repellents.

繊維 Water-repellent textile products and the like are sometimes coated with urethane resin or acrylic resin on predetermined portions. In this case, it is required that the fiber product has sufficient water repellency, but the coating portion is not easily peeled off at the portion to be coated. The difficulty in peeling the coating can be evaluated by measuring the stress (peel strength) required to peel the coating film from the water-repellent treated fiber base material. However, studies on such peel strength have not been sufficiently conducted, and there is room for further improvement in order to achieve a higher level of the above practical and actual performance and peel strength at the same time.

The present invention has been made in view of the above circumstances, and can impart excellent initial water repellency, durable water repellency, and water immersion preventing property to a fiber base material, and a fiber base provided with such properties. It is an object of the present invention to provide a water repellent composition for fibers that can provide a material having sufficient peel strength, a water repellent fiber product using the same, and a method for producing a water repellent fiber product.

As a result of intensive studies by the present inventors to solve the above problems, a specific resin, a specific silicone, and a water-repellent cloth using a water-repellent composition formulated by combining a wax are excellent. In addition to the initial water repellency, the present invention has been found to show good results in the evaluation of the durability water repellency after washing, the evaluation of the water immersion prevention property and the evaluation of the peel strength, and based on this finding, completed the present invention. I came to.

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

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

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

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

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

According to the water repellent composition for fibers of the present invention, it is possible to impart excellent initial water repellency, durable water repellency and water immersion prevention properties to the fiber base material, and it is sufficient while such properties are provided. A fiber substrate having a peel strength can be obtained. As a result, it is possible to realize a water-repellent fiber product having performance suitable for practical use and actual arrival.

In addition, the water repellent composition for fibers of the present invention imparts excellent water repellency (the effect of increasing the contact angle to water) while being a water repellent composition containing no compound having a fluoroalkyl group or fluorine. Therefore, it can be used as a substitute for the fluorine-based water repellent, and it is possible to eliminate concerns about the influence on the environment and the like. Further, according to the fiber water repellent composition of the present invention, while sufficiently maintaining the texture of the fiber base material, while the above-described excellent initial water repellency, durable water repellency and water immersion prevention properties are imparted, A fiber substrate having a sufficient peel strength can be obtained.

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

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

の一 Another aspect of the present invention relates to a water-repellent fiber product comprising a fiber base material and the water-repellent composition for fibers according to the present invention adhered to the fiber base material.

The water-repellent fiber product of the present invention is provided with excellent initial water repellency, durable water repellency and water immersion resistance by the water repellent composition for fibers according to the present invention, and further, when coated. Has sufficient peel strength. Therefore, the water-repellent fiber product of the present invention can have practical and practical performance.

更に Still another aspect of the present invention relates to a method for producing a water-repellent fiber product, comprising a step of bringing a treatment liquid containing the water-repellent composition according to the present invention into contact with a fiber base material.

According to the method for producing a water-repellent fiber product of the present invention, it is possible to obtain a water-repellent fiber product having excellent initial water repellency, durable water repellency and water immersion prevention properties, and having sufficient peel strength. Can be.

According to the present invention, it is possible to impart excellent initial water repellency, durable water repellency and water immersion preventing property to the fiber base material, and the fiber base material provided with such properties has sufficient peel strength. It is possible to provide a water-repellent composition for fibers that can be used as a water-repellent fiber product and a method for producing a water-repellent fiber product using the same.

Hereinafter, a preferred embodiment of the present invention will be described.

In the present specification, “(meth) acrylate” means “acrylate” or a corresponding “methacrylate”, and “(meth) acrylic acid”, “(meth) acrylamide” and the like are also used. It is synonymous.

において In the present specification, an ester group means a group represented by —O—CO—. An amide group means a group represented by -NH-CO-. The urethane group means a group represented by —O—CO—NH—. The urea group means a group represented by -NH-CO-NH-. The isocyanate group means a group represented by -N = C = O. The carbonyl group means a group represented by -CO-.

において In this specification, the term “fiber substrate” refers to an object to which water repellency is applied by the water repellent composition, and may be a fiber product or a fiber material constituting the fiber product.

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

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

成分 The component (α) contained in the water repellent composition according to the present embodiment will be described in detail below.

(Α) component is preferably an acrylic resin. When the component (α) is an acrylic resin, it is easy to enhance the initial water repellency, the durability water repellency, or both (hereinafter, also simply referred to as “water repellency”), and the water immersion preventing property.

Hereinafter, the acrylic resin will be described.

The (meth) acrylate monomer (A) (hereinafter, also referred to as “monomer (A)”) represented by the general formula (A-1) used in the present embodiment has a substituent. It has a monovalent hydrocarbon group having 12 or more carbon atoms which may be used. This hydrocarbon group may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may further be an alicyclic or aromatic cyclic group. May be provided. Among these, from the viewpoints of water repellency and prevention of water immersion, those having a linear chain are preferable, and those having a linear alkyl group are more preferable. When the monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, the substituent includes a hydroxy group, an amino group, a carboxy group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth) acryloyloxy group. And the like. In the exemplary embodiment, in the general formula (A-1), R ² is preferably an unsubstituted hydrocarbon group.

炭素 The hydrocarbon group preferably has 12 to 24 carbon atoms, and more preferably 12 to 22 carbon atoms. When the number of carbon atoms of the hydrocarbon group is in such a range, it is easy to enhance the water repellency and the water immersion preventing property imparted to the fiber base while sufficiently maintaining the feel of the fiber base. From the same viewpoint as above, the hydrocarbon group is more preferably a straight-chain alkyl group having 15 to 22 carbon atoms, and further preferably a straight-chain alkyl group having 15 to 20 carbon atoms. Is more preferable.

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

The monomer (A) may have at least one functional group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, an epoxy group, and an isocyanate group that can react with a crosslinking agent described below. In this case, it becomes easy to enhance the water repellency and the water immersion prevention property imparted to the fiber base material. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. When the monomer (A) has an amino group, the texture of the resulting fiber product can be further improved.

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

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

The monomer (A) is an acrylate monomer (a1) (hereinafter, also referred to as a “(a1) component”) from the viewpoint of improving the water repellency and the prevention of water immersion imparted to the fiber base material. And methacrylic acid ester monomer (a2) (hereinafter also referred to as “component (a2) component”). The ratio (a1) / (a2) between the mass of the component (a1) and the mass of the component (a2) to be blended is preferably 30/70 to 90/10, and more preferably 40/60 to 85/15. Is more preferably 50/50 to 80/20, particularly preferably 60/40 to 80/20. When (a1) / (a2) is within the above range, it becomes easy to enhance the water repellency and the water immersion preventing property imparted to the fiber base material.

When the water repellent composition of the present embodiment contains an acrylic resin as the component (α), the total constituent ratio of the monomer (A) in the acrylic resin may be 50 to 100% by mass, and the fiber base material From the viewpoint of improving the water repellency and the prevention of water immersion imparted to the acrylic resin, the amount is preferably 50 to 99% by mass, and more preferably 60 to 99% by mass based on the total amount of the monomer components constituting the acrylic resin. Is more preferable, and the content is more preferably 70 to 99% by mass.

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

において In the present embodiment, the melt viscosity of the acrylic resin at 105 ° C. is preferably 1,000 Pa · s or less. When the melt viscosity at 105 ° C. is 1000 Pa · s or less, a water-repellent fiber product having an excellent feeling tends to be easily obtained. Further, when the melt viscosity at 105 ° C. is 1,000 Pa · s or less, when the acrylic resin is emulsified or dispersed to form a water repellent composition, the acrylic resin can be prevented from being precipitated or settled, The storage stability of the liquid medicine composition tends to be improved. Further, the melt viscosity of the acrylic resin at 105 ° C. is more preferably 500 Pa · s or less. In this case, the obtained water-repellent fiber product and the like have a sufficient water repellency and a better feeling.

The acrylic resin is added to the monomer (A) from the viewpoint of improving water repellency and anti-water immersion, and improving the emulsion stability of the acrylic resin during and after emulsion polymerization or dispersion polymerization in the composition. (B1) a compound represented by the following general formula (B-1) having an HLB of 7 to 18, (B2) a compound represented by the following general formula (B-2) having an HLB of 7 to 18, And (B3) at least one reactive emulsifier (B) selected from compounds obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil having an HLB of 7 to 18 and having a hydroxy group and a polymerizable unsaturated group. ) (Hereinafter also referred to as “reactive emulsifier (B)”) as a monomer component.

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

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

“Reactive emulsifier” is an emulsifying dispersant having radical reactivity, that is, a surfactant having one or more polymerizable unsaturated groups in a molecule, such as a (meth) acrylate ester. It can be copolymerized with a monomer.

において In the specification of the present application, “HLB” means an HLB value calculated by the Griffin method by regarding an ethyleneoxy group as a hydrophilic group and all other groups as a lipophilic group, unless otherwise specified.

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

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

化合物 As the compound represented by the general formula (B-1), a compound represented by the following general formula (b-1) is preferable.

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

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

反応 The reactive emulsifier (B1) represented by the general formula (b-1) can be obtained by a conventionally known method, and is not particularly limited. In addition, it can be easily obtained from commercial products, and examples thereof include “Latemul PD-420”, “Latemul PD-430”, and “Latemul PD-450” manufactured by Kao Corporation.

In the reactive emulsifier (B2) represented by the general formula (B-2), R ⁴ is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and is a tridecenyl group; Examples include a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, and a heptadecatrienyl group. From the viewpoint of emulsion stability of the acrylic resin, R ⁴ is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

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

化合物 As the compound represented by the general formula (B-2), a compound represented by the following general formula (b-2) is preferable.

[In the formula (b-2), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and A ² O represents an alkyleneoxy group having 2 to 4 carbon atoms. And n can be appropriately selected so as to be within the above range of HLB. Specifically, it is preferably an integer of 1 to 50. When n is 2 or more, n A ² Os are the same. May also be different. ]

R ⁴ in the compound represented by the general formula (b-2) are the same as those for R ⁴ in formula (B-2).

A ² O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of emulsification stability of the acrylic resin, the type and combination of A ² O and the number of n can be appropriately selected so as to be within the above-mentioned HLB. From the viewpoint of the emulsion stability of the acrylic resin, 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 further preferably an integer of 8 to 14. When n is 2 or more, n A ² Os may be the same or different. When two or more kinds of A ² O are used, they may have a block addition structure or a random addition structure.

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

フェノール The corresponding phenol having an unsaturated hydrocarbon group includes not only a pure product or a mixture produced industrially, but also a pure product or a mixture extracted and purified from plants or the like. For example, 3- [8 (Z), 11 (Z), 14-pentadecatrienyl] phenol, 3- [8 (Z), 11 (Z), which is extracted from cashew nut shells and the like and is collectively referred to as cardanol. -Pentadecadienyl] phenol, 3- [8 (Z) -pentadecenyl] phenol and 3- [11 (Z) -pentadecenyl] phenol.

The reactive emulsifier (B3) is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a HLB of 7 to 18 and having a hydroxy group and a polymerizable unsaturated group. Fats and oils having a hydroxy group and a polymerizable unsaturated group may include unsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.). Good fatty acid mono- or diglycerides, fatty acid triglycerides containing at least one type of hydroxy-unsaturated fatty acid (such as ricinoleic acid, ricinoleic acid, and 2-hydroxytetracosenoic acid) can be mentioned. From the viewpoint of the emulsion stability of the acrylic resin, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one type of hydroxyunsaturated fatty acid is preferable, and an alkylene having 2 to 4 carbon atoms of a castor oil (triglyceride of a fatty acid containing ricinoleic acid). Oxide adducts are more preferred, and ethylene oxide adducts of castor oil are even more preferred. Further, the number of moles of the alkylene oxide to be added can be appropriately selected so as to be within the above-mentioned range of HLB, and from the viewpoint of emulsification stability of the acrylic resin, 20 to 50 mol is more preferable, and 25 to 45 mol is further preferable. preferable. When two or more alkylene oxides are used, they may have a block addition structure or a random addition structure.

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

The constituent ratio of the reactive emulsifier (B) in the acrylic resin is from 0.5 to 0.5 with respect to the total amount of the monomer components constituting the acrylic resin from the viewpoint of improving water repellency and emulsification stability of the acrylic resin. It is preferably 20% by mass, more preferably 1 to 15% by mass, and still more preferably 3 to 10% by mass.

When the water repellent composition contains an acrylic resin as the component (α), the acrylic resin contains the following (C1), (C2), (C3), in addition to the monomer (A), from the viewpoint of water repellency. At least one kind of the second (meth) acrylate monomer (C) (hereinafter, also referred to as “monomer (C)”) selected from the group consisting of (C4) and (C5) is a single monomer It is preferable to contain it as a body component.

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

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

(C2) is a (meth) acrylate monomer represented by the following general formula (C-2).

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

(C3) is a methacrylate monomer represented by the following general formula (C-3).

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

(C4) is a (meth) acrylate monomer represented by the following general formula (C-4).

[In the 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 1 having a polymerizable unsaturated group. Represents a valent organic group. ]

(C5) is a (meth) acrylate monomer represented by the following general formula (C-5).

[In the formula (C-5), R ¹⁵ represents hydrogen or a methyl group; R ¹⁶ has at least one functional group selected from the group consisting of a chloro group and a bromo group; Represents a monovalent chain-like saturated hydrocarbon group. ]

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

The chain hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, the chain hydrocarbon group may further have a substituent in addition to the above functional group. Above all, from the viewpoint of water repellency and texture, it is preferable that the compound is linear and / or a saturated hydrocarbon group.

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

The proportion of the monomer (C1) in the acrylic resin is preferably from 1 to 30% by mass, and more preferably from 3 to 30% by mass, based on the total amount of the monomer components constituting the acrylic resin from the viewpoint of water repellency. The content is more preferably 25% by mass, and further preferably 5 to 20% by mass.

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

The proportion of the monomer (C2) in the acrylic resin is preferably from 1 to 30% by mass, and more preferably from 3 to 30% by mass, based on the total amount of the monomer components constituting the acrylic resin from the viewpoint of water repellency. The content is more preferably 25% by mass, and further preferably 5 to 20% by mass.

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

The proportion of the monomer (C3) in the acrylic resin is preferably 1 to 30% by mass, and more preferably 3 to 30% by mass, based on the total amount of the monomer components constituting the acrylic resin from the viewpoint of water repellency. The content is more preferably 25% by mass, and further preferably 5 to 20% by mass.

単量体 The monomer (C4) is a (meth) acrylate monomer having three or more polymerizable unsaturated groups in one molecule. In the present embodiment, a polyfunctional (meth) acrylate ester having three or more (meth) acryloyloxy groups in one molecule, wherein T in the general formula (C-4) is a (meth) acryloyloxy group. Mers are preferred. In the formula (C-4), p Ts may be the same or different. Specific compounds include, for example, ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethanetetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like can be mentioned. One of these monomers may be used alone, or two or more thereof may be used in combination. Among them, from the viewpoint of water repellency, tetramethylol methane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferable.

The proportion of the monomer (C4) in the acrylic resin is preferably 1 to 30% by mass, and more preferably 3 to 30% by mass, based on the total amount of the monomer components constituting the acrylic resin, from the viewpoint of water repellency. The content is more preferably 25% by mass, and further preferably 5 to 20% by mass.

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

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

From the viewpoint of water repellency, the chain saturated hydrocarbon group preferably has one or two chloro groups and one hydroxy group, and one chloro group and one hydroxy group. It is more preferred to have. In addition, from the viewpoint of water repellency, the chain saturated hydrocarbon group has a hydroxy group at the β-position (the carbon atom next to the carbon atom bonded to CH ₂ ＣＲCR ¹⁵ (CO) O—). Is more preferred. Specific examples of the above-mentioned chain saturated hydrocarbon group include 3-chloro-2-hydroxylpropyl group, 3-chloro-2-hydroxybutyl group, 5-chloro-2-hydroxypentyl group and 3-chloro-2. -Hydroxy-2-methylpropyl group and 3-bromo-2-hydroxypropyl group.

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

From the viewpoint of water repellency, the constituent ratio of the monomer (C5) in the acrylic resin is preferably from 1 to 30% by mass relative to the total amount of the monomer components constituting the acrylic resin. The content is more preferably 25% by mass, and further preferably 5 to 20% by mass.

The total composition ratio of the monomer (C) in the acrylic resin is preferably from 1 to 30% by mass, based on the total amount of the monomer components constituting the acrylic resin, from the viewpoint of water repellency. The content is more preferably from 25 to 25% by mass, and still more preferably from 5 to 20% by mass.

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

Examples of the monomer (D) include (meth) acryloyl morpholine, (meth) acrylates having a hydrocarbon group other than the monomers (A) and (C), and (meth) acrylic acid. , Fumaric acid ester, maleic acid ester, fumaric acid, maleic acid, (meth) acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene and styrene, etc., except for the monomer (E) described below which does not contain fluorine And the like. The (meth) acrylic ester having a hydrocarbon group other than the monomer (A) and the monomer (C) may be a vinyl group, a hydroxy group, an amino group, an epoxy group, an isocyanate group, It may have a substituent such as a blocked isocyanate group or the like, may have a substituent other than a group capable of reacting with a crosslinking agent such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond. Or a urethane bond or the like. Examples of the (meth) acrylate other than the monomer (A) and the monomer (C) include, for example, methyl acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate and ethylene glycol di ( (Meth) acrylate and the like.

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

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

When the water repellent composition contains an acrylic resin, the acrylic resin may be used in addition to the monomer (A), and at least one of vinyl chloride and vinylidene chloride (E) from the viewpoint of peel strength. ) (Hereinafter also referred to as “monomer (E)”) as a monomer component.

少なくとも As the monomer (E) of at least one of vinyl chloride and vinylidene chloride used in the present embodiment, vinyl chloride is preferable from the viewpoint of maintaining the texture of the fiber base material.

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

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

アクリル For example, an acrylic resin can be obtained by emulsion polymerization or dispersion polymerization of the (meth) acrylate monomer (A) represented by the above general formula (A-1) in a medium. More specifically, for example, in the medium, the monomer (A) and, if necessary, the reactive emulsifier (B), the monomer (C), the monomer (D), and the monomer (E) and an emulsifying aid or a dispersing aid are added, 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 started, and the monomer and the reactive emulsifier can be polymerized. In addition, as a means for emulsifying or dispersing the above-mentioned mixed liquid, a homomixer, a high-pressure emulsifier, an ultrasonic wave or the like can be mentioned.

Examples of the emulsifying aid or dispersing aid (hereinafter, also referred to as “emulsifying aid and the like”) include nonionic surfactants other than the reactive emulsifier (B), cationic surfactants, anionic surfactants, and One or more selected from amphoteric surfactants can be used. The emulsifying aid and the like are preferably nonionic surfactants from the viewpoint of storage stability.

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

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

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

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

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

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

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

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

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

Among them, from the viewpoints of little effect on water repellency and water repellency, little effect on light fastness, and good emulsifiability of the acrylic resin, a linear or branched chain having 8 to 24 carbon atoms is preferred. Alcohols or alkenols and acetylene alcohols represented by the above general formula (AL-1) are preferable, and linear or branched alcohols having 8 to 24 carbon atoms, and acetylene alcohols represented by the above general formula (AL-1) are preferable. More preferred.

Examples of the alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide, epichlorohydrin, and the like. As the alkylene oxide, ethylene oxide and 1,2-propylene oxide are preferable, and ethylene oxide is more preferable, from the viewpoint that the effect on water repellency is small and the emulsifiability of the copolymer is improved.

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

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

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

The content of the emulsifying aid and the like is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the monomers constituting the acrylic resin. More preferably, it is 1 to 10 parts by mass. When the content of the emulsification aid or the like is 0.5 parts by mass or more, the dispersion stability of the mixed solution is further improved as compared with the case where the content of the emulsification aid is less than 0.5 part by mass. When the content of the emulsifying aid or the like is 30 parts by mass or less, the water repellency of the obtained water repellent composition is lower than when the content of the emulsifying aid or the like exceeds 30 parts by mass Tends to improve.

水 Water is preferred as a medium for emulsion polymerization or dispersion polymerization, and water and an organic solvent may be mixed as necessary. Examples of the organic solvent at this time include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, propylene glycol, dipropylene glycol, and tripropylene. And glycols such as glycol. It is preferable to use glycols because the water repellency and the water immersion preventing property imparted to the fiber base material are further improved. The ratio between water and the organic solvent is not particularly limited.

公知 As the above-mentioned polymerization initiator, a known polymerization initiator such as an azo type, a peroxide type, or a redox type can be appropriately used. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass based on 100 parts by mass of all the monomers constituting the acrylic resin. When the content of the polymerization initiator is within the above range, an acrylic resin having a weight average molecular weight of 100,000 or more can be efficiently produced.

連鎖 In the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight.

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

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

In the polymerization reaction, the weight average molecular weight of the obtained acrylic resin can be adjusted by increasing or decreasing the content of the above-described polymerization initiator, chain transfer agent, and polymerization inhibitor. It can be adjusted by increasing or decreasing the content of the polymer and the content of the polymerization initiator. In order to reduce the melt viscosity at 105 ° C., the content of a monomer having two or more polymerizable functional groups may be reduced or the content of a polymerization initiator may be increased.

The content of the acrylic resin in the emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is from 10 to 50% by mass based on the total amount of the emulsion or dispersion from the viewpoint of storage stability and handling properties of the composition. Preferably, the content is set to 20 to 40% by mass.

In the polymerization reaction, instead of performing the polymerization reaction using a polymerization initiator, for example, the polymerization reaction may be performed by photopolymerization that irradiates ionizing radiation such as ultraviolet rays, electron beams, and γ rays.

Next, the urethane resin will be described.

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

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

In the above general formula (I-1), when d is 2 or more, a plurality of W ¹ may be the same or different. A plurality of R ³² may be the same or different. A plurality of V ¹ may be the same or different.

R ³¹ represents a (d + e) -valent organic group. From the viewpoints of water repellency and water immersion prevention properties, R ³¹ preferably has 2 to 40 carbon atoms, and more preferably 4 to 12 carbon atoms. As R ³¹ , a group represented by the following chemical formula (1), a group represented by the following chemical formula (2), and a group represented by the following chemical formula (3) are preferable. (D + e) is preferably 3 to 4 from the viewpoint of easy handling of the urethane resin.

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

R represents an integer of 1 or more, and is preferably 1 to 3.

R ³¹ is a polyfunctional compound having (d + e) at least one kind of functional group selected from the group consisting of a hydroxy group, an amino group, and a carboxy group (hereinafter, referred to as “polyfunctional compound A”); It may be a residue excluding the number of functional groups. However, two or more of the (d + e) functional groups are a hydroxy group and / or an amino group.

Examples of the polyfunctional compound A include, for example, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, glycerin, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aminoethylethanolamine, diethanolamine, Triethanolamine and the like. Among these, trimethylolpropane, ditrimethylolpropane, diethanolamine and diethylenetriamine are preferred from the viewpoints of water repellency and anti-water immersion properties and the stability of the obtained urethane resin in emulsification and dispersion.

W ¹ represents a divalent group that is an ester group, an amide group, a urethane group or a urea group. W ¹ is preferably an ester group or a urethane group from the viewpoints of water repellency and water immersion prevention.

R ³² represents a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may have an alicyclic or aromatic ring. As the hydrocarbon group, a linear group is preferable, and a linear alkyl group is more preferable, from the viewpoints of water repellency and water immersion prevention. The carbon number of the hydrocarbon group is preferably from 10 to 24, more preferably from 12 to 22, and particularly preferably from 12 to 18. When the carbon number is in this range, it becomes easy to enhance the water repellency and the water immersion preventing property imparted to the fiber base while sufficiently maintaining the feel of the fiber base. As the hydrocarbon group, a linear alkyl group having 12 to 18 carbon atoms is particularly preferable.

The R ^32, for example, nonyl, decyl, undecyl, dodecyl (lauryl group), a myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group, nonadecyl group, eicosyl group, heneicosyl group, and behenyl group Is mentioned.

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

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

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

(4) Examples of the higher aliphatic monoisocyanate include decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, myristyl isocyanate, pentadecyl isocyanate, cetyl isocyanate, stearyl isocyanate, eicosyl isocyanate, and behenyl isocyanate.

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

V ¹ represents a hydroxy group, an amino group or a carboxy group. V ¹ is preferably a hydroxy group or an amino group from the viewpoint of water repellency.

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

The hydrophobic group represented by [-W ¹ -R ³² ] is, for example, one mole or more of the reactive hydrocarbon compound per 1 mole of the polyfunctional compound A, The compound can be introduced by a conventional synthesis method, that is, an esterification reaction, an amidation reaction, or a urethane reaction so that the number e is 2 or more.

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

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

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

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

In the polyfunctional compound represented by the general formula (I-2), when i is 2, a plurality of W ² may be the same or different. When i is 2, a plurality of R ⁴³ may be the same or different. When i is 2, a plurality of R ⁴⁴ may be the same or different. R ⁴⁴ corresponds to R ³² in the above general formula (I-1). A plurality of R ⁴² may be the same or different. V ² existing in plural numbers may be different, even the same.

In the polyfunctional compound represented by the above general formula (I-2), W ² is a divalent group which is an ester group, an amide group, a urethane group or a urea group. W ² is preferably an ester group or a urethane group from the viewpoints of water repellency and prevention of water immersion.

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

In the group represented by the general formula (4), V ³ is a hydroxy group, an amino group, or a carboxy group. V ³ is preferably a hydroxy group or an amino group from the viewpoint of water repellency.

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

In the group represented by the general formula (5), W ³ is a divalent group that is an ester group, an amide group, a urethane group, or a urea group. W ³ is preferably an ester group or a urethane group from the viewpoints of water repellency and water immersion prevention.

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

In the group represented by the general formula (6), W ⁴ is a divalent group that is an ester group, an amide group, a urethane group, or a urea group. W ⁴ is preferably an ester group, an amide group, or a urethane group from the viewpoints of water repellency and water immersion prevention.

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

In the group represented by the general formula (8), W ⁵ is a divalent group that is an ester group, an amide group, a urethane group, or a urea group. W ⁵ is preferably an ester group, an amide group or a urethane group from the viewpoints of water repellency and water immersion prevention.

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

Next, the isocyanate compound represented by the general formula (II-1) will be described.

R ³³ represents a f-valent organic group. The number of carbon atoms of R ^33, from the viewpoint of water repellency and water immersion viewed preventing property, preferably from 4 to 40, more preferably 6 to 18. As R ^33, a hexylene group is preferable. f may be an integer of 2 to 7, and is preferably 2 to 3 from the viewpoints of water repellency and prevention of water immersion.

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

The urethane resin obtained by reacting the polyfunctional compound represented by the general formula (I-1) with the isocyanate compound represented by the general formula (II-1) includes, for example, the following general formula (III) -1), urethane resins having partial structures represented by general formulas (III-2) and (III-3), and the like.

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

k1 represents an integer of 2 or more, and from the viewpoints of water repellency and prevention of water immersion, and further improves the emulsification and dispersion stability of the urethane resin, and further facilitates the handling of the urethane resin. It is preferably 100, more preferably 2 to 50.

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

k2 represents an integer of 2 or more, and from the viewpoints of water repellency and prevention of water immersion, and further improves the emulsification and dispersion stability of the urethane resin, and further facilitates the handling of the urethane resin. It is preferably 200, more preferably 2 to 100.

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

Wherein (III-3), k4 represents an integer of 2 or ^{more, R 114} represents a monovalent hydrocarbon group each independently a straight-chain or branched having 10 to 24 carbon atoms. ]

k4 represents an integer of 2 or more, and from the viewpoints of water repellency and prevention of water immersion, and further improves the emulsification and dispersion stability of the urethane resin, and further facilitates the handling of the urethane resin. It is preferably 200, more preferably 2 to 100.

として Examples of the urethane resin having a partial structure represented by the general formula (III-1) include a compound represented by the following formula (III-4).

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

k5 represents an integer of 2 or more, and from the viewpoints of water repellency and prevention of water immersion, and further improves the emulsification and dispersion stability of the urethane resin, and further facilitates the handling of the urethane resin. It is preferably 100, more preferably 2 to 50.

として Examples of the urethane resin having a partial structure represented by the general formula (III-2) include a compound represented by the following formula (III-5).

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

k6 represents an integer of 2 or more, and from the viewpoints of water repellency and prevention of water immersion, and further improves the emulsification and dispersion stability of the urethane resin, and further facilitates the handling of the urethane resin. It is preferably 200, more preferably 2 to 100.

k7 represents an integer of 1 or more, and from the viewpoints of water repellency and prevention of water immersion, and further improves the emulsification / dispersion stability of the urethane resin, and further facilitates handling of the urethane resin. It is preferably 3, and more preferably 1.

として Examples of the urethane resin having a partial structure represented by the general formula (III-3) include a compound represented by the following formula (III-6).

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

k8 represents an integer of 2 or more, and from the viewpoints of water repellency and prevention of water immersion, and further improves the emulsification and dispersion stability of the urethane resin, and further facilitates the handling of the urethane resin. It is preferably 200, more preferably 2 to 100.

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

として Examples of the blocked isocyanate group protected by the blocking agent include a group represented by the following general formula (10).

(-NH-CO-B) (10)
[In the formula (10), B is a group derived from a blocking agent. ]

Examples of the blocking agent include pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole and pyrazole; methanol, Alcohols such as ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol; phenol, methylphenol, chlorophenol, p-iso-butylphenol, p-tert-butylphenol Phenols such as p-iso-amylphenol, p-octylphenol, p-nonylphenol; dimethyl malonate, diethyl malonate, acetylacetone, methyl acetoacetate, ethyl acetoacetate Active methylene compounds; oximes such as formaldoxime, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime and benzophenone oxime; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam; N-substituted amides such as N-methylacetamide and acetanilide; imide compounds such as succinimide and phthalimide; and imidazole compounds such as imidazole and 2-methylimidazole. One type of blocking agent may be used alone, or two or more types may be used in combination. Among these, it is preferable to use at least one compound selected from the group consisting of pyrazoles, oximes and lactams from the viewpoint of versatility and reactivity of the blocked isocyanate group, and ease of blocking. Among them, it is more preferable to use at least one compound selected from the group consisting of dimethylpyrazole, methyl ethyl ketone oxime and caprolactam.

The weight average molecular weight of the urethane resin is preferably from 2,000 to 100,000, more preferably from 2,000 to 100,000, from the viewpoints of water repellency and prevention of water immersion, and further improving the emulsion dispersion stability of the urethane resin. It may be from 000 to 50,000, more preferably from 2,000 to 20,000.

When reacting the polyfunctional compound represented by the above general formula (I-1) having ^one hydroxy group and / or one amino group with the compound represented by the above general formula (II-1), The compounding amount of the compound represented by the formula (II-1) is (0.8 to 1.20) × 2 / e ^{1 with} respect to 1 mol of the polyfunctional compound represented by the general formula (I-1). mol are preferred, (0.80 ~ 0.99) × more preferably 2 / ^{e 1} mol, more preferably (0.85 ~ 0.95) × 2 / e 1 mol. Alternatively, (1.01 to 1.20) × 2 / e ¹ mol is more preferable, and (1.05 to 1.15) × 2 / e ¹ is more preferable.

から The urethane resin of the present embodiment is preferably emulsified or dispersed with an emulsifying aid or a dispersing aid from the viewpoint of water repellency and environment. The emulsion or dispersion containing the urethane resin of the present embodiment can be produced, for example, as follows.

乳化 An emulsification or dispersion can be obtained by adding a surfactant as an emulsifying aid or a dispersing aid to the urethane resin of the present embodiment to make it uniform, and gradually adding water thereto with stirring.

As the surfactant, at least one selected from conventionally known nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants can be used. The content of the emulsifying aid and the like is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and more preferably 20 to 30 parts by mass, based on 100 parts by mass of the urethane resin of the present embodiment. Is more preferable. When the content of the emulsification aid and the like is in the above range, it becomes easy to improve the emulsion dispersion stability of the urethane resin while maintaining the water repellency.

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

The obtained aqueous dispersion of urethane resin was prepared using a homomixer (manufactured by Primix Co., Ltd.), a homogenizer (manufactured by NIROSOAVI or APVGAULIN), a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), and an ultimateizer (manufactured by Sugino Machine Co., Ltd.) The particles can be homogenized by a high-pressure emulsifier such as Starburst (manufactured by Sugino Machine Co., Ltd.) or an ultrasonic emulsifier.

成分 The component (β) contained in the water repellent composition according to the present embodiment will be described in detail below.

において In the general formula (L-1), each structural unit may be a block, random, or may be arranged alternately.

In the component (β) of the present embodiment, the alkoxyl group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and a butoxy group. R ²²⁰ , R ^221, and R ²²² are each independently preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint that they are industrially easy to obtain and easily available.

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

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

アルキレン The above-mentioned alkylene group may be linear or branched.

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

アルキレン The above-mentioned alkylene group may be linear or branched.

The aralkyl group having 8 to 40 carbon atoms includes, for example, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group and naphthylethyl group. Among them, a phenylethyl group and a phenylpropyl group are preferable in that they are easily produced industrially and are easily available.

In the group represented by the general formula (L-2), R ²⁴⁰ is preferably an alkylene group having 2 to 4 carbon atoms, and a3 represents 0 or It is preferably 1, and more preferably 0.

In the group represented by the general formula (L-3), R ²⁴² is preferably an alkylene group having 2 to 4 carbon atoms, and a4 represents 0 or It is preferably 1, and more preferably 0.

As the hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms, the aralkyl group having 8 to 40 carbon atoms and the general formula ( The group represented by L-2) is preferable, and the above-mentioned aralkyl group having 8 to 40 carbon atoms is more preferable from the viewpoint of imparting water repellency and water immersion preventing property to the fiber base material.

アルキル The alkyl group having 3 to 22 carbon atoms may be linear or branched. Examples of the alkyl group having 3 to 22 carbon atoms include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, and stearyl. The alkyl group having 3 to 22 carbon atoms is preferably an alkyl group having 8 to 20 carbon atoms, and is preferably an alkyl group having 12 to 18 carbon atoms, from the viewpoint of imparting water repellency and preventing water immersion to the fiber base material. More preferred.

In the component (β) of the present embodiment, R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, It is a hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms, or an alkyl group having 3 to 22 carbon atoms. R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ^234, and R ²³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group, or a group having 1 carbon atom in terms of being easily produced industrially and easily available. It is preferably from 4 to 4 alkoxy groups, and more preferably a methyl group.

において In the component (β) of the present embodiment, a1 is an integer of 0 or more. A1 is preferably 40 or less, and more preferably 30 or less, from the viewpoint of being easily produced industrially, easily available, and imparting water repellency and water immersion preventing property to the fiber base material. preferable.

において In the component (β) of the present embodiment, (a1 + a2) is 10 to 200. (A1 + a2) is preferably from 20 to 100, and more preferably from 40 to 60, from the viewpoint of easy industrial production and easy availability. When (a1 + a2) is within the above range, the production and handling of the silicone itself tends to be easy.

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

Examples of the silicone having a SiH group include methyl hydrogen silicone having a degree of polymerization of 10 to 200, and a copolymer of dimethyl siloxane and methyl hydrogen siloxane. Among them, methyl hydrogen silicone is preferable in that it is easily produced industrially and is easily available.

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

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

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

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

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

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

ヒドロ The hydrosilylation reaction is preferably performed in an inert gas atmosphere. Examples of the inert gas include nitrogen, argon, and the like. Although the reaction proceeds even in the absence of a solvent, a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate and the like.

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

成分 The component (γ) contained in the water repellent composition according to the present embodiment will be described in detail below.

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

化合物 The compound constituting the component (γ) according to this embodiment is not particularly limited, and examples thereof include normal alkanes and normal alkenes. The component (γ) is preferably normal alkane from the viewpoint of water repellency and texture.

Examples of the normal alkane include trichosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosan, triacontan, hentriacontan, dotriacontan, tritriacontan, tetratriacontan, pentatriacontan, and hexatriacontan. Can be Normal alkanes are preferably triacontan, hentriacontan and dotriacontan from the viewpoint of water repellency and texture.

Examples of the normal alkene include 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacocene, 1-heptacosene, 1-octacocene, nonacocene, triaconten, hentriaconten, dotria Examples include content, tritria content, tetratria content, pentatria content, and hexatria content. Normal alkenes are preferably triaconten, hentriaconten and dotriaconten from the viewpoint of water repellency and texture.

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

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

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

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

The content ratio of the component (α) to the component (γ) according to the present embodiment is preferably 90:10 to 40:60 by mass, more preferably 80:20 to 50:50. More preferably, it is 70:30 to 60:40. When the content ratio of the component (α) to the component (γ) is within the above range, excellent water repellency and water immersion prevention can be imparted while sufficiently maintaining the texture of the fiber base material.

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

水 The water repellent composition according to the present embodiment may further include a crosslinking agent (hereinafter, also referred to as “(δ)” component) from the viewpoint of water repellency. The component (δ) will be described in detail below.

The component (δ) according to the present embodiment is not particularly limited, and examples thereof include a melamine resin, a glyoxal resin, and a compound having one or more isocyanate groups or blocked isocyanate groups. The compound having at least one isocyanate group or blocked isocyanate group as the component (δ) includes the structural unit derived from the polyfunctional compound represented by the general formula (I-1) and the general formula (II- A urethane resin having a structural unit derived from an isocyanate compound represented by 1) is not included. As the component (δ), one type can be used alone, or two or more types can be used in combination.

As the melamine resin, compounds having a melamine skeleton can be used, for example, polymethylolmelamines such as trimethylolmelamine and hexamethylolmelamine; and some or all of the methylol groups of the polymethylolmelamine have 1 to 6 carbon atoms. Alkoxymethylmelamine which has become an alkoxymethyl group having an alkyl group; acyloxymethylmelamine which has a part or all of the methylol group of polymethylolmelamine has become an acyloxymethyl group having an acyl group having 2 to 6 carbon atoms; No. These melamine resins may be any of monomers, multimers of dimers or more, or a mixture thereof. Further, melamine co-condensed with urea or the like can also be used. Such melamine resins include, for example, Beckamine APM, Beckamine M-3, Beckamine M-3 (60), Beckamine MA-S, Beckamine J-101, and Beckamine J-101LF manufactured by DIC Corporation, Union Chemical Industry Unika Resin 380K manufactured by Miki Riken Co., Ltd., and Riken Resin MM series manufactured by Miki Riken Kogyo Co., Ltd. are exemplified.

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

When a melamine resin and a glyoxal resin are used as the component (δ), the water-repellent composition according to the present embodiment preferably further contains a catalyst from the viewpoint of accelerating the reaction. The catalyst is not particularly limited as long as it is a commonly used catalyst, and examples thereof include borofluoride compounds such as ammonium borofluoride and borofluorite; and neutral metal salt catalysts such as magnesium chloride and magnesium sulfate. Inorganic acids such as phosphoric acid, hydrochloric acid, boric acid and the like; These catalysts may be used together with organic acids such as citric acid, tartaric acid, malic acid, maleic acid, lactic acid and the like as cocatalysts, if necessary. Examples of such a catalyst include Catalyst AX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, and Catalyst DIC manufactured by DIC Corporation. Catalyst NFC-1, Unica Catalyst 3-P manufactured by Union Chemical Industry Co., Ltd. and Unica Catalyst MC-109, Riken Fixer RC Series, Riken Fixer MX Series and Riken Fixer RZ- manufactured by Miki Riken Kogyo Co., Ltd. 5 and the like.

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

The polyfunctional isocyanate compound is not particularly limited as long as it has two or more isocyanate groups in the molecule, and a known polyisocyanate compound can be used. Examples of the polyfunctional isocyanate compound include diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimer or trimer of these diisocyanate compounds. The alkylene diisocyanate preferably has 1 to 12 carbon atoms.

Examples of the diisocyanate compound include 2,4 or 2,6-tolylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, and Methylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, phenylene diisocyanate, tolylene or naphthylene diisocyanate, 4,4′-methylene-bis (phenyl isocyanate), 2,4′-methylene-bis ( Phenylisocyanate), 3,4'-methylene-bis (phenylisocyanate), 4,4'-ethylene-bis (phenyliso Anate), ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylcyclohexane, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'- Diisocyanate-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanatecyclohexane, 4,4'-methylene-bis (cyclohexylisocyanate), 3-isocyanate-methyl-3,5,5-trimethylcyclohexylisocyanate, acid -Diisocyanate dimer, ω, ω'-diisocyanate diethylbenzene, ω, ω'-diisocyanate dimethyltoluene, ω, ω'-diisocyanate diethyltoluene, bis (2-isocyanateethyl) fumarate, 1,4-bis (2 -Isocyanate- LOP-2-yl) benzene, and 1,3-bis (2-isocyanate - prop-2-yl) benzene.

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

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

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

イソシアネート The isocyanate group of the polyfunctional isocyanate compound may be as it is, or may be a blocked isocyanate group blocked by a blocking agent. Examples of the blocking agent include pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole and pyrazole; phenol, methylphenol Phenols such as phenol, chlorophenol, iso-butylphenol, tert-butylphenol, iso-amylphenol, octylphenol and nonylphenol; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam; dimethyl malonate, diethyl malonate Active methylene compounds such as esters, acetylacetone, methyl acetoacetate, ethyl acetoacetate; formaldoxime, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexano Oxime, acetophenone oxime, oxime such as benzophenone oxime; imidazole, imidazole compounds such as 2-methylimidazole; and sodium bisulfite and the like. Of these, pyrazoles and oximes are preferred from the viewpoint of water repellency.

(4) As the polyfunctional isocyanate compound, a water-dispersible isocyanate obtained by imparting a water-dispersibility to the polyisocyanate by introducing a hydrophilic group into the polyisocyanate structure to have a surfactant effect can be used. Further, in order to promote the reaction, a known catalyst such as organic tin or organic zinc can be used in combination.

The content ratio of the component (α) to the component (δ) according to the present embodiment is preferably from 95: 5 to 60:40 by mass, more preferably from 95: 5 to 70:30. More preferably, it is 90:10 to 80:20. When the content ratio of the component (α) to the component (δ) is within the above range, excellent water repellency and water immersion-preventing property are imparted while sufficiently maintaining the texture of the fiber base material, and sufficient peeling is performed. It becomes easy to obtain a fiber base material having strength.

水 The water repellent composition according to the present embodiment may contain additives and the like as necessary. Additives include other water repellents, surfactants, defoamers, pH adjusters, antibacterial agents, fungicides, coloring agents, antioxidants, deodorants, various organic solvents, chelating agents, antistatic agents Agents, antibacterial deodorants, flame retardants, softeners, wrinkle inhibitors and the like.

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

Examples of the antifoaming agent include oil and fat antifoaming agents such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; fatty acid antifoaming agents such as stearic acid, oleic acid, and palmitic acid; isoamyl stearate, distearyl succinate , Ethylene glycol distearate, butyl stearate and other fatty acid ester-based defoamers; polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3-heptanol, 2-ethylhexanol and other alcohol-based defoamers; Ether-based antifoaming agents such as -t-amylphenoxyethanol 3-heptylcellosolve nonyl cellosolve 3-heptylcarbitol; phosphate-based antifoaming agents such as tributyl osphate and tris (butoxyethyl) phosphoate; amine-based antifoaming agents such as diamylamine Foaming agent; Real sharp emission amide, amide-based defoaming agent such as acylate polyamine; sulfate-based defoaming agents such as sodium lauryl sulfate; mineral oil, and the like. One of the defoaming agents can be used alone, or two or more can be used in combination.

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

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

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

水性 The water-repellent fiber product according to the present embodiment will be described.

水性 The water-repellent fiber product according to the present embodiment includes a fiber base material and the water-repellent composition according to the present embodiment adhered to the fiber base material.

The fiber substrate may be a fiber product or a fiber material constituting the fiber product.

The material of the fiber base material is not particularly limited, for example, natural fibers such as cotton, hemp, silk, wool, semi-synthetic fibers such as rayon, acetate, nylon, polyester, polyurethane, synthetic fibers such as polypropylene and the like. Examples include conjugate fibers and blended fibers.

形態 The form of the fiber base material is not particularly limited, but may be any form such as a fiber, a thread, a cloth, a nonwoven fabric, and a paper.

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

方法 A method for producing a water-repellent fiber product according to the present embodiment will be described.

製造 The method for producing a water-repellent fiber product according to the present embodiment includes a step of bringing a fiber base into contact with a treatment liquid containing the water-repellent composition according to the present embodiment.

方法 Examples of the method of treating the fiber base material with the above-mentioned treatment liquid include processing methods such as immersion, spraying, and application. When the water repellent composition contains water, it is preferable that the water repellent composition be dried after being attached to the fiber base material to remove water.

水性 In the water-repellent fiber product of the present embodiment, a predetermined portion can be coated. Examples of the coating process include a moisture permeable waterproof process and a windproof process for sports use and outdoor use. As a processing method, for example, in the case of moisture permeable waterproof processing, a coating liquid containing a urethane resin or acrylic resin other than those contained in the water repellent composition of the present invention and a medium, a water-repellent fiber product Can be processed by applying it to one side of and drying it.

The adhesion amount of the water repellent composition to the fiber base material can be appropriately adjusted according to the required degree of water repellency. However, while maintaining the texture of the fiber base material sufficiently, the water repellency and the prevention of water penetration are ensured. From the viewpoint of imparting properties and ensuring sufficient peel strength, the total adhesion amount of the component (α), the component (β), and the component (γ) contained in the water-repellent composition is 100 g with respect to 100 g of the fiber base material. The adjustment is preferably made to be 0.01 to 10 g, more preferably 0.05 to 5 g.

After the water repellent composition of the present embodiment is attached to the fiber base material, it is preferable to appropriately perform heat treatment. The temperature condition is not particularly limited, but when the water repellent composition of the present embodiment is used, the fiber substrate can exhibit sufficiently good water repellency under mild conditions of 100 to 130 ° C. The temperature condition may be a high temperature treatment of 130 ° C. or more (preferably up to 200 ° C.), but in such a case, the treatment time can be shortened as compared with the conventional case using a fluorine-based water repellent. . Therefore, according to the method for producing a water-repellent fiber product of the present embodiment, deterioration of the fiber base material due to heat is suppressed, the feel of the fiber base material during water-repellent treatment becomes flexible, and mild heat treatment conditions, that is, Under low temperature curing conditions, sufficient water immersion preventing properties can be imparted to the fiber base material.

When the water repellent composition of the present embodiment contains the component (δ), the reaction of the cross-linking agent proceeds sufficiently to more effectively impart water repellency and water immersion prevention properties, and the peel strength is improved. From the viewpoint of improving the quality, it is preferable to heat the fiber substrate to which the component (δ) is attached at 110 to 180 ° C. for 1 to 5 minutes. The attachment amount of the component (δ) to the fiber base is preferably 0.1 to 50% by mass, more preferably 0.1 to 10% by mass, based on the weight of the fiber base.

各 Each component contained in the water repellent composition according to the present embodiment may be separately contained in a plurality of treatment liquids. For example, it can be divided into a treatment liquid containing the (α) component, the (β) component and the (γ) component, and a treatment liquid containing the (δ) component.

The water-repellent fiber product obtained by the production method of the present embodiment, even when used outdoors for a long time, can exhibit sufficient water repellency, is excellent in texture, and the water-repellent fiber product Since no fluorine-based compound is used, it can be environmentally friendly.

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

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

<Preparation of acrylic resin dispersion>
Using the materials shown in Tables 1 and 2 (where the numerical values indicate (g) in the tables), polymerization was carried out by the following procedure to obtain an acrylic resin dispersion.

(Synthesis example 1)
In a 0.5 L autoclave, 15 g of stearyl acrylate, 5 g of stearyl methacrylate, 0.5 g of Surfynol 465 (manufactured by Nissin Chemical Co., Ltd., HLB = 13), 1 g of Surfynol 440 (manufactured by Nissin Chemical Co., Ltd., HLB = 8), Neugen XL- 0.5 g of 40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5), 1 g of stearyltrimethylammonium sulfate, 15 g of tripropylene glycol and 54.9 g of water were added, and the mixture was heated at 45 ° C. The mixture was stirred to obtain a mixed solution. The mixture was irradiated with ultrasonic waves to emulsify and disperse all monomers. Next, 0.15 g of azobis (isobutylamidine) dihydrochloride was added to the mixture, and 7 g of vinyl chloride was continuously injected under a nitrogen atmosphere so that the internal pressure of the autoclave was maintained at 0.3 MPa. And reacted for 6 hours to obtain an acrylic resin dispersion containing 27% by mass of an acrylic resin.

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

(Synthesis Example 14)
In a 1000 ml flask, 206.74 g of ditrimethylolpropane, 469.87 g of stearic acid, and 3.4 g of p-toluenesulfonic acid were put. Next, the temperature was raised to 140 ° C. in a nitrogen atmosphere, and then a dehydration reaction was performed at 140 to 190 ° C. for 5 hours in a nitrogen stream at a rate of about 0.4 ° C./min. The nitrogen flow rate is 5 ml per minute. After the reaction, the acid value of the synthesized product was measured. The acid value was 2.0 mgKOH / g.

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

In the urethane resin contained in the obtained urethane resin dispersion, R ³¹ in the general formula (I-1) is a residue obtained by removing four hydroxy groups from ditrimethylolpropane, d is 2, e is 2, and W ¹ Is an ester group, R ³² is a heptadecyl group, V ¹ is a hydroxy group, and an isocyanate compound in which R ³³ is a hexylene group and f is 2 in the general formula (II-1). After that, the isocyanate group remaining without reacting is blocked with 3,5-dimethylpyrazole to obtain a compound.

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

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

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

In the urethane resin contained in the obtained urethane resin dispersion, R ³¹ in the general formula (I-1) is a residue obtained by removing three hydroxy groups from trimethylolpropane, d is 1, e is 2, W ¹ Is an ester group, R ³² is a heptadecyl group, V ¹ is a hydroxy group, and an isocyanate compound in which R ³³ is a hexylene group and f is 2 in the general formula (II-1). After that, the isocyanate group remaining without reacting is blocked with 3,5-dimethylpyrazole to obtain a compound.

<Preparation of organo-modified silicone emulsion>
(Synthesis Example 16)
63.2 g of methyl hydrogen silicone having a SiH group equivalent of 63.2 g / mol and a degree of polymerization of 50 was placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel. Then, the mixture was flushed with nitrogen and heated until the temperature reached 65 ° C., and mixed until uniform. As a hydrosilylation catalyst, a mixed solution of platinum (IV) chloride and ethylene glycol monobutyl ether / toluene was added so that the platinum concentration was 5 ppm with respect to the reactants in the system. When the temperature of the reaction product reached 120 ° C., 168.3 g of 1 mol of 1-dodecene was added dropwise and reacted at 120 ° C. for 6 hours. The completion of the addition reaction was confirmed by performing FT-IR analysis of the obtained organo-modified silicone and confirming that the absorption spectrum derived from the SiH group of methyl hydrogen silicone had disappeared. Thus, in the general formula (L-1), a1 is 0, a2 is 50, ^R222 is a methyl group, ^R223 is a dodecyl group, ^R230 , ^R231 , ^R232 , ^R233 , ^R234, and ^R235 are methyl. The resulting organo-modified silicone was obtained. Further, to 20 parts by mass of the obtained organo-modified silicone, 3 parts by mass of 9 mol of an ethylene oxide adduct of a branched higher alcohol having 12 to 14 carbon atoms were added and mixed. Next, 77 parts by weight of water was added little by little while mixing and emulsified in water to obtain an organo-modified silicone emulsion containing 20% by weight of the organo-modified silicone.

(Synthesis Example 17)
An organo-modified silicone and an organo-modified silicone emulsion were obtained in the same manner as in Synthesis Example 16, except that 14.2 mol of 1-hexene was used instead of 168.3 g of 1 mol of 1-dodecene. In the organo-modified silicone, a1 in the general formula (L-1) is 0, a2 is 50, ^R222 is a methyl group, ^R223 is a hexyl group, ^R230 , ^R231 , ^R232 , ^R233 , and ^R234. And an organo-modified silicone in which R ²³⁵ is a methyl group.

(Synthesis Example 18)
An organo-modified silicone and an organo-modified silicone emulsion were obtained in the same manner as in Synthesis Example 16, except that 25 mol of 1 mol of 1-octadecene was used instead of 168.3 g of 1 mol of 1-dodecene. In the organo-modified silicone, a1 in the general formula (L-1) is 0, a2 is 50, ^R222 is a methyl group, ^R223 is an octadecyl group, ^R230 , ^R231 , ^R232 , ^R233 , and ^R234. And an organo-modified silicone in which R ²³⁵ is a methyl group.

(Synthesis Example 19)
In the same manner as in Synthesis Example 16 except that 84.2 g of 0.5 mol of 1-dodecene and 126.2 g of 0.5 mol of 1-octadecene were used instead of 168.3 g of 1 mol of 1-dodecene. Thus, an organo-modified silicone and an organo-modified silicone emulsion were obtained. In the organo-modified silicone, a1 in the formula (L-1) is 0, a2 is 50, ^R222 is a methyl group, ^R223 is a dodecyl group or an octadecyl group, ^R230 , ^R231 , ^R232 , and ^R233. , ^R234 and ^R235 were methyl groups.

(Synthesis example 20)
140.5 g of a copolymer of dimethylsiloxane and methylhydrogensiloxane was used in place of 63.2 g of methyl hydrogen silicone, and 1 mole of 1-dodecene was used instead of 168.3 g of 1 mole of 1-dodecene. An organo-modified silicone and an organo-modified silicone emulsion were obtained in the same manner as in Synthesis Example 17 except that 252.5 g of octadecene was used. The copolymer of dimethylsiloxane and methylhydrogensiloxane had an SiH group equivalent of 140.5 g / mol and a degree of polymerization of 50. In the organo-modified silicone, a1 in the general formula (L-1) is 25, a2 is 25, ^R220 and ^R221 are methyl groups, ^R222 is a methyl group, ^R223 is an octadecyl group, ^R230 and ^R231. , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ were methyl groups.

<Production example of wax emulsion>
(Production Example 1)
In a high-pressure reactor, paraffin wax (melting point 69 ° C., penetration 12 (25 ° C.)) 150 g, pure water 350 g, polyoxyethylene stearyl ether (HLB = 10.7) 8.5 g, polyoxyalkylene branched decyl ether (HLB) = 14.7) 6.5 g was sealed and sealed. Next, the temperature was raised to 110 to 120 ° C. while stirring the inside of the container. Thereafter, high-pressure emulsification was performed for 30 minutes while maintaining the inside of the container at a high pressure to obtain an aqueous dispersion of paraffin wax. Further, the wax content was adjusted to 30% by mass with pure water to obtain a wax emulsion.

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

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

<Preparation of test solution>
(Example 1)
The acrylic resin dispersion obtained in Synthesis Example 1, the organo-modified silicone emulsion obtained in Synthesis Example 18, the wax emulsion obtained in Production Example 2, butyl diglycol as a medium, and Nicepol FE-26 (JP) as an antistatic agent (Kana Chemical Co., Ltd.) was mixed so as to have the composition (parts by mass) shown in Table 3 to obtain a test solution. In addition, the compounding amounts of the acrylic resin, the organo-modified silicone and the wax in the test liquid of Example 1 were respectively 20 parts by mass × 27 parts by mass = 5.4 parts by mass, 10 parts by mass × 20 parts by mass = 2 parts by mass, and Calculated as 10 parts by mass × 30% by mass = 3 parts by mass.

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

(Examples 2 to 23 and Comparative Examples 1 to 8)
Test liquids were obtained in the same manner as in Example 1 except that the materials shown in Tables 3 to 6 were used.

I. Evaluation of initial water repellency of water-repellent fiber product by spraying method A test was performed at a shower water temperature of 20 ° C by the same method as the spraying method of JIS L 1092 (2009). In this test, the total content of the acrylic resin, other acrylic resin, urethane resin, organo-modified silicone, dimethyl silicone, wax, and other waxes was 1% by mass with the test solutions prepared with the compositions of Examples and Comparative Examples. As described above to obtain a treatment liquid. Next, the dyed 100% polyester or nylon 100% cloth was immersed (pickup ratio: 60% by mass) in the obtained processing solution. Next, the cloth subjected to the immersion treatment was dried at 130 ° C. for 2 minutes, and further heat-treated at 170 ° C. for 1 minute to obtain a water-repellent fiber product. The water repellency of the water repellent fiber product was evaluated. The results were visually evaluated according to the following grades. Tables 3 to 6 show the evaluation results.
Water repellency: State 5: No adhesion on the surface 4: Slight adhesion on the surface 3: Partially wetting on the surface 2: What is wet on the surface 1: Wetting on the whole surface Thing 0: Both sides are completely wet

II. Evaluation of Durable Water Repellency of Water Repellent Fiber Products by Spray Method To a test solution prepared with the compositions of Examples and Comparative Examples, NK Assist NY-30 (manufactured by Nika Chemical Co., Ltd.) was used as a crosslinking agent at 3 g / L. Added. Next, the test liquid is diluted with water so that the total content of acrylic resin, other acrylic resin, urethane resin, organo-modified silicone, dimethyl silicone, wax, other wax and cross-linking agent is 1% by mass, and the treatment liquid is adjusted. did. The dyed 100% polyester or nylon 100% cloth was immersed (pickup ratio: 60% by mass) using a treatment liquid. Next, the immersed cloth was dried at 130 ° C. for 2 minutes, and further heat-treated at 170 ° C. for 1 minute to obtain a water-repellent fiber product. The obtained water-repellent fiber product was washed 10 times (L-10) according to the JIS L 0217 (1995) 103 method, and the water repellency after air-drying was evaluated in the same manner as in the above-described water repellency evaluation method. Tables 3 to 6 show the evaluation results.

III. Measurement of Contact Angle for Water Repellent Fiber Products II. A water-repellent fiber product was obtained in the same manner as in the evaluation of the durability of the water-repellent fiber product. 20 μl of ion-exchanged water was dropped on the obtained water-repellent fiber product, and the contact angle of the formed water droplet was measured. An automatic contact angle meter DSA25 manufactured by KRUSS was used for measuring the contact angle. Tables 3 to 6 show the evaluation results.

IV. Evaluation of water-repellent properties of water-repellent fiber products II. A water-repellent fiber product was obtained in the same manner as in the evaluation of the durability of the water-repellent fiber product. The obtained water-repellent fiber product was placed on a horizontal and flat place, and 200 μl of water droplets were dropped on the water-repellent fiber product three drops at a time and left at room temperature. After 10, 30, 60, and 120 minutes, the number of droplets remaining on the water-repellent fiber product in the form of water droplets having a contact angle of 90 ° or more was evaluated. Tables 3 to 6 show the evaluation results.

V. Texture evaluation of water-repellent fiber product The water-repellent fiber product of 100% polyester described in II was evaluated by handling in the following five stages. The evaluation criteria were determined such that the texture of the water-repellent fiber product in Comparative Example 1 was 2, and the texture of the water-repellent fiber product in Comparative Example 2 was 5. Tables 3 to 6 show the evaluation results.
1: Hard ~ 5: Soft

VI. Evaluation of peel strength for water-repellent fiber product A test was performed in accordance with JIS K 6404-5 (1999). First, NK Assist NY-30 (manufactured by Nichika Chemical Co., Ltd.) was added as a cross-linking agent to the test solutions prepared with the compositions of Examples and Comparative Examples so as to be 3 g / L. Next, the test liquid is diluted with water so that the total content of acrylic resin, other acrylic resin, urethane resin, organo-modified silicone, dimethyl silicone, wax, other wax and cross-linking agent is 3% by mass, and the treatment liquid is adjusted. did. Next, immersion treatment (pickup ratio: 60% by mass) was performed using the treatment solution obtained for the dyed 100% nylon cloth. Next, the immersed cloth was dried at 130 ° C. for 2 minutes, and further heat-treated at 160 ° C. for 30 seconds to obtain a base cloth. A seam tape (“MELCO tape” manufactured by San Kasei Co., Ltd.) was heat-bonded to the obtained base fabric at 150 ° C. for 1 minute using a thermocompression bonding apparatus, and the peel strength between the base fabric and the seam tape was measured. It was measured by an autograph (AG-IS, manufactured by Shimadzu Corporation). The moving speed of the gripper was pulled at 100 mm / min, and the average value of the stress was defined as the peel strength [N / inch]. The results are shown in Tables 3 to 6.

Claims

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

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

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