KR20210104881A - Water repellent composition, water repellent fiber product, and method for producing water repellent fiber product - Google Patents

Abstract

[화학식 (A-1) 중, R¹은 수소 또는 메틸기를 나타내고, R²는 치환기를 갖고 있어도 좋은 탄소수 12 내지 30의 1가 탄화수소기를 나타낸다]
[화학식 (A-2)]

[화학식 (A-2) 중, R¹¹은 수소 또는 메틸기를 나타내고, R¹²는 탄소수 1 내지 6의 2가 탄화수소기를 나타내고, Z는 에스테르기 또는 아미드기를 나타내고, W는 -CO-R¹³(식 중, R¹³은 탄소수 1 내지 4의 1가 탄화수소기를 나타낸다)으로 표시되는 기, -NH-CO-NH₂로 표시되는 기 또는 화학식 (A-3)으로 표시되는 기를 나타낸다]
[화학식 (A-3)]

A water repellent composition is a ratio containing a structural unit derived from the (meth)acrylic acid ester monomer (A1) represented by the formula (A-1) and a structural unit derived from the compound (A2) represented by the formula (A-2) A fluorine-based polymer (α), and
silicone resin (β).
[Formula (A-1)]

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

[In formula (A-2), R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, W represents -CO-R ¹³ (Formula wherein R ¹³ represents a group represented by a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH ₂ , or a group represented by the general formula (A-3)]
[Formula (A-3)]

Description

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

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

Conventionally, a fluorine-based water-repellent agent containing a fluorine-based compound is known, and by treating such a fluorine-based water-repellent agent to a textile product or the like, a textile product in which water repellency is imparted to the surface thereof is known. These fluorine-based water repellents are generally prepared by polymerizing or copolymerizing a monomer (monomer) having a fluoroalkyl group. Textile products treated with a fluorine-based water repellent agent exhibit excellent water repellency, but since it has become clear that a monomer having a fluoroalkyl group is concerned about environmental impact, it does not contain a fluorine-based compound and exhibits high-performance water-repellent performance comparable to that of a fluorine-based water repellent agent. Fluorine-based water repellents have become internationally demanded.

Therefore, in recent years, research has been conducted on a non-fluorine-based water repellent that does not contain a fluorine-based compound. For example, the following Patent Document 1 discloses a surface treatment agent that is an aqueous emulsion comprising a liquid medium containing a non-fluorine polymer having a repeating unit derived from a specific (meth)acrylate ester monomer, a specific surfactant, and water, have. In Patent Document 2 below, as a polymerizable monomer not containing fluorine, a water repellent containing an acrylic copolymer in which a specific (meth)acrylate and a specific aromatic ring, or a specific cycloalkane-containing polymerizable monomer are polymerized in a specific ratio. A composition is disclosed. Patent Document 3 below discloses a processing agent for fibers containing at least one of a silicone compound, a wax compound, and a wax-zirconium compound.

Japanese Patent Laid-Open No. 2015-172198 Japanese Patent Laid-Open No. 2015-221952 Japanese Patent Laid-Open No. 2006-124866

Conventional non-fluorine-based water repellents need to treat textile products under conditions in which the water repellent component becomes high in concentration in order to impart sufficient water repellency to textile products. Textile products treated under such conditions have a problem in that the texture becomes hard and nail marks (also referred to as chalk marks) tend to appear when the fiber surface is rubbed with a fingernail.

In addition, textile products have a problem that water permeates when water droplets adhering to the surface remain for a long time. Therefore, the water repellent fiber product is required not only to have water repellency and durable water repellency, but also to have water repelling properties from which water droplets adhering to the fiber surface immediately roll down.

The present invention has been made in view of the above circumstances, and is excellent in water repellency, durable water repellency and water repellency, has a good feel, and is less prone to chalk marks, and a water repellent composition and water repellent fiber that enable the realization of the water repellent fiber product An object of the present invention is to provide a method for manufacturing a product.

The present invention relates to a ratio containing a structural unit derived from a (meth)acrylic acid ester monomer (A1) represented by the formula (A-1) and a structural unit derived from a compound (A2) represented by the formula (A-2) Provided is a water repellent composition comprising a fluorine-based polymer (α) and a silicone resin (β).

[Formula (A-1)]

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

[Formula (A-2)]

[In formula (A-2), R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, W represents -CO-R ¹³ (Formula (A-2) R ¹³ represents a group represented by a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH ₂ , or a group represented by the general formula (A-3)]

[Formula (A-3)]

According to the water-repellent composition of the present invention, by including the specific non-fluorine-based polymer (α) and the silicone resin (β) in combination, a water-repellent fiber product excellent in water repellency, durable water repellency, water repellency and feel can be obtained, and the fiber obtained The product is difficult to produce chalk marks. The present inventors guess as follows about the reason such an effect is acquired. The non-fluorine-based polymer (α) is considered to have a property of aggregation easily by having an ester group or an amide group, a urea group or a ketone group as a structural unit derived from the compound (A2). It is thought that the fiber treated with the composition containing the polymer (α) and the silicone resin (β) is likely to have an uneven structure on the fiber surface. Therefore, even if the non-fluorine-based polymer (α) and silicone resin (β) are adhered to the fiber under processing conditions at a low concentration that does not impair the feel of the fiber and does not easily cause chalk marks, a concave-convex structure is formed, resulting in sufficient water repellency and durability. The present inventors think that water repellency and water repellency can be provided.

By the way, the processing of coating a urethane resin, an acrylic resin, etc. to a predetermined part of the textile product etc. which carried out water-repellent processing may be performed. Although the textile product in this case has sufficient water repellency, it is calculated|required that the coating is hard to peel off the part to which the coating is performed. The difficulty of peeling off of a coating can be evaluated by measuring the stress (peel strength) required for peeling a coating film from the textile product which carried out the water repellency process. According to the water repellent composition of this invention, the textile product obtained can become what has sufficient peeling strength with respect to a coating.

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

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

The water-repellent textile product of the present invention is excellent in water repellency, durable water repellency, water repellency and feel, and is difficult to produce chalk marks. Further, the water-repellent fiber product of the present invention can be one having sufficient peel strength for coating.

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

ADVANTAGE OF THE INVENTION According to the manufacturing method of the water-repellent fiber product of this invention, while it is excellent in water repellency, durable water repellency, water repellency, and a feel, it is possible to obtain a water-repellent fiber product which is hard to produce a chalk mark. In addition, the water-repellent fiber product produced by the method of the present invention can be one having sufficient peel strength for the coating.

According to the present invention, there is provided a water-repellent fiber product that is excellent in water repellency, durable water repellency and water repellency, has a good feel, and is less prone to chalk marks, and a water-repellent composition and a method for producing a water-repellent fiber product that enable the realization thereof can do.

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

<Non-fluorine-based polymer (α)>

The fluorine-free polymer (α) is a structural unit derived from the (meth)acrylic acid ester monomer (A1) (hereinafter also referred to as “component (A1)”) represented by the general formula (A-1) and the general formula (A-2) contains a structural unit derived from the compound (A2) represented by (hereinafter also referred to as "component (A2)").

[Formula (A-1)]

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

[Formula (A-2)]

[In the formula (A-2), R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, W represents -CO-R ¹³ (R ¹³ represents a group represented by a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH ₂ , or a group represented by the general formula (A-3)]

[Formula (A-3)]

Here, "(meth)acrylic acid ester" means "acrylic acid ester" or the corresponding "methacrylic acid ester", and is synonymous also in "(meth)acrylic acid", "(meth)acrylamide", etc.

The component (A1) has a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. The hydrocarbon group may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and further may have an alicyclic or aromatic ring. Among these, from a viewpoint of water repellency and a feeling, it is preferable that it is linear, and it is more preferable that it is a linear alkyl group. In this case, the water repellency becomes more excellent. When the monovalent hydrocarbon group having 12 to 30 carbon atoms has a substituent, the substituent includes at least one of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloyloxy group. can be heard In this embodiment, in general formula (A-1), ^{it is preferable that R<2>} is an unsubstituted hydrocarbon group.

It is preferable that carbon number of the said hydrocarbon group is 12-24 from a viewpoint similar to the above.

As for carbon number of the said hydrocarbon group, it is more preferable that it is 12-22. When carbon number is such a range, it becomes the thing excellent in water repellency and a feel especially. Especially preferable as a hydrocarbon group is a C18-C22 linear alkyl group.

As said component (A1), for example, (meth)stearyl acrylate, (meth)acrylic acid cetyl, (meth)acrylic acid lauryl, (meth)acrylic acid myristyl, (meth)acrylic acid pentadecyl, (meth)acrylic acid Heptadecyl, (meth)acrylic acid nonadecyl, (meth)acrylic acid eicosyl, (meth)acrylic acid heneicosyl, and (meth)acrylic acid behenyl are mentioned.

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

It is preferable that the said (A1) component is a monofunctional (meth)acrylic acid ester monomer which has one polymerizable unsaturated group in 1 molecule.

The said (A1) component may be used individually by 1 type, and may be used in combination of 2 or more type.

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

In Formula (A-2), when Z is an ester group, R ¹² is a hydrocarbon group having 2 to 4 carbon atoms, and W is _{a group represented by -NH-CO-NH 2} or a group represented by Formula (A-3) It is preferable to be a group. When Z is an amide group, R ¹² is a hydrocarbon group having 2 to 4 carbon atoms, W is a group represented by ^{-CO-R 13 , and R 13} preferably has 1 to 2 carbon atoms.

Although it does not specifically limit as said (A2) component, For example, diacetone acrylamide, 2-methylpropenoic acid [2-(2-oxo-2-imidazolidinyl) ethyl], N-[2-( 2-oxoimidazolidin-3-yl)ethyl]methacrylamide. Among these, from a viewpoint of the durable water repellency of textiles, as said (A2) component, diacetone acrylamide and 2-methylpropenoic acid [2-(2-oxo-2-imidazolidinyl) ethyl] are preferable.

Said (A2) component may be used individually by 1 type, and may be used in combination of 2 or more type.

The content ratio of the structural unit derived from the component (A1) and the structural unit derived from the component (A2) in the non-fluorinated polymer (α) of the present embodiment is the mass of the component (A1) to be blended and the component (A2) It is preferable that ratio (A1)/(A2) of mass is 99.9/0.1-70/30, It is more preferable that it is 99.8/0.2-80/20, It is more preferable that it is 99.7/0.3-90/10. When (A1)/(A2) is in the said range, the durable water repellency of the textile product obtained and water repellency become more favorable.

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

The fluorine-free polymer (α) is, in addition to the component (A1) and component (A2), from the viewpoint of peel strength, at least any one monomer (VC) of vinyl chloride and vinylidene chloride (hereinafter “(VC) component”). ') as a monomer component.

(VC) As for a component, a viewpoint of maintaining the feel of textiles to vinyl chloride is preferable.

The mass of the component (VC) to be blended is preferably 10 parts by mass or more from the viewpoint of water repellency, durable water repellency and peel strength with respect to a total of 100 parts by mass of the mass of the component (A1) and the mass of the component (A2) to be blended. And it is more preferable that it is 20 mass parts or more. The mass of the component (VC) to be blended is preferably 100 parts by mass or less from the viewpoint of water repellency, durable water repellency and feel with respect to a total of 100 parts by mass of the mass of the component (A1) and the mass of the component (A2) to be blended. , it is more preferable that it is 75 mass parts or less.

The non-fluorine-based polymer (α) can improve the emulsion stability in the composition during and after the emulsion polymerization or dispersion polymerization of the non-fluorine-based polymer (α). B1) a compound represented by the formula (I-1) having an HLB of 7 to 18, (B2) a compound represented by the formula (II-1) having an HLB of 7 to 18, and (B3) a compound represented by the formula (II-1) having an HLB of 7 to 18; At least one reactive emulsifier (B) selected from compounds obtained by adding an alkylene oxide having 2 to 4 carbon atoms to oils and fats having a hydroxyl group and a polymerizable unsaturated group (hereinafter also referred to as “component (B)”) It is preferable to contain as a monomer component.

[Formula (I-1)]

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

[Formula (II-1)]

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

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

In addition, "HLB" points out the HLB value computed by the Griffin method by considering an ethyleneoxy group as a hydrophilic group, and all other than that regarded as a lipophilic group.

The HLB of the compounds of (B1) to (B3) used in the present embodiment is 7 to 18, and the emulsion stability in the composition during and after polymerization during emulsion polymerization or dispersion polymerization of the non-fluorine-based polymer (α) of the present embodiment ( Hereinafter, 9 to 15 are preferable in terms of emulsion stability). Moreover, it is more preferable to use together 2 or more types of reactive emulsifiers (B) which have different HLB within the said range from the point of the storage stability of a water repellent composition.

In the reactive emulsifier (B1) represented by the formula (I-1) used in the present embodiment, R ³ is hydrogen or a methyl group, and a methyl group from the viewpoint of copolymerizability with the component (A1) and/or the component (A2). It is more preferable that X is a C1-C6 linear or branched alkylene group, and a C2-C3 linear alkylene group is more preferable from the point of the emulsion stability of the non-fluorine-type polymer ((alpha)) of this embodiment. Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. About the kind, combination, and addition number of the alkyleneoxy group in Y<^1> , it can select suitably so that it may become in the range of said HLB. Further, when two or more kinds of alkyleneoxy groups are present, they may have a block addition structure or a random addition structure.

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

[Formula (I-2)]

[In formula (I-2), R ³ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, A ¹ O represents an alkyleneoxy group having 2 to 4 carbon atoms, 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 pieces of A ¹ O may be the same or different]

In the compound represented by the formula (I-2), R ³ is hydrogen or a methyl group, more preferably a methyl group from the viewpoint of copolymerizability with the component (A1) and/or the component (A2). X is a C1-C6 linear or branched alkylene group, and a C2-C3 linear alkylene group is more preferable from the point of the emulsion stability of the non-fluorine-type polymer ((alpha)) of this embodiment. A ¹ O is an alkyleneoxy group having 2 to 4 carbon atoms. About ^{the type and combination of A 1} O, and the number of m, it can select suitably so that it may become in the range of the said HLB. From the point of the emulsion stability of the non-fluorine-type polymer ((alpha)) of this embodiment, the integer of 1-80 is preferable and, as for m, it is more preferable that it is an integer of 1-60. When m is 2 or more, m pieces of A ¹ O may be same or different. Further, when A ¹ O is two or more types, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the formula (I-2) can be obtained by a conventionally known method, and is not particularly limited. Moreover, it can obtain easily from a commercial item, for example, "Lattemul PD-420", "Lattemul PD-430", "Lattemul PD-450" by Kao Corporation, etc. are mentioned.

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

Y ² is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. About the kind, combination, and addition number of the alkyleneoxy group in Y<^2> , it can select suitably so that it may become in the range of said HLB. Further, when two or more kinds of alkyleneoxy groups are present, they may have a block addition structure or a random addition structure. From the viewpoint of emulsion stability of the non-fluorine-based polymer (α) of the present embodiment, the alkyleneoxy group is more preferably an ethyleneoxy group.

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

[Formula (II-2)]

[In the formula (II-2), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, A ² O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n is the range of the above HLB I may be selected such that, specifically, an integer from 1 to 50, and preferably, n is 2 n of a ² O may be the same or different when more than;

^{Examples of R 4} in the compound represented by the formula (II-2) are the same as those ^{of R 4} in the formula (II-1).

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

The reactive emulsifier (B2) represented by the formula (II-2) used in the present embodiment can be synthesized by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group by a conventionally known method, which is particularly limited no. For example, it can synthesize|combine by adding alkylene oxide of predetermined amount at 120-170 degreeC under pressure using alkali catalysts, such as caustic soda and caustic potassium.

The phenols having the corresponding unsaturated hydrocarbon group include those present as pure products or mixtures extracted and purified from plants or the like in addition to industrially manufactured pure products or mixtures. For example, 3-[8 (Z), 11 (Z), 14-pentadecatrienyl] phenol, 3-[8 (Z), 11 (Z)-pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol, etc. are mentioned.

The reactive emulsifier (B3) used in this embodiment is the compound which added the C2-C4 alkylene oxide to the fats and oils which HLB is 7-18, and has a hydroxyl group and a polymerizable unsaturated group. Fats and oils having a hydroxyl group and a polymerizable unsaturated group may contain hydroxyunsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.) and mono- or diglycerides of fatty acids and triglycerides of fatty acids containing at least one type of hydroxy unsaturated fatty acid (ricinoleic acid, ricinoleic acid, 2-hydroxytetracocenic acid, etc.). From the viewpoint of the emulsion stability of the non-fluorinated polymer (α) of the present embodiment, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one type of hydroxyunsaturated fatty acid is preferable, and castor oil (including ricinoleic acid) A C2-C4 alkylene oxide adduct of the triglyceride of a fatty acid to be mentioned) is more preferable, and the ethylene oxide adduct of castor oil is still more preferable. Moreover, the added mole number of alkylene oxide can be suitably selected so that it may become in the range of the said HLB, From the point of the emulsion stability of the non-fluorine-type polymer ((alpha)) of this embodiment, 20-50 moles are more preferable, and 25- 45 moles is more preferable. Moreover, when 2 or more types of alkylene oxides are used, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B3) used in this embodiment can be synthesize|combined by adding an alkylene oxide to the fats and oils which have a hydroxyl group and a polymerizable unsaturated group by a conventionally well-known method, It is not specifically limited. For example, by using an alkali catalyst such as caustic soda and caustic potassium to triglyceride of fatty acid containing ricinoleic acid, that is, castor oil, and adding a predetermined amount of alkylene oxide at 120 to 170° C. under pressure. can do.

The composition ratio of the monomer of the component (B) in the non-fluorine-based polymer (α) of the present embodiment is the water repellency of the resulting textile product and the composition after polymerization and during emulsion polymerization or dispersion polymerization of the non-fluorine-based polymer (α) of the present embodiment From the viewpoint of improving the emulsion stability in the fluorine-free polymer (α), with respect to the total amount of the monomer components constituting the non-fluorine-based polymer (α), preferably 0.5 to 20 mass %, more preferably 1 to 15 mass %, 3 It is more preferable that it is -10 mass %.

The non-fluorine-based polymer (α) contained in the water repellent composition of the present embodiment, in addition to the component (A1) and the component (A2), from the viewpoint of improving the durable water repellency of the resulting textile product, (C1), (C2) ), (C3) and (C4), it is preferable to contain at least one second (meth)acrylic acid ester monomer (C) (hereinafter also referred to as “component C”) as a monomer component. .

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

[Formula (C-1)]

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

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

[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) methacrylic acid ester monomer represented by formula (C-3)

[Formula (C-3)]

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

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

[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 a monovalent organic group having a polymerizable unsaturated group ]

The monomer of (C1) has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group in the ester moiety. It is a (meth)acrylic acid ester monomer which has a monovalent|monohydric chain hydrocarbon group. From the viewpoint of reacting with the crosslinking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. When a non-fluorinated polymer (α) containing a monomer of (C1) having a group capable of reacting with these crosslinking agents is treated with a fiber product together with a crosslinking agent, the durability of water repellency can be improved while maintaining the texture of the resulting textile product. . The isocyanate group may be a blocked isocyanate group protected by a blocking agent.

A linear or branched form may be sufficient as the said chain|strand-shaped hydrocarbon group, and a saturated hydrocarbon group or an unsaturated hydrocarbon group may be sufficient as it. Moreover, the chain hydrocarbon group may further have a substituent other than the said functional group. Especially, it is preferable that it is a linear thing and/or a saturated hydrocarbon group at the point which can improve the durable water repellency of the textile product obtained.

Specific examples of the monomer of (C1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. can be heard These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Especially, from the point which can improve the durable water repellency of the textile product obtained, (meth)acrylic-acid 2-hydroxyethyl, (meth)acrylic-acid glycidyl, and 1, 1-bis (acryloyloxymethyl) ethyl isocyanate are preferable. do. Moreover, the point which improves the feel of the textile obtained to (meth)acrylate dimethylaminoethyl is preferable.

The mass of the component (C1) to be blended is preferably 3 parts by mass or more from the viewpoint of water repellency, and 5 parts by mass or more with respect to a total of 100 parts by mass of the mass of the component (A1) and the mass of the component (A2) to be blended. more preferably. The mass of the component (C1) to be blended is preferably 30 parts by mass or less from the viewpoint of water repellency, and 25 parts by mass or less with respect to 100 parts by mass of the total of the mass of the component (A1) and the mass of the component (A2) to be blended. more preferably.

The monomer of (C2) is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester portion, and examples of the cyclic hydrocarbon group include an isobornyl group, a cyclohexyl group, and a dicyclopentanyl group. can These cyclic hydrocarbon groups may have substituents, such as an alkyl group. However, when a substituent is a hydrocarbon group, the hydrocarbon group used as the sum total of carbon number of a substituent and a cyclic hydrocarbon group being 11 or less is selected. Moreover, it is preferable from a viewpoint of durable water repellency improvement that these cyclic hydrocarbon groups are couple|bonded directly with an ester bond. The cyclic hydrocarbon group may be alicyclic or aromatic, and when alicyclic, a saturated hydrocarbon group or an unsaturated hydrocarbon group may be sufficient as it. As a specific monomer, (meth)acrylic-acid isobornyl, (meth)acrylic-acid cyclohexyl, (meth)acrylic-acid dicyclopentanyl, etc. are mentioned. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Especially, since the durable water-repellent property of the textile product obtained can be improved, (meth)acrylic-acid isobornyl and methacrylic acid cyclohexyl are preferable, and methacrylic acid isobornyl is more preferable.

The mass of the component (C2) to be blended is preferably 3 parts by mass or more, and 5 parts by mass or more from the viewpoint of water repellency with respect to 100 parts by mass of the total of the mass of the component (A1) and the mass of the component (A2) to be blended. more preferably. The mass of the component (C2) to be blended is preferably 30 parts by mass or less from the viewpoint of water repellency, and 25 parts by mass or less with respect to 100 parts by mass in total of the mass of the component (A1) and the mass of the component (A2) to be blended. more preferably.

The monomer of (C3) is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester moiety. As the C1-C4 chain hydrocarbon group, a C1-C2 linear hydrocarbon group and a C3-C4 branched hydrocarbon group are preferable. As a C1-C4 chain hydrocarbon group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group etc. are mentioned, for example. Specific examples of the compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. . These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Especially, from the point which can improve the durable water repellency of the textile product obtained, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferable, and methyl methacrylate is more preferable.

The mass of the component (C3) to be blended is preferably 3 parts by mass or more, and 5 parts by mass or more from the viewpoint of water repellency with respect to 100 parts by mass of the total of the mass of the component (A1) and the mass of the component (A2) to be blended. more preferably. The mass of the component (C3) to be blended is preferably 30 parts by mass or less from the viewpoint of water repellency, and 25 parts by mass or less with respect to 100 parts by mass in total of the mass of the component (A1) and the mass of the component (A2) to be blended. more preferably.

The monomer of (C4) is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In this embodiment, the polyfunctional (meth)acrylic acid ester monomer which has 3 or more (meth)acryloyloxy groups in 1 molecule whose T in general formula (C-4) is a (meth)acryloyloxy group is preferable do. In the general formula (C-4), p pieces of T may be the same or different. Specific examples of the compound include ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are mentioned. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Especially, from the point which can improve the durable water repellency of the textile product obtained, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric-acid triacrylate are more preferable.

The mass of the component (C4) to be blended is preferably 3 parts by mass or more from the viewpoint of water repellency, and is preferably 5 parts by mass or more with respect to 100 parts by mass of the total of the mass of the component (A1) and the mass of the component (A2) to be blended. more preferably. The mass of the component (C4) to be blended is preferably 30 parts by mass or less from the viewpoint of water repellency, and 25 parts by mass or less with respect to a total of 100 parts by mass of the mass of the component (A1) and the mass of the component (A2) to be blended. more preferably.

The total composition ratio of the monomers of the component (C) in the non-fluorine-based polymer (α) of the present embodiment is based on the total amount of the monomer components constituting the non-fluorine-based polymer (α) from the viewpoint of water repellency and texture of the resulting textile product. With respect to it, it is preferable that it is 1-30 mass %, It is more preferable that it is 3-25 mass %, It is still more preferable that it is 5-20 mass %.

The mass of component (C) to be blended is preferably 3 parts by mass or more, and 5 parts by mass or more from the viewpoint of water repellency with respect to 100 parts by mass in total of the mass of component (A1) and the mass of component (A2) to be blended. more preferably. The mass of component (C) to be blended is preferably 30 parts by mass or less from the viewpoint of water repellency, and 25 parts by mass or less with respect to a total of 100 parts by mass of the mass of the component (A1) and the mass of the component (A2) to be blended. more preferably.

The fluorine-free polymer (α) contained in the water repellent composition of the present embodiment is, in addition to the component (A1) and the component (A2), a monofunctional monomer (D) copolymerizable with them (hereinafter also referred to as “component (D)”) ) can be contained within a range not impairing the effects of the present invention.

(D) As a component, (meth)acrylic acid ester which has hydrocarbon groups other than (meth)acryloylmorpholine, (A) component, and (C)component, (meth)acrylic acid, fumarate ester, maleic acid ester, for example, , fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, vinyl monomers other than fluorine-free (VC) components such as ethylene and styrene. have. In addition, the (meth)acrylic acid ester having a hydrocarbon group other than component (A) and component (C) may have a substituent such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, and a blocked isocyanate group in the hydrocarbon group. It may have a substituent other than a group which can react with crosslinking agents, such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond, a urethane bond, etc. As (meth)acrylic acid ester other than (A) component and (C)component, for example, methyl acrylate, (meth)acrylate 2-ethylhexyl, (meth)acrylate benzyl, ethylene glycol di(meth)acrylate, etc. can be heard Especially, (meth)acryloylmorpholine is more preferable at the point which can improve the peeling strength with respect to the coating of the textile product obtained.

The mass of the component (D) to be blended is preferably 3 parts by mass or more, and 5 parts by mass or more from the viewpoint of water repellency with respect to 100 parts by mass in total of the mass of the component (A1) and the mass of the component (A2) to be blended. more preferably. The mass of the monomer of (D) to be blended is preferably 40 parts by mass or less from the viewpoint of water repellency, and 35 parts by mass with respect to a total of 100 parts by mass of the mass of the component (A1) and the mass of the component (A2) to be blended. It is more preferable that it is less than part.

The fluorine-free polymer (α) of the present embodiment has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group capable of reacting with a crosslinking agent. It is preferable because it improves. The isocyanate group may form the blocked isocyanate group protected by the blocking agent. Moreover, since a non-fluorine-type polymer ((alpha)) also improves the feel of the textile product obtained by having an amino group, it is preferable.

It is preferable that the weight average molecular weight of the non-fluorine-type polymer ((alpha)) of this embodiment is 30,000 or more. There exists a tendency for the water repellency of the textile product obtained as a weight average molecular weight to be 30,000 or more to improve further. Moreover, as for the weight average molecular weight of a non-fluorine-type polymer ((alpha)), it is more preferable that it is 100,000 or more. In this case, the obtained textile product can exhibit water repellency more fully. As for the upper limit of the weight average molecular weight of a non-fluorine-type polymer ((alpha)), about 5 million is preferable.

The weight average molecular weight of the non-fluorinated polymer (α) is determined by adding tetrahydrofuran to the eluent at a column temperature of 40° C. and a flow rate of 1.0 ml/min using a GPC apparatus (GPC “HLC-8020” manufactured by Tosoh Corporation). Measured using a standard polystyrene equivalent. In addition, as a column, what connected three of the Tosoh Corporation brand names TSK-GEL G5000HHR, G4000HHR, and G3000HHR is used.

In this embodiment, it is preferable that the melt viscosity at 105 degreeC of a non-fluorine-type polymer ((alpha)) is 1,000 Pa.s or less. When melt viscosity in 105 degreeC is 1,000 Pa*s or less, there exists a tendency for it to become easy to keep the feel of the textile product obtained favorable. In addition, when the melt viscosity of the non-fluorine-based polymer (α) is 1,000 Pa·s or less, when the non-fluorine-based polymer (α) is emulsified or dispersed to obtain a water repellent composition, the non-fluorine-based polymer (α) is prevented from precipitating or settling Therefore, there exists a tendency for it to become easy to maintain the storage stability of a water repellent composition favorably. Moreover, as for melt viscosity in 105 degreeC, it is more preferable that it is 500 Pa*s or less. In this case, the obtained textile products etc. become a thing excellent also in a feel, fully exhibiting water repellency.

The "melt viscosity at 105° C." refers to 1 g of a fluorine-free polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm) using an expensive flow tester (for example, CFT-500 manufactured by Shimadzu Corporation). It refers to the viscosity when put in, maintained at 105° C. for 6 minutes, and measured by applying a load of ^{100 kg·f/cm 2 with a plunger.}

<Silicone resin (β)>

Silicone resin and silicone oil are mentioned as a silicone resin (beta). The silicone resin is an organopolysiloxane containing MQ, MDQ, MT, MTQ, MDT, or MDTQ as a component, in a solid state at 25°C, and having a three-dimensional structure. Here, M, D, T and Q represent (R'') ₃ SiO _0.5 unit, (R'') ₂ SiO unit, R''SiO _1.5 unit, and SiO ₂ unit, respectively. R'' represents a C1-C10 monovalent aliphatic hydrocarbon group or a C6-C15 monovalent aromatic hydrocarbon group.

A silicone resin is generally known as MQ resin, MT resin, or MDT resin, and may have a part represented by MDQ, MTQ, or MDTQ.

Silicone resin can be obtained also as a solution which melt|dissolved this in a suitable solvent. Examples of the solvent include methylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and solvents thereof having a relatively low molecular weight. mixtures and the like.

As a silicone resin solution, for example, KF7312J (trimethylsilyl group-containing polysiloxane:decamethylcyclopentasiloxane = 50:50 mixture) commercially available from Shin-Etsu Chemical Co., Ltd., KF7312F (trimethylsilyl group-containing polysiloxane:octane) methylcyclotetrasiloxane = 50:50 mixture), KF9021L (trimethylsilyl group-containing polysiloxane: low-viscosity methylpolysiloxane = 50:50 mixture), KF7312L (trimethylsilyl group-containing polysiloxane: low-viscosity methylpolysiloxane = 50:50 mixture), etc. can be heard

As the silicone resin alone, for example, MQ-1600 solid Resin (trimethylsilyl group-containing polysiloxane) commercially available from Toray Dow Corning Co., Ltd., MQ-1640 Flake Resin (trimethylsilyl group-containing polysiloxane, polypropylsilsesquioxane) ) and the like. The said commercial item contains a trimethylsilyl group containing polysiloxane, and contains MQ, MDQ, MT, MTQ, MDT, or MDTQ.

The silicone oil is a linear organopolysiloxane, and may have an organic group in at least one of a side chain and a terminal of the organopolysiloxane. Examples of such silicone oils include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil; Amino modified silicone oil, epoxy modified silicone oil, carbinol modified silicone oil, mercapto modified silicone oil, carboxyl modified silicone oil, polyether modified silicone oil, alkyl modified silicone oil, aralkyl modified silicone oil, alkylaralkyl modified silicone oil and modified silicone oils such as higher fatty acid ester-modified silicone oil, higher aliphatic amide-modified silicone oil, and organo-modified silicone oil represented by the general formula (1). In addition, in general formula (1), each structural unit may be a block or random, or may be arranged alternately.

[Formula (1)]

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

Among these silicone resins, silicone oil is preferable from the viewpoint of water repellency and dispersibility of the water repellent composition into an aqueous medium, and methylhydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carbinol-modified silicone oil, carboxyl-modified silicone Oil, mercapto-modified silicone oil, and alkylaralkyl-modified silicone oil are more preferable, and since they further improve the water repellency and durable water repellency of the resulting textile product, the alkyl-modified silicone or the resulting textile product further improves the feel, and chalk Since the occurrence of marks can be further reduced, amino-modified silicone, methylhydrogen silicone, and dimethyl silicone are more preferable.

In the organo-modified silicone oil represented by the general formula (1), the alkoxyl group having 1 to 4 carbon atoms may be linear or branched. As a C1-C4 alkoxyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. are mentioned, for example. In that it is easy to manufacture industrially, easily available, R ^20, R ²¹ and R ²² are, each independently, preferably a hydrogen atom or a methyl group, more preferably a methyl group.

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

[Formula (2)]

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

The said alkylene group may be linear or branched form may be sufficient as it.

[Formula (3)]

[In the formula (3), R ⁴² represents an alkylene group having 2 to 6 carbon atoms, R ⁴³ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and d represents an integer of 0 to 3. When d is 2 or 3, two or more R ⁴³ may be the same or different]

The said alkylene group may be linear or branched form may be sufficient as it.

Examples of the aralkyl group having 8 to 40 carbon atoms include a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, and a naphthylether group. Especially, a phenylethyl group and a phenylpropyl group are preferable at the point that it is easy to manufacture industrially and an acquisition is easy.

In the group represented by the general formula (2), from the viewpoint of being easy to manufacture industrially and readily available, R ⁴⁰ is preferably an alkylene group having 2 to 4 carbon atoms, c is preferably 0 or 1, and 0 It is more preferable that

In the group represented by the formula (3), from the viewpoint of being easy to manufacture industrially and readily available, R ⁴² is preferably an alkylene group having 2 to 4 carbon atoms, d is preferably 0 or 1, and 0 It is more preferable that

As the hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, the aralkyl group having 8 to 40 carbon atoms and the group represented by the general formula (2) are preferable from the viewpoint of being easy to manufacture industrially and easy to obtain, and the obtained fiber From the viewpoint of improving the water repellency of the product, the aralkyl group having 8 to 40 carbon atoms is more preferable.

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 a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a myristyl group, a cetyl group, and a stear group. As a C3-C22 alkyl group, a C8-C20 alkyl group is preferable at the point which can improve the water repellency of the textile product obtained, and a C12-C18 alkyl group is more preferable.

In the organo-modified silicone oil represented by Formula (1), R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently a hydrogen atom, a methyl group, an ethyl group, or an alkoxy having 1 to 4 carbon atoms. group, a hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms having an aromatic ring. In terms of industrial production and easy availability, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms. It is preferable, and it is more preferable that it is a methyl group especially.

In the organo-modified silicone oil represented by the general formula (1), a is an integer of 0 or more. It is preferable that it is 40 or less, and, as for a, it is preferable that it is 40 or less at the point which it is easy to manufacture industrially, is easy to acquire, and the peeling strength with respect to the resin coating of the textile product obtained is more preferable.

In the organo-modified silicone oil represented by the formula (1), (a+b) is 10-200. It is preferable that it is 20-100, and, as for (a+b), it is more preferable that it is easy to manufacture industrially and it is more preferable that it is 40-60 at the point that an acquisition is easy. When (a+b) is within the above range, the production and handling of silicon itself tends to be easy.

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

Examples of the silicone having a SiH group include methyl hydrogen silicone having a polymerization degree of 10 to 200, or a copolymer of dimethyl siloxane and methyl hydrogen siloxane. Among these, methyl hydrogen silicone is preferable from the point of being easy to manufacture industrially and an acquisition is easy.

The aromatic compound having a vinyl group is a compound derived from a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring ^{in R 23 in the general formula (1).} Examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allylphenyl ether, allylnaphthyl ether, allyl-p-cumylphenyl ether, allyl-o-phenylphenyl ether, allyl-tri( phenylethyl)-phenylether, allyl-tri(2-phenylpropyl)phenylether, etc. are mentioned.

The α-olefin is a compound derived from an alkyl group having 3 to 22 carbon atoms ^{in R 23 in the general formula (1).} Examples of the α-olefin include propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1 -C3-C22 alpha-olefins, such as tetradecene, 1-hexadecene, and 1-octadecene, are mentioned.

If necessary, the hydrosilylation reaction may be carried out by reacting the above-mentioned aromatic compound having a vinyl group and the above-mentioned ?-olefin with the silicone having a SiH group in the presence of a catalyst stepwise or all at once.

The amount of silicon having a SiH group, an aromatic compound having a vinyl group, and α-olefin used in the hydrosilylation reaction may be appropriately selected depending on the SiH group equivalent or number average molecular weight of the silicon having a SiH group, respectively.

As a catalyst used for hydrosilylation reaction, compounds, such as platinum and palladium, are mentioned, for example, Especially, a platinum compound is preferable. As a platinum compound, platinum (IV) chloride etc. are mentioned, for example.

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

In addition, it is preferable to perform hydrosilylation reaction in an inert gas atmosphere. As an inert gas, nitrogen, argon, etc. are mentioned, for example. The reaction proceeds even in the absence of a solvent, but a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate and the like.

Examples of the amino-modified silicone oil include compounds having an organic group containing an amino group and/or an imino group in at least one of the side chain and the terminal of the organopolysiloxane. Examples of such _{an organic group include an organic group represented by -R-NH 2} and an organic group represented by -R-NH-R'-NH 2 . As R and R', divalent groups, such as an ethylene group and a propylene group, are mentioned. Some or all of the amino group and/or imino group may be blocked amino groups and/or imino groups. Capped amino and/or imino groups are obtained, for example, by treating amino and/or imino groups with a sequestering agent. As a sequestering agent, a C2-C22 fatty acid, a C2-C22 fatty acid acid anhydride, a C2-C22 fatty acid acid halide, a C1-C22 aliphatic monoisocyanate etc. are mentioned, for example.

From the viewpoint of water repellency, the functional group equivalent of the amino-modified silicone oil is preferably 100 to 20,000 g/mol, more preferably 150 to 12,000 g/mol, and still more preferably 200 to 4,000 g/mol.

The amino-modified silicone oil is preferably liquid at 25°C. Kinematic viscosity at 25 ℃ of the amino-modified silicone oil, 10 to 100,000mm ² / s is not preferable, more preferably of 10 to 30,000mm ² / s is not preferable, and 10 to 5,000mm ² / s more. When the kinematic viscosity at 25°C is 100,000 mm ² /s or less, it tends to be easy to ensure workability. The kinematic viscosity at 25°C means a value measured by the method described in JIS K 2283:2000 (Uberode viscometer).

As amino-modified silicone oil, it is possible to obtain easily also as a commercial item. As a commercial item, For example, KF8005, KF-868, KF-864, KF-393, KF-8021 (all are the Shin-Etsu Chemical Co., Ltd. product, brand names), TSF-4709, XF42-B1989 (Momentive performance matte) Reals Japan (manufactured by Co., Ltd., brand name), BY16-872, SF-8417, BY16-853U, BY16-892 (all are manufactured by Toray Dow Corning Co., Ltd., brand name), etc. are mentioned.

In addition, silicone oils other than amino-modified silicone oil can also be easily obtained as a commercial item similarly. As a commercial item, KF-101 (Shin-Etsu Chemical Co., Ltd. product, brand name, epoxy-modified silicone oil), X-22-3701E (Shin-Etsu Chemical Co., Ltd. product, brand name, carboxyl-modified silicone oil) are, for example, , SF8428 (manufactured by Toray Dow Corning, trade name, carbinol-modified silicone oil), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, methylhydrogen silicone oil), X-22-715 (Shin-Etsu Chemical Co., Ltd.) Kaku Kogyo Co., Ltd. product name, higher fatty acid ester-modified silicone oil), KF-96-3000cp (Shin-Etsu Chemical Co., Ltd. product name, dimethyl silicone oil), SF8416 (Toray Dow Corning Co., Ltd. product name) , alkyl-modified silicone oil), SH203 (manufactured by Toray Dow Corning Co., Ltd., trade name, alkyl aralkyl-modified silicone oil), SF8410 (manufactured by Toray Dow Corning Co., Ltd., trade name, polyether-modified silicone oil), and the like. .

You may use a silicone resin ((beta)) individually by 1 type or in combination of 2 or more type.

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

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

It is also possible to add an additive etc. to the water repellent composition of this embodiment as needed. Examples of additives include other water repellents, surfactants, defoamers, pH adjusters, antibacterial agents, mildew inhibitors, colorants, antioxidants, deodorants, various organic solvents, chelating agents, antistatic agents, catalysts, crosslinking agents, antibacterial deodorants, flame retardants, softeners, spindles (防皺劑) and the like.

As surfactant, well-known nonionic surfactant, anionic surfactant, cationic surfactant, and amphoteric surfactant can be used. Surfactant can be used individually by 1 type or in combination of 2 or more type.

As an antifoaming agent, For example, oil-fat system antifoamers, such as castor oil, sesame oil, flaxseed oil, animal and vegetable oil; fatty acid-based antifoaming agents such as stearic acid, oleic acid, and palmitic acid; Fatty acid ester antifoaming agents, such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, and butyl stearate; alcohol-based antifoaming agents such as polyoxyalkylene monohydric alcohol, di-t-amylphenoxyethanol, 3-heptanol, and 2-ethylhexanol; ether antifoaming agents such as di-t-amylphenoxyethanol, 3-heptyl cellosolve, nonyl cellosolve, and 3-heptyl carbitol; phosphate ester antifoaming agents such as tributyl phosphate and tris (butoxyethyl) phosphate; amine-based antifoaming agents such as diamylamine; amide antifoaming agents such as polyalkyleneamide and acylate polyamine; Sulfuric acid ester type antifoaming agents, such as sodium lauryl sulfate; Mineral oil etc. are mentioned. An antifoaming agent can be used individually by 1 type or in combination of 2 or more types.

Examples of the pH adjuster include organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, citric acid, malic acid, sulfonic acid, methanesulfonic acid, and toluenesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; and bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolamine, pyridine and morpholine. A pH adjuster can be used individually by 1 type or in combination of 2 or more type.

As an organic solvent, For example, C1-C8 aliphatic alcohols, such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, hexyl alcohol, and 2-ethylhexyl alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and diacetone alcohol; esters such as ethyl acetate, methyl acetate, butyl acetate, methyl lactate, and ethyl lactate; ethers such as diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tertiary butyl ether, and butyl carbitol; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and 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 ; glycol esters such as ethylene glycol monomethyl 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. An organic solvent can be used individually by 1 type or in combination of 2 or more type.

As an antistatic agent, it is good to use the thing which does not impair water-repellent performance easily. Examples of the antistatic agent include cationic surfactants such as higher alcohol sulfate ester salts, sulfuric oil, sulfonic acid salts, quaternary ammonium salts and imidazoline quaternary salts, and nonionics such as polyethylene glycol type and polyhydric alcohol ester type. Amphoteric surfactants, such as surfactant, imidazoline type quaternary salt, alanine type, and betaine type, high molecular compound type antistatic polymer, polyalkylamine, etc. are mentioned. An antistatic agent can be used individually by 1 type or in combination of 2 or more type.

Next, the manufacturing method of the water repellent composition of this embodiment is demonstrated.

The composition containing a non-fluorine-type polymer ((alpha)) can be manufactured by the radical polymerization method. Moreover, it is preferable to superpose|polymerize by the emulsion polymerization method or the dispersion polymerization method from the point of the performance and environment of the water repellent obtained among this radical polymerization method.

For example, the fluorine-free polymer (?) can be obtained by emulsion polymerization or dispersion polymerization of the component (A1) and the component (A2) in a medium. More specifically, for example, component (A1), component (A2) and, if necessary, component (B), component (C) and component (D), and an emulsification auxiliary or dispersing auxiliary agent are added to the medium, and this mixture solution 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 a monomer and a reactive emulsifier can be polymerized. Moreover, as a means for emulsifying or dispersing the said liquid mixture, a homomixer, a high pressure emulsifier, an ultrasonic wave, etc. are mentioned.

As the emulsifying aid or dispersing aid (hereinafter also referred to as “emulsifying aid, etc.”), at least one selected from nonionic surfactants other than the reactive emulsifier (B), cationic surfactants, anionic surfactants, and amphoteric surfactants. can be used It is preferable that content of an emulsification auxiliary agent etc. is 0.5-30 mass parts with respect to 100 mass parts of all monomers, It is more preferable that it is 1-20 mass parts, It is more preferable that it is 1-10 mass parts. When content of the said emulsification auxiliary agent etc. is 0.5 mass part or more, compared with the case where content of the emulsification auxiliary agent etc. is less than 0.5 mass part, there exists a tendency for the dispersion stability of a liquid mixture to improve further. When the content of the emulsification aid is 30 parts by mass or less, the water repellency of the obtained non-fluorine-based polymer tends to be further improved compared with the case where the content of the emulsification aid or the like exceeds 30 parts by mass.

Examples of the cationic surfactant include monoalkyltrimethylammonium salts having 8 to 24 carbon atoms, dialkyldimethylammonium salts having 8 to 24 carbon atoms, monoalkylamine acetate salts having 8 to 24 carbon atoms, dialkylamine acetate salts having 8 to 24 carbon atoms, and dialkylamine acetate salts having 8 to 24 carbon atoms. The alkylimidazoline quaternary salt of 24 etc. are mentioned. Among these, a C12-C18 monoalkyltrimethylammonium salt and a C12-18 dialkyldimethylammonium salt are preferable from a viewpoint of emulsification property and process stability.

These cationic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

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

Examples of the alcohols include linear or branched C8-C24 alcohols or alkenols, acetylene alcohols represented by the general formula (AL-1) or the general formula (AL-2), and the like.

[Formula (AL-1)]

[Wherein, R ⁵¹ and R ⁵² each independently represent an alkyl group having a straight or branched chain having 1 to 8 carbon atoms or an alkenyl group having a straight or branched chain having 2 to 8 carbon atoms]

[Formula (AL-2)]

[wherein, R ⁵³ represents an alkyl group having a straight or branched chain having 1 to 8 carbon atoms or an alkenyl group having a straight or branched chain having 2 to 8 carbon atoms]

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

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

As fatty acids, a linear or branched C8-C24 fatty acid etc. are mentioned.

As polyhydric alcohol fatty acid ester, the condensation reaction product of a polyhydric alcohol and C2-C30 (carbon of a carboxyl group is included) carboxylic acid is mentioned. Examples of such polyhydric alcohol fatty acid esters include sorbitan esters composed of sorbitan (alcohol) and carboxylic acid having 2 to 30 carbon atoms (including carbon in a carboxyl group).

Carbon number of the carboxylic acid which comprises sorbitan ester is 2-30, and it is preferable that it is 5-21. The sorbitan ester may be a monocarboxylic acid ester of sorbitan and one carboxylic acid, a dicarboxylic acid ester of sorbitol and two carboxylic acids, or a tricarboxylic acid ester of sorbitol and three carboxylic acids, and is preferably a monocarboxylic acid ester.

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

[Formula (4)]

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

[Formula (5)]

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

Examples of the compound represented by the formula (4) or (5) include sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquistearate, Sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitic acid, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitate tristearate heartburn, etc. are mentioned.

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

Among these, from the viewpoint of having little effect on water repellency, little effect on light resistance, and good emulsification of the copolymer, a straight or branched chain alcohol or alkenol having 8 to 24 carbon atoms, and general formula (AL-1) ) or acetylene alcohol represented by formula (AL-2) is preferred, and straight or branched chain alcohols having 8 to 24 carbon atoms, and acetylene alcohol represented by formula (AL-1) or formula (AL-2) are more preferred. desirable.

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. have. From a viewpoint that there is little influence on water repellency and the emulsification property of a fluorine-free polymer ((alpha)) becomes favorable, as an alkylene oxide, ethylene oxide and 1,2-propylene oxide are preferable and ethylene oxide is more preferable.

As for the added mole number of an alkylene oxide, 1-200 are preferable, More preferably, it is 3-100, More preferably, it is 5-50. When the added mole number of alkylene oxide is in the said range, it will become easy to obtain water repellency and product stability at a high level.

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

HLB = (hydrophilic group × 20) / molecular weight

The HLB of the nonionic surfactant used in the present embodiment is 7 to 18, and the emulsion stability (hereinafter, simply emulsion stability) in the composition during and after the emulsion polymerization or dispersion polymerization of the non-fluorine-based polymer (α) of the present embodiment. 9 to 15 are preferable from the point of). Moreover, it is more preferable to use together 2 or more types of nonionic surfactant which has different HLB within the said range from the point of the storage stability of a water repellent composition. Moreover, it is preferable to use together a cationic surfactant and a nonionic surfactant from a viewpoint of emulsion stability and water repellency.

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

As said polymerization initiator, well-known polymerization initiators, such as an azo type, a peroxide type, or a redox type, can be used suitably. It is preferable that content of a polymerization initiator is 0.01-2 mass parts of polymerization initiators with respect to 100 mass parts of all monomers. If content of a polymerization initiator is the said range, a weight average molecular weight can manufacture 30,000 or more non-fluorine-type polymer ((alpha)) efficiently.

Moreover, in a polymerization reaction, for the purpose of molecular weight adjustment, you may use chain transfer agents, such as dodecyl mercaptan and t-butyl alcohol. It is preferable that it is 0.3 mass part or less with respect to 100 mass parts of all monomers, and, as for content of a chain transfer agent, it is more preferable that it is 0.1 mass part or less. When the content of the chain transfer agent is 0.3 parts by mass or less, it is possible to suppress an excessive decrease in molecular weight, and it tends to become easy to efficiently produce a non-fluorinated polymer (α) having a weight average molecular weight of 30,000 or more.

In addition, you may use a polymerization inhibitor for molecular weight adjustment. By addition of a polymerization inhibitor, the non-fluorine-type polymer (alpha) which has a desired weight average molecular weight can be obtained easily.

The temperature of the polymerization reaction is preferably 20°C to 150°C. When the temperature is 20°C or higher, compared with the case where the temperature is lower than 20°C, it tends to become easy to sufficiently advance polymerization. When the temperature is 150°C or less, control of the heat of reaction becomes easier compared with the case where the temperature exceeds 150°C.

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

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

The water repellent composition of this embodiment can be prepared by mixing the composition containing the non-fluorine-type polymer ((alpha)) obtained by the said method, and a silicone resin ((beta)). The silicone resin (β) may be a commercially available product or the like.

The water-repellent fiber product of this embodiment consists of the fiber product to which the non-fluorine-type polymer ((alpha)) of this embodiment and silicone resin ((beta)) adhered.

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

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

As a method of processing a textile product with the said processing liquid, processing methods, such as immersion, spraying, and application|coating, are mentioned, for example. Further, in the case where the water repellent composition contains water, it is preferably dried to remove the water after adhesion to the textile product.

The amount of adhesion of the water repellent composition to the textile product can be appropriately adjusted depending on the degree of water repellency required, but from the viewpoint of water repellency and feel, per 100 g of the textile product, the non-fluorine-based polymer (α) and silicone resin ( It is preferable to adjust so that the adhesion amount of the sum total of (beta)) may be 0.01-10 g, and it is more preferable to adjust so that it may become 0.05-5 g.

In addition, after making the non-fluorine-type polymer (alpha) and silicone resin (beta) of this embodiment adhere to a textile product, it is preferable to heat-process suitably. Although there is no restriction|limiting in particular as for temperature conditions, If the water repellent composition of this embodiment is used, sufficient water repellency can be expressed in textile products by 100-130 degreeC mild conditions. The temperature condition may be a high-temperature treatment of 130°C or higher (preferably up to 200°C). Therefore, according to the water-repellent fiber product of this embodiment, the deterioration of the fiber product due to heat is suppressed, the texture of the fiber product at the time of water repellency treatment becomes soft, and furthermore, sufficient water repellency for the fiber product under mild heat treatment conditions, that is, low temperature curing conditions can be given

In particular, when it is desired to improve durable water repellency, the above process of treating textile products with a treatment liquid containing a water repellent composition, and a melamine resin, glyoxal resin, isocyanate group or a compound having one or more blocked isocyanate groups. It is preferable to water-repellent a textile product by the method including the process of making a crosslinking agent adhere to a textile product, and heating this. Moreover, when it is desired to further improve durable water repellency, it is preferable that the water repellent composition contains the non-fluorine-type polymer ((alpha)) which copolymerized the monomer which has the functional group which can react with the said crosslinking agent.

As melamine resin, the compound which has a melamine skeleton can be used, For example, Polymethylolmelamine, such as trimethylolmelamine and hexamethylolmelamine; alkoxymethylmelamine in which some or all of the methylol groups of polymethylolmelamine are alkoxymethyl groups having an alkyl group having 1 to 6 carbon atoms; The acyloxymethylmelamine etc. in which a part or all of the methylol groups of polymethylolmelamine became the acyloxymethyl groups which have a C2-C6 acyl group are mentioned. Any of a monomer or a dimer or more multimer may be sufficient as these melamine resin, or these mixtures may be used. Moreover, what co-condensed urea etc. to a part of melamine can be used. As such a melamine resin, DIC Corporation Beccamine APM, Becamine M-3, Becamine M-3 (60), Becamine MA-S, Beccamine J-101, and Becamine J- are made, for example, by DIC Corporation, for example. 101LF, Union Kagaku Kogyo Co., Ltd. Unica Resin 380K, Mickey Linken Co., Ltd. Rikken Resin MM series, etc. are mentioned.

As glyoxal resin, a conventionally well-known thing can be used. Examples of the glyoxal resin include 1,3-dimethylglyoxalurea-based resin, dimethyloldihydroxyethyleneurea-based resin, and dimethyloldihydroxypropyleneurea-based resin. The functional groups of these resins may be substituted with other functional groups. Examples of such glyoxal resins include Beccamine N-80, Becamine NS-11, Becamine LF-K, Beccamine NS-19, Becamine LF-55P Conck, Beccamine NS manufactured by DIC Corporation. -210L, Beccamine NS-200 and Beccamine NF-3, Uni Resin GS-20E manufactured by Union Chemical Co., Ltd., Riken Resin RG series and Riken Resin MS series manufactured by Mickey Linken Kogyo Co., Ltd., etc. can

It is preferable to use a catalyst for a melamine resin and a glyoxal resin from a viewpoint of accelerating|stimulating reaction. It will not restrict|limit especially if it is a catalyst normally used as such a catalyst, For example, borofluoride compounds, such as ammonium borofluoride and a fluoroboride salt; neutral metal salt catalysts such as magnesium chloride and magnesium sulfate; Inorganic acids, such as phosphoric acid, hydrochloric acid, and boric acid, etc. are mentioned. If necessary, organic acids such as citric acid, tartaric acid, malic acid, maleic acid, and lactic acid may be used in combination with such a catalyst as a cocatalyst. As such a catalyst, for example, ketalyst ACX, ketalyst 376, ketalyst O, ketalyst M, ketalyst G(GT) manufactured by DIC Corporation, ketalyst X-110, ketalyst GT-3 and ketalst Liszt NFC-1, Unica Catalyst 3-P and Unica Catalyst MC-109 manufactured by Union Kagaku Kogyo Co., Ltd., Riken Fixer RC Series, Riken Fixer MX Series and Riken Fixer RZ-, manufactured by Miki Rinken 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.

It will not specifically limit, if it is a compound which has two or more isocyanate groups in a molecule|numerator as a polyfunctional isocyanate compound, A well-known polyisocyanate compound can be used. Examples of the polyfunctional isocyanate compound include diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimers or trimers of these diisocyanate compounds. It is preferable that carbon number of alkylene diisocyanate is 1-12.

Examples of the diisocyanate compound include 2,4 or 2,6-trylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, Hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, phenylene diisocyanate, tolylene or naphthylene diisocyanate, 4,4'- methylene-bis(phenylisocyanate), 2,4'-methylene-bis(phenylisocyanate), 3,4'-methylene-bis(phenylisocyanate), 4,4'-ethylene-bis(phenylisocyanate), ω,ω '-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylcyclohexane, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate -1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanatecyclohexane, 4,4'-methylene-bis(cyclohexylisocyanate), 3-isocyanate-methyl-3,5,5-trimethylcyclo Hexyl isocyanate, acid-diisocyanate dimer, ω,ω'-diisocyanatediethylbenzene, ω,ω'-diisocyanatedimethyltoluene, ω,ω'-diisocyanatediethyltoluene, bis(2-isocyanateethyl) fumarate esters, 1,4-bis(2-isocyanate-prop-2-yl)benzene and 1,3-bis(2-isocyanate-prop-2-yl)benzene.

As a triisocyanate compound, triphenylmethane triisocyanate, dimethyl triphenylmethane tetraisocyanate, tris (isocyanate phenyl) -thiophosphite etc. are mentioned, for example.

The modified polyisocyanate compound derived from the diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups, for example, a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, an allophanate structure, and a trimer. The polyisocyanate which has a sieve structure etc., the adduct body of the aliphatic isocyanate of trimethylol propane, etc. are mentioned. Polymeric MDI (MDI = diphenylmethane diisocyanate) can also be used as the polyfunctional isocyanate compound.

A polyfunctional isocyanate compound can be used individually by 1 type or in combination of 2 or more type.

The isocyanate group which a polyfunctional isocyanate compound has may be as it is, and the blocked isocyanate group blocked by the blocking agent may be sufficient as it. 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; phenols such as phenol, methylphenol, chlorophenol, iso-butylphenol, tert-butylphenol, iso-amylphenol, octylphenol, and nonylphenol; lactams such as ε-caprolactam, δ-valerolactam and γ-butyrolactam; Active methylene compounds, such as malonic acid dimethyl ester, malonic acid diethyl ester, acetylacetone, methyl acetoacetate, and ethyl acetoacetate; Oximes, such as form aldoxime, aceto aldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; imidazole compounds such as imidazole and 2-methylimidazole; Soda bisulfite, etc. are mentioned. Among these, from a viewpoint of water repellency, pyrazoles and oximes are preferable.

As the polyfunctional isocyanate compound, a water-dispersible isocyanate in which water dispersibility is imparted to the polyisocyanate by introducing a hydrophilic group into the polyisocyanate structure to have a surfactant effect can also be used. Moreover, in order to accelerate|stimulate reaction, you may use together well-known catalysts, such as organotin and organozinc.

A crosslinking agent and a catalyst can be used individually by 1 type or in combination of 2 or more type.

The crosslinking agent is, for example, a crosslinking agent dissolved in an organic solvent, immersed in a treatment liquid emulsified and dispersed in water, and the object to be treated (textile product) is dried by a method of drying the treatment liquid adhering to the object to be treated. Can be attached to water. Then, by heating the crosslinking agent adhering to the object to be treated, the reaction between the crosslinking agent, the object and the non-fluorine-based polymer (?) can proceed. In order to sufficiently advance the reaction of the crosslinking agent to more effectively improve washing durability, heating at this time is preferably performed at 110 to 180° C. for 1 to 5 minutes. You may perform the process of adhesion of a crosslinking agent and a heating simultaneously with the process of treating with the treatment liquid containing the said water repellent composition. When carrying out at the same time, for example, a treatment liquid containing a water repellent composition and a crosslinking agent is made to adhere to a to-be-processed object, and after water is removed, the crosslinking agent adhering to a to-be-processed object is further heated. When the simplification of the water-repellent processing process, reduction of heat quantity, and economic efficiency are considered, it is preferable to carry out simultaneously with the treatment process of a water-repellent agent composition.

Moreover, when a crosslinking agent is used excessively, there exists a possibility that a feel may be impaired. It is preferable to use the said crosslinking agent in the quantity of 0.1-50 mass % with respect to the to-be-processed object (textile product), and it is especially preferable to use it in the quantity of 0.1-10 mass %.

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

The water-repellent fiber product of this embodiment can coat a predetermined part. As a coating process, the moisture-permeable waterproofing process in a sports use or an outdoor use, a windproof process, etc. are mentioned. As a processing method, for example, in the case of moisture-permeable waterproofing, it can process by apply|coating the coating liquid containing a medium, such as a urethane resin, an acrylic resin, etc. to the single side|surface of the water-repellent-treated textile product, and drying.

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

For example, in the case of producing the non-fluorine-based polymer (α) contained in the water repellent composition of the present invention, in the above embodiment, the polymerization reaction is performed by radical polymerization, but ionizing radiation such as ultraviolet rays, electron beams, and γ rays You may perform a polymerization reaction by photopolymerization by irradiating a etc.

Further, in the present invention, the water repellent composition is treated to a textile product to obtain a water repellent fiber product.

In this case, the method for attaching the water-repellent composition to the article and the amount of the water-repellent agent to be adhered can be arbitrarily determined according to the type of the object to be treated or the like.

Example

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

<Preparation of polymer dispersion>

A liquid mixture having the components shown in Tables 1 and 2 (in the table, the numerical value indicates (g)) was polymerized according to the procedure shown below to obtain a dispersion of a polymer or a hydrophobic compound.

(Synthesis Example 1)

In an autoclave, 23.4 g of stearyl acrylate, 0.6 g of diacetone acrylamide, 0.2 g of Neugen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7) 0.2 g, Neugen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5) 1.3 g, Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched Decyl ether, HLB = 10.5) 0.5 g, stearyl trimethylammonium sulfate 0.4 g, tripropylene glycol 12.5 g, and water 54.9 g were put, mixed and stirred at 45 degreeC, and it was set as the liquid mixture. The mixed solution was irradiated with ultrasonic waves to emulsify and disperse all monomers. Then, 0.2 g of azobis (isobutylamidine) dihydrochloride was added to the mixture, and under a nitrogen atmosphere, 6 g of vinyl chloride was continuously pressurized to maintain the internal pressure of an autoclave of 0.3 MPa while radical polymerization at 60 ° C. for 6 hours. , a fluorine-free polymer (α) dispersion containing 30.0% by mass of the fluorine-free polymer (α) was obtained.

(Synthesis Examples 2 to 8)

Polymerization was carried out in the same manner as in Synthesis Example 1 except that the materials shown in Table 1 were used to obtain dispersions of non-fluorine-based polymers (α) containing 30.0 mass% of non-fluorine-based polymers (α), respectively.

(Comparative Synthesis Examples 1 to 5)

Polymerization was carried out in the same manner as in Synthesis Example 1 except that the materials shown in Table 2 were used to obtain dispersions of other non-fluorine-based polymers containing 30.0% by mass of other non-fluorine-based polymers, respectively.

(Comparative Synthesis Example 6)

In a 1,000 mL flask, 240.3 g of 1,4-butanediol, 758.5 g of stearic acid, and 1.2 g of p-toluenesulfonic acid were put, and the product was dehydrated at 130 to 200°C under a nitrogen stream for 4 hours to obtain a product. As a result of measuring the acid value and hydroxyl value of the obtained product, the acid value was 0.5 mg KOH/g, and the hydroxyl value was 162.1 mg KOH/g. In another container, 574.1 g of the above product, 270.5 g of hexamethylene diisocyanate, and 0.9 g of a bismuth-based catalyst (Nitto Kasei Co., Ltd., Neostan U-600) were put, and the reaction was performed at 80°C for 3 hours. The reaction was carried out until NCO% became 8.0. After the reaction, the temperature was lowered to 40°C, then, 154.6 g of 3,5-dimethylpyrazole was added, and the reaction was performed at 40°C for 1 hour to obtain a hydrophobic compound. In a 500 mL stainless steel container, 40 g of the obtained hydrophobic compound, 50 g of methyl ethyl ketone, 5 g of Decaglin 1-L (nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku), 5 g of Decaglin 1-SV (nonionic surfactant, Daiichi Kogyo Seiya) 5 g (manufactured by Ku) and 5 g of Arcado T-28 (cation surfactant, manufactured by Lion Specialty Chemicals) were added and dissolved by heating at 50 °C. Next, 295 g of 80 degreeC hot water was added, and it emulsified for 20 minutes, maintaining 80 degreeC using the ultrasonic emulsifier US-600E (Nippon Seiki Co., Ltd.). Thereafter, it cooled to obtain a 10% dispersion of the hydrophobic compound.

In addition, each polymer in the polymer dispersion liquid obtained in Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 to 5 was 98% or more of all monomers by gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation). This polymerization was confirmed.

Details of the data shown in Tables 1 and 2 are as follows.

Neugen XL-100 (14.7) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7)

Neugen XL-60 (12.5) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5)

Neugen XL-40 (10.5) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5)

<Preparation of dispersion liquid containing silicone resin>

(Preparation Example 1)

As a silicone resin, 20 parts by mass of SF 8416 (alkyl-modified silicone, manufactured by Tore Dow Corning Co., Ltd.) and 1 part by mass of SPAN60 (sorbitan-based nonionic surfactant, HLB = 4.7, manufactured by Kao Corporation), TWEEN80 (Sorbitan type nonionic surfactant, HLB=15.0, Kao Co., Ltd. product) 1 mass part and 5 mass parts of butyldiglycol were mixed. Then, it added, mixing 73.0 mass parts of water little by little to the obtained mixture, and obtained the dispersion liquid containing 20 mass % of silicone resins ((beta)).

(Preparation Examples 2 to 4)

Except having used the following resin as a silicone resin, it carried out similarly to Preparation Example 1, and obtained the silicone resin dispersion liquid containing 20 mass % of silicone resins.

(Preparation Example 2) BY 16-872 (amino silicone, manufactured by Toray Dow Corning Co., Ltd., trade name)

(Preparation Example 3) KF-9901 (methylhydrogen silicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name)

(Preparation Example 4) KF-96-3000cs (dimethyl silicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name)

(Preparation Example 5)

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

To 15 parts by mass of MQ-1600 (silicone resin = trimethylsilyl group-containing polysiloxane, manufactured by Toray Dow Corning Co., Ltd., trade name), 15 parts by mass of dimethyl silicone (6cs, manufactured by Tore Dow Corning Co., Ltd., brand name) was added, and silicone The resin was mixed until dissolved to obtain a mixture. 18.5 mass parts of the obtained mixture and 0.5 mass parts of ethylene oxide 5 mol adducts of a C12-C14 branched alcohol were mixed. Then, it added, mixing 81 mass parts of water little by little, and obtained the dispersion liquid which contains 18.5 mass % of silicone resin and dimethyl silicone in total in total.

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

<Preparation of water repellent composition>

(Examples 1 to 15 and Comparative Examples 1 to 9)

A non-fluorine-based polymer (α) dispersion and other non-fluorine-based polymer dispersions or hydrophobic compound dispersions and silicone resin (β) dispersions and water so as to have the compositions shown in Tables 3 to 5 (in the tables, numerical values indicate (mass %)) were mixed to obtain a water repellent composition, respectively.

(Evaluation of water repellency of textile products)

According to the spray method of JIS L 1092 (2009), the shower water temperature was set to 20 degreeC, and the test was carried out. In this test, dyed polyester 100% fabric or polyester (PET)/polyurethane (PU) blend fabric (polyester/polyurethane = 80/20) was immersed in the water repellent composition of Examples and Comparative Examples. Then, it dried at 130 degreeC for 2 minutes, heat-processed at 170 degreeC for 30 second conditions, and evaluated the water repellency of the obtained cloth. The results were visually evaluated on the following scale. In addition, when the characteristic is slightly good, "+" is attached to the grade, and when the characteristic is slightly inferior, "-" is attached to the grade. The results are shown in Tables 3-5.

Water repellency: condition

5: No adhesion wetting on the surface

4: Showing some adhesion wetting on the surface

3: Showing partial wetting on the surface

2: Showing wetting on the surface

1: Showing wetting over the entire surface

0: Both surfaces are completely wet

(Evaluation of the texture of textile products)

The texture was evaluated using the dyed polyester 100% cloth, which was immersed in the water repellent composition of Examples and Comparative Examples in a treatment solution, dried at 130° C. for 2 minutes, and further heat-treated at 170° C. for 30 seconds. . The results were evaluated in five stages shown below in terms of handling. The results are shown in Tables 3-5.

1: Hard ~ 5: Soft

(Evaluation of durability and water repellency of textile products)

According to the spray method of JIS L 1092 (2009), the shower water temperature was set to 20 degreeC, and the test was carried out. Blocked isocyanate type crosslinking agent (NK assist NY-50) was added to the water repellent composition of an Example and a comparative example so that it might become a density|concentration of 0.03 mass %, and the processing liquid was prepared. Next, the dyed polyester 100% cloth was immersed in the prepared processing liquid. After the immersion treatment, the cloth (L-0) obtained by drying at 130°C for 2 minutes, and further heat-treating at 170°C for 60 seconds and washing according to method 103 of JIS L 0217 (1995) 30 times (L-30) were performed. The water repellency of the subsequent fabric was evaluated in the same manner as in the water repellency evaluation method. Also, in the case of polyester (PET)/polyurethane (PU) blend fabric (polyester/polyurethane = 80/20), except for changing the heat treatment temperature from 170°C to 160°C, in the case of 100% polyester fabric was evaluated as The results are shown in Tables 3-5.

(Peel strength for coatings on textile products)

The test was done based on JISK6404-5 (1999). In this test, the dyed 100% nylon cloth was immersed in the water repellent compositions of Examples and Comparative Examples, dried at 130° C. for 2 minutes, and further heat treated at 170° C. for 30 seconds. did with Using a thermocompression device, a hot melt adhesive tape (“MELCO Tape” manufactured by San Kasei Co., Ltd.) was thermally bonded to the obtained fabric at 150° C. for 1 minute using a thermocompression device, and the peel strength between the fabric and the seam tape was autographed ( It measured by AG-IS, Shimadzu Corporation make). The moving speed of household tools was pulled at 100 mm/min, and the average value of stress was made into peeling strength [N/inch]. The results are shown in Tables 3-5.

(Evaluation of repelling properties of textile products)

According to the spray method of JIS L 1092 (2009), the shower water temperature was 20 degreeC, the test was done, the water repelling degree at the time of spray water repellency was visually confirmed, and it evaluated in 5 steps shown below. In this test, the dyed polyester/polyurethane blend fabric (polyester/polyurethane = 80/20) was immersed in the water repellent compositions of Examples and Comparative Examples, and then dried at 130° C. for 2 minutes, and further The repulsion property of the obtained cloth was evaluated by heat-processing at 170 degreeC in the furnace for 30 seconds. In addition, when the characteristic is slightly good, "+" is attached to the grade, and when the characteristic is slightly inferior, "-" is attached to the grade. The results are shown in Tables 3-5.

Bounceability: Status

5: Water in contact with the fabric maintains a fine water droplet shape, and water is splashing from the fabric surface

4: Water in contact with the fabric maintains a fine water droplet shape and rolls down the fabric surface

3: Water in contact with the fabric maintains the shape of a large water droplet and rolls off the fabric surface

2: Water in contact with the fabric does not maintain the shape of a droplet, and falls directly on the surface of the fabric

1: Water in contact with the fabric does not retain water droplets, but falls off while meandering

(Evaluation of chalk marks in textile products)

The chalk mark was evaluated using a dyed 100% polyester cloth, which was immersed in the water repellent compositions of Examples and Comparative Examples, dried at 130° C. for 2 minutes, and further heat-treated at 170° C. for 30 seconds. The surface of the processing cloth was scratched with a nail and visually evaluated in five grades shown below. The results are shown in Tables 3-5.

5: Clear nail marks are confirmed

4: Nail marks are confirmed

3: Slight nail marks are confirmed

2: Almost no nail marks

1: No nail marks

Claims (4)

A fluorine-free polymer (α) containing a structural unit derived from the (meth)acrylic acid ester monomer (A1) represented by the formula (A-1) and a structural unit derived from the compound (A2) represented by the formula (A-2) (α) )Wow,
A water repellent composition comprising a silicone resin (β).
[Formula (A-1)]

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

[In formula (A-2), R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, W represents -CO-R ¹³ (Formula (A-2) R ¹³ represents a group represented by a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH ₂ , or a group represented by the general formula (A-3)]
[Formula (A-3)]

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