Water repellant composition, water-repellent fiber product, and method for manufacturing water-repellent fiber product

Abstract

To provide: a water-repellent fiber product that is excellent in water repellency, durable water repellency and water beading properties, has a good texture, and reduces the occurrence of chalk marks; and a water repellent composition that enables materialization thereof.SOLUTION: The water repellant composition comprises: a non-fluorinated polymer (α) containing constituent units derived from a (meth)acrylic acid ester monomer (A1) represented by general formula (A-1) in the figure and constituent units derived from a compound (A2) represented by general formula (A-2) in the figure; and a silicone resin (β). [In formula (A-2), Z represents an ester group or an amide group, and W represents a group represented by -CO-R13, a group represented by -NH-CO-NH2, or the like.]SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a water repellent composition, a water repellent textile product using the same, and a method for producing the water repellent textile product. [Background technology]

[0002] Conventionally, fluorine-based water repellents containing fluorine-based compounds have been known, and textile products, etc., have been treated with such fluorine-based water repellents to impart water repellency to the surface thereof. Such fluorine-based water repellents are generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group. Although textile products treated with fluorine-based water repellents exhibit excellent water repellency, concerns about the environmental impact of monomers having fluoroalkyl groups have become evident, and therefore there has been an international demand for non-fluorine-based water repellents that do not contain fluorine-based compounds and that exhibit high-performance water repellency comparable to that of fluorine-based water repellents.

[0003] Therefore, in recent years, research has been conducted on non-fluorine-based water repellents that do not contain fluorine-based compounds. For example, the following Patent Document 1 discloses a surface treatment agent that is an aqueous emulsion containing a non-fluorine polymer having a repeating unit derived from a specific (meth)acrylate ester monomer, a specific surfactant, and a liquid medium containing water. The following Patent Document 2 discloses a water repellent composition that contains an acrylic copolymer in which a polymerizable monomer containing a specific (meth)acrylate and a specific aromatic ring or a specific cycloalkane is polymerized in a specific ratio as a fluorine-free polymerizable monomer. The following Patent Document 3 discloses a fiber processing agent that contains at least one of a silicon-based compound, a wax-based compound, and a wax-zirconium-based compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2015-172198 A [Patent Document 2] JP 2015-221952 A [Patent Document 3] JP 2006-124866 A Summary of the Invention [Problem to be solved by the invention]

[0005] Conventional non-fluorinated water repellents require textile products to be treated under conditions where the water repellent components are highly concentrated in order to provide sufficient water repellency to the textile products.Textile products treated under such conditions have a hard texture and are prone to leaving claw marks (also known as chalk marks) when the textile surface is rubbed with a fingernail.

[0006] Furthermore, textile products have a problem in that if water droplets remain on the surface for a long time, water will seep in. Therefore, water-repellent textile products are required to have not only water repellency and durable water repellency, but also water repellency that allows water droplets adhering to the fiber surface to quickly roll off.

[0007] The present invention has been made in consideration of the above circumstances, and aims to provide a water-repellent textile product that is excellent in water repellency, durable water repellency, and water repellency, has a good texture, and is less likely to cause chalk marks, as well as a water repellent composition that makes it possible to realize the same, and a method for producing the water-repellent textile product. [Means for solving the problem]

[0008] The present invention provides a water repellent composition comprising a non-fluorinated polymer (α) containing a structural unit derived from a (meth)acrylic acid ester monomer (A1) represented by the following general formula (A-1) and a structural unit derived from a compound (A2) represented by the following general formula (A-2), and a silicone resin (β).

[0009] [ka] [In formula (A-1), R 1represents hydrogen or a methyl group, R 2 represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent.]

[0010] [ka] [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, and W represents -CO-R 13 (In the formula, R 13 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH2, or a group represented by the following formula (A-3). [ka] ]

[0011] According to the water repellent composition of the present invention, by containing 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 texture can be obtained, and the obtained fiber product is less likely to cause chalk marks. The present inventors speculate as follows about the reason for such an effect. The non-fluorine-based polymer (α) is considered to have a property of being easily aggregated by having an ester group or an amide group and a ureido group or a ketone group as a constituent unit derived from the compound (A2), and it is considered that a fiber treated with a composition containing a non-fluorine-based polymer (α) having such a property and a silicone resin (β) is likely to form an uneven structure on the fiber surface. Therefore, the present inventors consider that even if the non-fluorine-based polymer (α) and the silicone resin (β) are attached to the fiber under treatment conditions at a low concentration where the texture of the fiber is not impaired and chalk marks are less likely to occur, sufficient water repellency, durable water repellency and water repellency can be imparted by forming an uneven structure.

[0012] Meanwhile, water-repellent textile products and the like may be subjected to a process of coating a urethane resin, an acrylic resin, or the like on a predetermined portion. In this case, the textile product is required to have sufficient water repellency, while the coating is required to be difficult to peel off from the coated portion. The difficulty of peeling off the coating can be evaluated by measuring the stress (peel strength) required to peel off the coating film from the water-repellent textile product. According to the water repellent composition of the present invention, the obtained textile product can have sufficient peel strength against the coating.

[0013] From the viewpoints of water repellency, durable water repellency and peel strength, the non-fluorinated polymer (α) may further contain a structural unit derived from at least one monomer (VC) of vinyl chloride and vinylidene chloride.

[0014] The present invention also provides a water-repellent textile product comprising a textile product having the water repellent composition according to the present invention adhered thereto.

[0015] The water-repellent textile product of the present invention is excellent in water repellency, durable water repellency, water repellency and texture, and is less likely to cause chalk marks. Furthermore, the water-repellent textile product of the present invention can have sufficient peel strength against coatings.

[0016] The present invention also provides a method for producing a water-repellent textile product, comprising a step of treating a textile product with a treatment liquid containing the water repellent composition according to the present invention.

[0017] According to the method for producing a water-repellent textile product of the present invention, it is possible to obtain a water-repellent textile product that is excellent in water repellency, durable water repellency, water repellency, and texture, and is less likely to cause chalk marks. Furthermore, the water-repellent textile product produced by the method of the present invention can have sufficient peel strength against coatings. Effect of the Invention

[0018] According to the present invention, it is possible to provide a water-repellent textile product that is excellent in water repellency, durable water repellency and water repellency, has a good texture and is less likely to cause chalk marks, as well as a water repellent composition that makes it possible to realize the same, and a method for producing the water-repellent textile product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The water repellent composition of the present embodiment contains a non-fluorinated polymer (α) and a silicone resin (β).

[0020] <Non-fluorinated polymer (α)> The non-fluorinated polymer (α) contains a structural unit derived from a (meth)acrylic acid ester monomer (A1) (hereinafter also referred to as "component (A1)") represented by the following general formula (A-1), and a structural unit derived from a compound (A2) (hereinafter also referred to as "component (A2)") represented by the following general formula (A-2).

[0021] [ka] [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.]

[0022] [ka] [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, and W represents -CO-R 13 (R 13 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH2, or a group represented by the following formula (A-3). [ka] ]

[0023] Here, the term "(meth)acrylic acid ester" means an "acrylic acid ester" or the corresponding "methacrylic acid ester", and has the same meaning as "(meth)acrylic acid", "(meth)acrylamide", etc.

[0024] The (A1) component 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 or unsaturated hydrocarbon group, and may further have an alicyclic or aromatic ring. Among these, from the viewpoint of water repellency and texture, a linear one is preferable, and a linear alkyl group is more preferable. In this case, the water repellency is more excellent. When the monovalent hydrocarbon group having 12 to 30 carbon atoms has a substituent, the substituent may be one or more 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. In this embodiment, in the general formula (A-1), R 2 is preferably an unsubstituted hydrocarbon group.

[0025] The number of carbon atoms in the hydrocarbon group is preferably 12 to 24, from the same viewpoint as above.

[0026] The carbon number of the hydrocarbon group is more preferably 12 to 22. When the carbon number is within this range, the water repellency and feel are particularly excellent. A linear alkyl group having a carbon number of 18 to 22 is particularly preferred as the hydrocarbon group.

[0027] Examples of the component (A1) include stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, and behenyl (meth)acrylate.

[0028] The (A1) component 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 that can react with a crosslinking agent. In this case, the durable water repellency of the resulting textile product can be further improved. The isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. In addition, when the (A1) component has an amino group, the texture of the resulting textile product can be further improved.

[0029] The component (A1) is preferably a monofunctional (meth)acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

[0030] The component (A1) may be used alone or in combination of two or more.

[0031] In the above formula (A-2), R 12 may be linear or branched, may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic ring.

[0032] In the above formula (A-2), when Z is an ester group, R 12 is preferably a hydrocarbon group having 2 to 4 carbon atoms, and W is preferably a group represented by -NH-CO-NH2 or a group represented by the above formula (A-3). When Z is an amide group, R 12 is a hydrocarbon group having 2 to 4 carbon atoms, and W is -CO-R 13 R 13 It is preferable that the carbon number is 1 to 2.

[0033] The (A2) component is not particularly limited, but examples thereof include diacetone acrylamide, 2-methylpropenoic acid [2-(2-oxo-2-imidazolidinyl)ethyl], and N-[2-(2-oxoimidazolidin-3-yl)ethyl]methacrylamide. Among these, from the viewpoint of durable water repellency of textile products, diacetone acrylamide and 2-methylpropenoic acid [2-(2-oxo-2-imidazolidinyl)ethyl] are preferred as the (A2) component.

[0034] The component (A2) may be used alone or in combination of two or more.

[0035] Regarding the content ratio of the structural units derived from the (A1) component and the structural units derived from the (A2) component in the non-fluorinated polymer (α) of this embodiment, the ratio (A1) / (A2) of the mass of the (A1) component to the mass of the (A2) component to be blended is preferably 99.9 / 0.1 to 70 / 30, more preferably 99.8 / 0.2 to 80 / 20, and even more preferably 99.7 / 0.3 to 90 / 10. When (A1) / (A2) is within the above range, the durable water repellency and water repellency of the obtained textile product are improved.

[0036] The total mass of the (A1) component and the (A2) component is preferably 60 to 100 mass%, more preferably 70 to 99 mass%, and even more preferably 80 to 98 mass%, based on the total amount of the monomer components constituting the non-fluorinated polymer (α).

[0037] From the viewpoint of peel strength, the non-fluorinated polymer (α) preferably contains, in addition to the components (A1) and (A2), at least one monomer (VC) of vinyl chloride and vinylidene chloride (hereinafter also referred to as "component (VC)") as a monomer component.

[0038] The (VC) component is preferably vinyl chloride from the viewpoint of maintaining the texture of the textile product.

[0039] The mass of the (VC) component is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, based on the total mass of the (A1) and (A2) components to be blended, from the viewpoints of water repellency, durable water repellency, and peel strength, based on 100 parts by mass of the (A1) and (A2) components to be blended. The mass of the (VC) component is preferably 100 parts by mass or less, and more preferably 75 parts by mass or less, based on 100 parts by mass of the (A1) and (A2) components to be blended, from the viewpoints of water repellency, durable water repellency, and texture.

[0040] The non-fluorinated polymer (α) preferably contains, in addition to the components (A1) and (A2), at least one reactive emulsifier (B) (hereinafter also referred to as "component (B)") selected from (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18, and (B3) a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, and the compound has an HLB of 7 to 18, in order to improve emulsion stability during emulsion polymerization or dispersion polymerization of the non-fluorinated polymer (α) and in the composition after polymerization.

[0041] [ka] [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, Y 1 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

[0042] [ka] [In formula (II-1), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group; Y 2 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

[0043] The term "reactive emulsifier" refers to an emulsifying / dispersing agent having radical reactivity, i.e., a surfactant having one or more polymerizable unsaturated groups in the molecule, which can be copolymerized with a monomer such as a (meth)acrylic acid ester.

[0044] In addition, "HLB" refers to the HLB value calculated by the Griffin method, assuming that the ethyleneoxy group is a hydrophilic group and all other groups are lipophilic groups.

[0045] The HLB of the compounds (B1) to (B3) used in this embodiment is 7 to 18, and from the viewpoint of emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the non-fluorinated polymer (α) of this embodiment (hereinafter simply referred to as emulsion stability), it is preferably 9 to 15. Furthermore, from the viewpoint of storage stability of the water repellent composition, it is more preferable to use two or more reactive emulsifiers (B) having different HLB within the above range in combination.

[0046] In the reactive emulsifier (B1) represented by the above general formula (I-1) used in this embodiment, R 3 is hydrogen or a methyl group, and is preferably a methyl group in terms of copolymerizability with the (A1) component and / or the (A2) component. X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of the emulsion stability of the non-fluorinated polymer (α) of this embodiment. Y 1 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 1 The type, combination and number of alkyleneoxy groups in may be appropriately selected so as to fall within the above HLB range. When there are two or more types of alkyleneoxy groups, they may have a block addition structure or a random addition structure.

[0047] As the compound represented by the above general formula (I-1), a compound represented by the following general formula (I-2) is preferable.

[0048] [ka] [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 fall within the above HLB range, and specifically, an integer of 1 to 80 is preferable. When m is 2 or more, m A 1 O may be the same or different.]

[0049] In the compound represented by the above general formula (I-2), R 3 is hydrogen or a methyl group, and is preferably a methyl group in terms of copolymerizability with the (A1) component and / or the (A2) component. X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of the emulsion stability of the non-fluorinated polymer (α) of this embodiment. A 1 O is an alkyleneoxy group having 2 to 4 carbon atoms. 1 The types and combinations of O and the number m can be appropriately selected so as to fall within the above HLB range. From the viewpoint of emulsion stability of the non-fluorinated polymer (α) of the present embodiment, m is preferably an integer of 1 to 80, more preferably an integer of 1 to 60. When m is 2 or more, m A 1 O may be the same or different. 1 When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0050] The reactive emulsifier (B1) represented by the above general formula (I-2) can be obtained by a conventionally known method and is not particularly limited. It can also be easily obtained from commercial products, such as "Latemul PD-420", "Latemul PD-430", and "Latemul PD-450" manufactured by Kao Corporation.

[0051] In the reactive emulsifier (B2) represented by the above general formula (II-1) used in this embodiment, R 4is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, and examples thereof include a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, and a heptadecatrienyl group. In terms of the emulsion stability of the non-fluorinated polymer (α) of this embodiment, R 4 is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

[0052] Y 2 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 2 The type, combination and number of alkyleneoxy groups in the above formula (1) can be appropriately selected so as to be within the above HLB range. When the alkyleneoxy groups are of two or more types, they may have a block addition structure or a random addition structure. In terms of emulsion stability of the non-fluorinated polymer (α) of the present embodiment, the alkyleneoxy group is preferably an ethyleneoxy group.

[0053] As the compound represented by the above general formula (II-1), a compound represented by the following general formula (II-2) is preferable.

[0054] [ka] [In formula (II-2), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n can be appropriately selected so as to fall within the above HLB range. Specifically, an integer of 1 to 50 is preferable. When n is 2 or more, n A 2 O may be the same or different.]

[0055] R in the compound represented by the above general formula (II-2) 4 is R in the above general formula (II-1). 4 The same can be mentioned.

[0056] A 2 O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of emulsion stability of the non-fluorinated polymer (α) of this embodiment, A 2 The types and combinations of O and the number of n can be appropriately selected so as to be within the above HLB range. 2 O is more preferably an ethyleneoxy group, and n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and further preferably an integer of 8 to 14. When n is 2 or more, n A 2 O may be the same or different. 2 When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0057] The reactive emulsifier (B2) represented by the above general formula (II-2) used in this embodiment can be synthesized by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group by a conventionally known method, and is not particularly limited. For example, it can be synthesized by adding a predetermined amount of alkylene oxide under pressure at 120 to 170°C using an alkali catalyst such as caustic soda or caustic potassium.

[0058] The above-mentioned phenols having the corresponding unsaturated hydrocarbon group include not only pure products or mixtures produced industrially, but also those present as pure products or mixtures extracted and purified from plants, etc. Examples include 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., which are extracted from cashew nut shells, etc. and are collectively called cardanol.

[0059] The reactive emulsifier (B3) used in this embodiment is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group, and the fat or oil has an HLB value of 7 to 18. Examples of the fat or oil having a hydroxyl group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids which may contain hydroxyunsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), and triglycerides of fatty acids containing at least one kind of hydroxyunsaturated fatty acid (ricinoleic acid, ricinoelaidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of emulsion stability of the non-fluorinated polymer (α) of this embodiment, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one hydroxy unsaturated fatty acid is preferred, an alkylene oxide adduct of castor oil (triglyceride of a fatty acid containing ricinoleic acid) having 2 to 4 carbon atoms is more preferred, and an ethylene oxide adduct of castor oil is even more preferred. Furthermore, the number of moles of the alkylene oxide added can be appropriately selected so as to be within the above-mentioned HLB range, and from the viewpoint of emulsion stability of the non-fluorinated polymer (α) of this embodiment, 20 to 50 moles is more preferred, and 25 to 45 moles is even more preferred. Furthermore, when there are two or more kinds of alkylene oxides, they can have a block addition structure or a random addition structure.

[0060] The reactive emulsifier (B3) used in this embodiment can be synthesized by adding an alkylene oxide to an oil having a hydroxyl group and a polymerizable unsaturated group by a conventionally known method, and is not particularly limited. For example, it can be synthesized by adding a predetermined amount of alkylene oxide to a triglyceride of a fatty acid containing ricinoleic acid, that is, castor oil, using an alkali catalyst such as caustic soda or caustic potassium under pressure at 120 to 170°C.

[0061] From the viewpoint of improving the water repellency of the obtained textile product and the emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the non-fluorinated polymer (α) of the present embodiment, the constituent ratio of the monomer of the component (B) in the non-fluorinated polymer (α) of the present embodiment is preferably 0.5 to 20 mass%, more preferably 1 to 15 mass%, and further preferably 3 to 10 mass%, based on the total amount of monomer components constituting the non-fluorinated polymer (α).

[0062] The non-fluorinated polymer (α) contained in the water repellent composition of the present embodiment preferably contains, in addition to the components (A1) and (A2), at least one second (meth)acrylic acid ester monomer (C) (hereinafter also referred to as "component C") selected from the group consisting of the following (C1), (C2), (C3) and (C4) as a monomer component, in order to improve the durable water repellency of the resulting textile product.

[0063] (C1) A (meth)acrylic acid ester monomer represented by the following general formula (C-1): [ka] [In formula (C-1), R 5 represents hydrogen or a methyl group, R 6 represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group, provided that the number of (meth)acryloyloxy groups in the molecule is 2 or less.]

[0064] (C2) A (meth)acrylic acid ester monomer represented by the following general formula (C-2): [ka] [In formula (C-2), R 7 represents hydrogen or a methyl group, R 8 represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent.]

[0065] (C3) A methacrylic acid ester monomer represented by the following general formula (C-3): [ka] [In formula (C-3), R 9 represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms.]

[0066] (C4) A (meth)acrylic acid ester monomer represented by the following general formula (C-4): [ka] [In formula (C-4), R 10 represents hydrogen or a methyl group, p represents an integer of 2 or greater, S represents a (p+1)-valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group.

[0067] The monomer (C1) is a (meth)acrylic acid ester monomer having a monovalent chain hydrocarbon group having 1 to 11 carbon atoms, which 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. From the viewpoint of being capable of reacting with a crosslinking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. When a non-fluorine-based polymer (α) containing the monomer (C1) having a group capable of reacting with these crosslinking agents is treated with a crosslinking agent to a textile product, the durable water repellency of the resulting textile product can be improved while maintaining the texture. The isocyanate group may be a blocked isocyanate group protected with a blocking agent.

[0068] The chain hydrocarbon group may be linear or branched, and may be a saturated or unsaturated hydrocarbon group. The chain hydrocarbon group may further have a substituent in addition to the functional group. Among them, it is preferable that the chain hydrocarbon group is linear and / or a saturated hydrocarbon group, in order to improve the durable water repellency of the obtained textile product.

[0069] Specific examples of the monomer (C1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. These monomers may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred in terms of improving the durable water repellency of the resulting textile product. Furthermore, dimethylaminoethyl (meth)acrylate is preferred in terms of improving the feel of the resulting textile product.

[0070] The mass of the (C1) component is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, based on the total mass of the (A1) and (A2) components (100) from the viewpoint of water repellency. The mass of the (C1) component is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, based on the total mass of the (A1) and (A2) components (100) from the viewpoint of water repellency.

[0071] The monomer (C2) is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester moiety, and examples of the cyclic hydrocarbon group include isobornyl, cyclohexyl, and dicyclopentanyl groups. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group in which the total number of carbon atoms of the substituent and the cyclic hydrocarbon group is 11 or less is selected. In addition, from the viewpoint of improving durable water repellency, it is preferable that these cyclic hydrocarbon groups are directly bonded to an ester bond. The cyclic hydrocarbon group may be alicyclic or aromatic, and when it is alicyclic, it may be a saturated or unsaturated hydrocarbon group. Specific examples of the monomer include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. These monomers may be used alone or in combination of two or more. Among these, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferred, and isobornyl methacrylate is more preferred, in terms of improving the durable water repellency of the resulting textile product.

[0072] The mass of the (C2) component is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, based on 100 parts by mass of the total of the (A1) and (A2) components, from the viewpoint of water repellency. The mass of the (C2) component is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, based on 100 parts by mass of the total of the (A1) and (A2) components, from the viewpoint of water repellency.

[0073] The monomer (C3) is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester moiety. The chain hydrocarbon group having 1 to 4 carbon atoms is preferably a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Specific examples of the compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. One of these monomers may be used alone, or two or more of them may be used in combination. Among these, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferred, and methyl methacrylate is more preferred, in that they can improve the durable water repellency of the resulting textile product.

[0074] The mass of the (C3) component is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, based on 100 parts by mass of the total of the (A1) and (A2) components, from the viewpoint of water repellency. The mass of the (C3) component is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, based on 100 parts by mass of the total of the (A1) and (A2) components, from the viewpoint of water repellency.

[0075] The monomer (C4) is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In this embodiment, a polyfunctional (meth)acrylic acid ester monomer having three or more (meth)acryloyloxy groups in one molecule, in which T in the above general formula (C-4) is a (meth)acryloyloxy group, is preferred. In formula (C-4), p Ts 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, and dipentaerythritol hexamethacrylate. These monomers may be used alone or in combination of two or more. Among these, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred in terms of improving the durable water repellency of the resulting textile product.

[0076] The mass of the (C4) component is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, based on 100 parts by mass of the total of the (A1) and (A2) components, from the viewpoint of water repellency. The mass of the (C4) component is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, based on 100 parts by mass of the total of the (A1) and (A2) components, from the viewpoint of water repellency.

[0077] The total constituent ratio of the monomers of the component (C) in the non-fluorinated polymer (α) of the present embodiment is, from the viewpoints of water repellency and feel of the obtained textile product, preferably from 1 to 30 mass%, more preferably from 3 to 25 mass%, and further preferably from 5 to 20 mass%, based on the total amount of the monomer components constituting the non-fluorinated polymer (α).

[0078] The mass of the (C) component is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, based on 100 parts by mass of the total of the (A1) and (A2) components, from the viewpoint of water repellency. The mass of the (C) component is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, based on 100 parts by mass of the total of the (A1) and (A2) components, from the viewpoint of water repellency.

[0079] The non-fluorinated polymer (α) contained in the water repellent composition of the present embodiment may contain, in addition to the components (A1) and (A2), a monofunctional monomer (D) (hereinafter also referred to as "component (D)") copolymerizable therewith, within a range that does not impair the effects of the present invention.

[0080] Examples of the (D) component include (meth)acryloylmorpholine, (meth)acrylic acid esters having a hydrocarbon group other than the (A) and (C) components, (meth)acrylic acid, fumaric acid esters, maleic acid esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other vinyl monomers not containing fluorine other than the (VC) component. The (meth)acrylic acid esters having a hydrocarbon group other than the (A) and (C) components may have a substituent such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, or a blocked isocyanate group in the hydrocarbon group, or may have a substituent other than a group reactive with a crosslinking agent such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond, or a urethane bond. Examples of (meth)acrylic acid esters other than the components (A) and (C) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, etc. Among these, (meth)acryloylmorpholine is more preferred in that it can improve the peel strength of the resulting fiber product against the coating.

[0081] The mass of the (D) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, relative to 100 parts by mass of the total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency. The mass of the (D) monomer to be blended is preferably 40 parts by mass or less, and more preferably 35 parts by mass or less, relative to 100 parts by mass of the total of the (A1) and (A2) components to be blended, from the viewpoint of water repellency.

[0082] The non-fluorinated polymer (α) of the present embodiment 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 that can react with a crosslinking agent, since this improves the durable water repellency of the resulting textile product. The isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. In addition, the non-fluorinated polymer (α) preferably has an amino group, since this improves the feel of the resulting textile product.

[0083] The weight average molecular weight of the non-fluorinated polymer (α) of this embodiment is preferably 30,000 or more. When the weight average molecular weight is 30,000 or more, the water repellency of the obtained textile product tends to be further improved. Furthermore, the weight average molecular weight of the non-fluorinated polymer (α) is more preferably 100,000 or more. In this case, the obtained textile product can exhibit more sufficient water repellency. The upper limit of the weight average molecular weight of the non-fluorinated polymer (α) is preferably about 5 million.

[0084] The weight average molecular weight of the non-fluorinated polymer (α) is measured using a GPC device (GPC "HLC-8020" manufactured by Tosoh Corporation) under conditions of a column temperature of 40°C and a flow rate of 1.0 ml / min, using tetrahydrofuran as an eluent, and is expressed in terms of standard polystyrene. The columns used are three columns connected together, which are manufactured by Tosoh Corporation under the trade names TSK-GEL G5000HHR, G4000HHR, and G3000HHR.

[0085] In this embodiment, the melt viscosity of the non-fluorinated polymer (α) at ​​105°C is preferably 1000 Pa·s or less. When the melt viscosity at 105°C is 1000 Pa·s or less, the texture of the obtained textile product tends to be easily maintained. In addition, when the non-fluorinated polymer (α) has a melt viscosity of 1000 Pa·s or less, when the non-fluorinated polymer (α) is emulsified or dispersed to prepare a water repellent composition, the non-fluorinated polymer (α) can be prevented from precipitating or settling, so that the storage stability of the water repellent composition tends to be easily maintained. The melt viscosity at 105°C is more preferably 500 Pa·s or less. In this case, the obtained textile product etc. exhibits sufficient water repellency and has a better texture.

[0086] "Melt viscosity at 105°C" is measured by placing 1 g of a non-fluorinated polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm) using an elevated flow tester (e.g. Shimadzu CFT-500), holding the temperature at 105°C for 6 minutes, and measuring the melt viscosity at 100 kgf / cm using a plunger. 2 This refers to the viscosity measured when a load of 100 mm is applied.

[0087] <Silicone resin (β)> Examples of the silicone resin (β) include silicone resin and silicone oil. Silicone resin is an organopolysiloxane that contains MQ, MDQ, MT, MTQ, MDT, or MDTQ as a constituent, is solid at 25°C, and has a three-dimensional structure. Here, M, D, T, and Q are each (R'')3SiO 0.5 Unit, (R'')2SiO unit, R''SiO 1.5 units and SiO2 units. R'' represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

[0088] Silicone resins are commonly known as MQ resins, MT resins or MDT resins, and may have moieties designated as MDQ, MTQ or MDTQ.

[0089] Silicone resins are also available as solutions in suitable solvents, such as relatively low molecular weight methylpolysiloxanes, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and mixtures of these solvents.

[0090] Examples of silicone resin solutions include KF7312J (a 50:50 mixture of trimethylsilyl group-containing polysiloxane:decamethylcyclopentasiloxane), KF7312F (a 50:50 mixture of trimethylsilyl group-containing polysiloxane:octamethylcyclotetrasiloxane), KF9021L (a 50:50 mixture of trimethylsilyl group-containing polysiloxane:low-viscosity methylpolysiloxane), and KF7312L (a 50:50 mixture of trimethylsilyl group-containing polysiloxane:low-viscosity methylpolysiloxane), all of which are commercially available from Shin-Etsu Chemical Co., Ltd.

[0091] Examples of silicone resins alone include MQ-1600 solid resin (trimethylsilyl group-containing polysiloxane) and MQ-1640 flake resin (trimethylsilyl group-containing polysiloxane, polypropylsilsesquioxane), both of which are commercially available from Dow Corning Toray Co., Ltd. The above commercially available products contain trimethylsilyl group-containing polysiloxane, and include MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0092] Silicone oil is a linear organopolysiloxane, and may have an organic group at least in one of the side chain and the end of the organopolysiloxane. Examples of such silicone oil 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, higher fatty acid ester-modified silicone oil, higher aliphatic amide-modified silicone oil, and modified silicone oils such as organo-modified silicone oil represented by the following general formula (1). In the following general formula (1), each structural unit may be arranged in a block, random, or alternate arrangement.

[0093] [ka] [In formula (1), R 20 , R 21 and R 22 each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms; R 23 represents a hydrocarbon group having 8 to 40 carbon atoms and 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 each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; a represents an integer of 0 or more; b represents an integer of 1 or more; (a+b) is 10 to 200; when a is 2 or more, a plurality of R 20 and R 21may be the same or different, and when b is 2 or more, there are multiple R 22 and R 23 may be the same or different.]

[0094] Among such silicone resins, silicone oils are preferred from the viewpoints of water repellency and dispersibility of the water repellent composition in an aqueous medium, and methyl hydrogen silicone oil, amino modified silicone oil, epoxy modified silicone oil, carbinol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, and alkyl aralkyl modified silicone oil are more preferred, and alkyl modified silicones are preferred because they further improve the water repellency and durable water repellency of the resulting textile product, or amino modified silicones, methyl hydrogen silicones, and dimethyl silicones are even more preferred because they further improve the feel of the resulting textile product and can further reduce the occurrence of chalk marks.

[0095] 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. Examples of the alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. R 20 , R 21 and R 22 are each independently preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0096] Examples of the above-mentioned hydrocarbon group having 8 to 40 carbon atoms and having an aromatic ring include aralkyl groups having 8 to 40 carbon atoms and groups represented by the following general formula (2) or (3).

[0097] [ka] [In formula (2), R 40 represents an alkylene group having 2 to 6 carbon atoms, R 41represents 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, a plurality of R 41 may be the same or different.]

[0098] The alkylene group may be linear or branched.

[0099] [ka] [In 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, a plurality of R 43 may be the same or different.]

[0100] The alkylene group may be linear or branched.

[0101] 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, a naphthylethyl group, etc. Among these, the phenylethyl group and the phenylpropyl group are preferred in terms of ease of industrial production and availability.

[0102] Among the groups represented by the above general formula (2), R 40 is preferably an alkylene group having 2 to 4 carbon atoms, and c is preferably 0 or 1, and more preferably 0.

[0103] Among the groups represented by the above general formula (3), R 42 is preferably an alkylene group having 2 to 4 carbon atoms, and d is preferably 0 or 1, and more preferably 0.

[0104] As the above-mentioned hydrocarbon group having 8 to 40 carbon atoms and having an aromatic ring, the above-mentioned aralkyl group having 8 to 40 carbon atoms and the group represented by the above-mentioned general formula (2) are preferred in that they are easy to produce industrially and are readily available, and the above-mentioned aralkyl group having 8 to 40 carbon atoms is more preferred in that it can improve the water repellency of the obtained textile product.

[0105] 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 stearyl group. As the alkyl group having 3 to 22 carbon atoms, an alkyl group having 8 to 20 carbon atoms is preferable, and an alkyl group having 12 to 18 carbon atoms is more preferable, in terms of improving the water repellency of the obtained textile product.

[0106] In the organo-modified silicone oil represented by the above general 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, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms. 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and among these, a methyl group is more preferable.

[0107] In the organo-modified silicone oil represented by the above general formula (1), a is an integer of 0 or more. In terms of ease of industrial production, ease of availability, and superior peel strength of the resulting textile product against resin coating, a is preferably 40 or less, and more preferably 30 or less.

[0108] In the organo-modified silicone oil represented by the above general formula (1), (a+b) is 10 to 200. From the viewpoint of ease of industrial production and availability, (a+b) is preferably 20 to 100, and more preferably 40 to 60. When (a+b) is within the above range, the production and handling of the silicone itself tends to be easier.

[0109] The organo-modified silicone oil represented by the above general formula (1) can be synthesized by a conventionally known method. For example, the organo-modified silicone oil represented by the above general formula (1) can be obtained by subjecting a silicone having a SiH group to a hydrosilylation reaction with an aromatic compound having a vinyl group and / or an α-olefin.

[0110] Examples of silicones having a SiH group include methylhydrogensilicones having a degree of polymerization of 10 to 200, and copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicones are preferred because they are easy to produce industrially and are readily available.

[0111] The aromatic compound having a vinyl group is represented by the formula (1) R 23 In the above formula, it is a compound from which a hydrocarbon group having an aromatic ring and a carbon number of 8 to 40 is derived. Examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumyl phenyl ether, allyl-o-phenyl phenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.

[0112] The above α-olefin is represented by the formula (1) R 23In the above formula, it is a compound from which an alkyl group having 3 to 22 carbon atoms is derived. Examples of the α-olefin include α-olefins having 3 to 22 carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.

[0113] The hydrosilylation reaction may be carried out by reacting the silicone having a SiH group with the aromatic compound having a vinyl group and the α-olefin in a stepwise manner or all at once, if necessary, in the presence of a catalyst.

[0114] The amounts of the SiH group-containing silicone, the vinyl group-containing aromatic compound, and the α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent or number average molecular weight of the SiH group-containing silicone, etc.

[0115] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, and among these, platinum compounds are preferred, such as platinum(IV) chloride.

[0116] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be appropriately adjusted. The reaction temperature is, for example, 10 to 200° C., and preferably 50 to 150° C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150° C.

[0117] The hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of the inert gas include nitrogen and argon. The reaction proceeds without a solvent, but a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0118] The amino-modified silicone oil may be a compound having an organic group containing an amino group and / or an imino group at least on one of the side chains and the terminals of the organopolysiloxane. Such an organic group may be an organic group represented by -R-NH2 or an organic group represented by -R-NH-R'-NH2. Examples of R and R' include divalent groups such as an ethylene group and a propylene group. A part or all of the amino group and / or the imino group may be a blocked amino group and / or an imino group. The blocked amino group and / or the imino group may be obtained, for example, by treating the amino group and / or the imino group with a blocking agent. Examples of the blocking agent include fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, acid halides of fatty acids having 2 to 22 carbon atoms, and aliphatic monoisocyanates having 1 to 22 carbon atoms.

[0119] The functional group equivalent of the amino-modified silicone oil is preferably from 100 to 20,000 g / mol, more preferably from 150 to 12,000 g / mol, and still more preferably from 200 to 4,000 g / mol, from the viewpoint of water repellency.

[0120] The amino-modified silicone oil is preferably liquid at 25° C. The kinetic viscosity of the amino-modified silicone oil at 25° C. is 10 to 100,000 mm 2 / s is preferably 10 to 30,000 mm 2 / s is more preferable, and 10 to 5,000 mm 2 More preferably, the kinematic viscosity at 25°C is 100,000 mm 2 When the kinematic viscosity is equal to or less than 25° C., workability tends to be ensured easily. The kinematic viscosity at 25° C. means a value measured by the method described in JIS K 2283:2000 (Ubbelohde viscometer).

[0121] The amino-modified silicone oil can be easily obtained as a commercial product, such as KF8005, KF-868, KF-864, KF-393, KF-8021 (all of which are trade names of Shin-Etsu Chemical Co., Ltd.), TSF-4709, XF42-B1989 (all of which are trade names of Momentive Performance Materials Japan Co., Ltd.), BY16-872, SF-8417, BY16-853U, BY16-892 (all of which are trade names of Dow Corning Toray Co., Ltd.), etc.

[0122] Silicone oils other than amino-modified silicone oils are also easily available as commercially available products. Examples of commercially available products include KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: epoxy-modified silicone oil), X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: carboxyl-modified silicone oil), SF8428 (manufactured by Dow Corning Toray Co., Ltd., trade name: carbinol-modified silicone oil), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: methyl hydrogen silicone oil), and X-22-715 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: methyl hydrogen silicone oil). , higher fatty acid ester modified silicone oil), KF-96-3000cp (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, dimethyl silicone oil), SF8416 (manufactured by Dow Corning Toray Co., Ltd., trade name, alkyl modified silicone oil), SH203 (manufactured by Dow Corning Toray Co., Ltd., trade name, alkyl aralkyl modified silicone oil), SF8410 (manufactured by Dow Corning Toray Co., Ltd., trade name, polyether modified silicone oil).

[0123] The silicone resin (β) may be used alone or in combination of two or more kinds.

[0124] With regard to the contents of the non-fluorinated polymer (α) and the silicone resin (β) contained in the water repellent composition of the present embodiment, in terms of the water repellency, texture and chalk mark of the obtained textile product, the ratio (α) / (β) of the mass of the non-fluorinated polymer (α) to the mass of the silicone resin (β) is preferably 2.5 / 97.5 to 97.5 / 2.5, more preferably 5 / 95 to 95 / 5, further preferably 10 / 90 to 90 / 10, and particularly preferably 15 / 85 to 85 / 15.

[0125] The water repellent composition of the present embodiment may also contain silica modified with a hydrophilizing agent and a hydrophobizing agent (silica having hydrophilic and hydrophobic groups on the silica surface). Examples of silica having hydrophilic and hydrophobic groups on the silica surface include Reolosil HG-09 (Tokuyama Corporation, product name), AEROSIL NA50H, RA200H, and RA200HS (all Nippon Aerosil Co., Ltd., product names).

[0126] Additives can be added to the water repellent composition of the present embodiment as needed. Examples of additives include other water repellents, surfactants, defoamers, pH adjusters, antibacterial agents, antifungal agents, colorants, antioxidants, deodorants, various organic solvents, chelating agents, antistatic agents, catalysts, crosslinking agents, antibacterial and deodorant agents, flame retardants, softeners, and wrinkle inhibitors.

[0127] As the surfactant, known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used. The surfactants can be used alone or in combination of two or more.

[0128] Examples of the defoaming agent include oil-based defoaming agents such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; fatty acid-based defoaming agents such as stearic acid, oleic acid, and palmitic acid; fatty acid ester-based defoaming agents such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, and butyl stearate; alcohol-based defoaming agents such as polyoxyalkylene monohydric alcohol, di-t-amylphenoxyethanol, 3-heptanol, and 2-ethylhexanol; ether-based defoaming agents such as di-t-amylphenoxyethanol, 3-heptyl cellosolve, nonyl cellosolve, and 3-heptyl carbitol; phosphate-based defoaming agents such as tributyl phosphate and tris(butoxyethyl)phosphate; amine-based defoaming agents such as diamylamine; amide-based defoaming agents such as polyalkylene amide and acylate polyamine; sulfate-based defoaming agents such as sodium lauryl sulfate; and mineral oil. The antifoaming agents can be used alone or in combination of two or more.

[0129] 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, alkanolamines, pyridine, and morpholine. The pH adjuster can be used alone or in combination of two or more.

[0130] Examples of the organic solvent include aliphatic alcohols having 1 to 8 carbon atoms, such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, hexyl alcohol, and 2-ethylhexyl alcohol; 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; and ethylene glycol, diethylene glycol, triethylene glycol, and the like. Examples of the organic solvent include glycols such as ethanol, propylene glycol, and dipropylene glycol; glycol ethers such as ethylene 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. The organic solvent may be used alone or in combination of two or more.

[0131] It is preferable to use an antistatic agent that does not easily impair water repellency. Examples of the antistatic agent include cationic surfactants such as higher alcohol sulfate salts, sulfated oils, sulfonates, quaternary ammonium salts, and imidazoline quaternary salts, nonionic surfactants such as polyethylene glycol and polyhydric alcohol ester types, amphoteric surfactants such as imidazoline quaternary salts, alanine and betaine types, antistatic polymers of polymeric compounds, and polyalkylamines. The antistatic agent can be used alone or in combination of two or more.

[0132] Next, a method for producing the water repellent composition of the present embodiment will be described.

[0133] The composition containing the non-fluorinated polymer (α) can be produced by a radical polymerization method. Among these radical polymerization methods, emulsion polymerization or dispersion polymerization is preferred from the viewpoints of the performance of the resulting water repellent and the environment.

[0134] For example, the non-fluorinated polymer (α) can be obtained by emulsion polymerization or dispersion polymerization of the (A1) component and the (A2) component in a medium. More specifically, for example, the (A1) component, the (A2) component, and optionally the (B), (C) component, and (D) component, as well as an emulsifying aid or a dispersing aid, are added to the medium, and the mixture is emulsified or dispersed to obtain an emulsion or dispersion. A polymerization initiator is added to the obtained emulsion or dispersion to initiate a polymerization reaction, and the monomer and the reactive emulsifier can be polymerized. Examples of means for emulsifying or dispersing the above-mentioned mixture include a homomixer, a high-pressure emulsifier, and ultrasonic waves.

[0135] As the emulsifying aid or dispersing aid (hereinafter also referred to as "emulsifying aid, etc."), one or more selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants other than the reactive emulsifier (B) can be used. The content of the emulsifying aid, etc. is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total monomers. When the content of the emulsifying aid, etc. is 0.5 parts by mass or more, the dispersion stability of the mixed liquid tends to be further improved compared to when the content of the emulsifying aid, etc. is less than 0.5 parts by mass. When the content of the emulsifying aid, etc. is 30 parts by mass or less, the water repellency of the obtained non-fluorinated polymer tends to be further improved compared to when the content of the emulsifying aid, etc. is more than 30 parts by mass.

[0136] Examples of the cationic surfactant include monoalkyltrimethylammonium salts having 8 to 24 carbon atoms, dialkyldimethylammonium salts having 8 to 24 carbon atoms, monoalkylamine acetates having 8 to 24 carbon atoms, dialkylamine acetates having 8 to 24 carbon atoms, and alkylimidazoline quaternary salts having 8 to 24 carbon atoms. Among these, from the viewpoints of emulsifiability and processing stability, monoalkyltrimethylammonium salts having 12 to 18 carbon atoms and dialkyldimethylammonium salts having 12 to 18 carbon atoms are preferred.

[0137] These cationic surfactants may be used alone or in combination of two or more.

[0138] Examples of the nonionic surfactant include alkylene oxide adducts of alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, fats and oils, and polypropylene glycol.

[0139] Examples of the alcohols include linear or branched alcohols or alkenols having 8 to 24 carbon atoms, and acetylene alcohols represented by the following general formula (AL-1) or (AL-2).

[0140] [ka] [In the formula, R 51 and R 52 each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 2 to 8 carbon atoms.]

[0141] [ka] [In the formula, R 53 represents a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 2 to 8 carbon atoms.]

[0142] Examples of polycyclic phenols include monohydric phenols such as phenol and naphthol which may have a hydrocarbon group having 1 to 12 carbon atoms, their styrene (styrene, α-methylstyrene, vinyltoluene) adducts, and their benzyl chloride reaction products. Examples of amines include linear or branched aliphatic amines having 8 to 44 carbon atoms.

[0143] Examples of the amides include linear or branched fatty acid amides having 8 to 44 carbon atoms.

[0144] Examples of fatty acids include linear or branched fatty acids having 8 to 24 carbon atoms.

[0145] Examples of polyhydric alcohol fatty acid esters include condensation products of polyhydric alcohols and carboxylic acids having 2 to 30 carbon atoms (including the carbon of the carboxyl group). Examples of such polyhydric alcohol fatty acid esters include sorbitan esters composed of sorbitan (alcohol) and carboxylic acids having 2 to 30 carbon atoms (including the carbon of the carboxyl group).

[0146] The number of carbon atoms in the carboxylic acid constituting the sorbitan ester is 2 to 30, and preferably 5 to 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, a tricarboxylic acid ester of sorbitol and three carboxylic acids, or the like, and is preferably a monocarboxylic acid ester.

[0147] The sorbitan ester may be a compound represented by the following general formula (4) or the following general formula (5).

[0148] [ka] [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; R64 , R 65 and R 66 is hydrogen, -CO-R 61 or -(CH2CH2O) e -(R 62 O) f -R 63 (R 62 represents an alkylene group having 3 or more carbon atoms, and 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.

[0149] [ka] [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; R 64 , R 65 and R 66 is hydrogen, -CO-R 61 or -(CH2CH2O) e -(R 62 O) f -R 63 (R 62 represents an alkylene group having 3 or more carbon atoms, and 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.

[0150] Examples of the compound represented by the above general formula (4) or (5) include sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquistearate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan tristearate.

[0151] Examples of the fats and oils include vegetable fats and oils, animal fats and oils, vegetable waxes, animal waxes, mineral waxes, and hardened oils.

[0152] Among these, from the viewpoints of having little effect on water repellency, having little effect on light resistance, and having good emulsifiability of the copolymer, linear or branched alcohols or alkenols having 8 to 24 carbon atoms, and acetylene alcohols represented by the above general formula (AL-1) or (AL-2) are preferred, and linear or branched alcohols having 8 to 24 carbon atoms, and acetylene alcohols represented by the above general formula (AL-1) or (AL-2) are more preferred.

[0153] 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, etc. From the viewpoints of having little effect on water repellency and improving the emulsifiability of the non-fluorinated polymer (α), the alkylene oxide is preferably ethylene oxide or 1,2-propylene oxide, and more preferably ethylene oxide.

[0154] The number of moles of alkylene oxide added is preferably 1 to 200, more preferably 3 to 100, and even more preferably 5 to 50. When the number of moles of alkylene oxide added is within the above range, high levels of water repellency and product stability can be easily obtained.

[0155] In the non-fluorinated polymer (α) according to this embodiment, a better aqueous dispersion can be obtained when a nonionic surfactant having an HLB of 7 to 18 is used as the nonionic surfactant. Here, the HLB is based on Griffin's HLB and is obtained by modifying the Griffin's formula to the following formula. Here, the hydrophilic group refers to an ethylene oxide group. HLB=(hydrophilic group×20) / molecular weight

[0156] The HLB of the nonionic surfactant used in this embodiment is 7 to 18, and from the viewpoint of emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the non-fluorinated polymer (α) of this embodiment (hereinafter simply referred to as emulsion stability), it is preferably 9 to 15. Furthermore, from the viewpoint of storage stability of the water repellent composition, it is more preferable to use two or more nonionic surfactants having different HLB within the above range in combination. Also, from the viewpoint of emulsion stability and water repellency, it is preferable to use a cationic surfactant and a nonionic surfactant in combination.

[0157] The medium for emulsion polymerization or dispersion polymerization is preferably water, and water and an organic solvent may be mixed as necessary.The organic solvent is not particularly limited as long as it is an organic solvent that can be mixed with water, and examples thereof include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol.The ratio of water to organic solvent is not particularly limited.

[0158] As the polymerization initiator, known polymerization initiators such as azo-based, peroxide-based, or redox-based initiators can be appropriately used. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the total monomers. When the content of the polymerization initiator is within the above range, a non-fluorine-based polymer (α) having a weight average molecular weight of 30,000 or more can be efficiently produced.

[0159] In addition, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight. The content of the chain transfer agent is preferably 0.3 parts by mass or less, more preferably 0.1 parts by mass or less, relative to 100 parts by mass of the total monomers. When the content of the chain transfer agent is 0.3 parts by mass or less, it is possible to prevent the molecular weight from decreasing too much, and it tends to be easy to efficiently produce a non-fluorinated polymer (α) having a weight average molecular weight of 30,000 or more.

[0160] A polymerization inhibitor may be used to adjust the molecular weight. By adding a polymerization inhibitor, a non-fluorinated polymer (α) having a desired weight average molecular weight can be easily obtained.

[0161] The temperature of the polymerization reaction is preferably 20° C. to 150° C. When the temperature is 20° C. or higher, the polymerization tends to proceed more easily than when the temperature is lower than 20° C. When the temperature is 150° C. or lower, the reaction heat can be easily controlled than when the temperature exceeds 150° C.

[0162] In the polymerization reaction, the weight average molecular weight of the resulting non-fluorinated polymer (α) can be adjusted by increasing or decreasing the contents of the above-mentioned polymerization initiator, chain transfer agent, and polymerization inhibitor, and the melt viscosity at 105° C. can be adjusted by increasing or decreasing the content of the polyfunctional monomer and the content of the polymerization initiator. 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.

[0163] 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 %, more preferably 20 to 40 mass %, based on the total amount of the emulsion or dispersion, from the viewpoints of storage stability and handleability of the composition.

[0164] The water repellent composition of the present embodiment can be prepared by mixing the composition containing the non-fluorinated polymer (α) obtained by the above method with a silicone resin (β). The silicone resin (β) may be a commercially available product.

[0165] The water-repellent textile product of this embodiment is a textile product to which the above-mentioned non-fluorinated polymer (α) of this embodiment and silicone resin (β) are adhered.

[0166] A method for producing the water-repellent textile product of this embodiment will be described.

[0167] The water-repellent textile product of this embodiment is obtained by treating the textile product with a treatment liquid containing the water repellent composition described above, thereby adhering the non-fluorinated polymer (α) and the silicone resin (β) to the textile product. The material of such textile products is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, and synthetic fibers such as nylon, polyester, polyurethane, and polypropylene, as well as composite fibers and blended fibers thereof. The form of the textile product may be any of fibers, threads, cloth, nonwoven fabric, and paper.

[0168] Examples of the method for treating a textile product with the treatment liquid include processing methods such as immersion, spraying, coating, etc. When the water repellent composition contains water, it is preferable to dry the textile product after it has been applied thereto in order to remove the water.

[0169] The amount of the water repellent composition applied to the textile product can be appropriately adjusted depending on the level of water repellency required. From the viewpoints of water repellency and texture, the total amount of the non-fluorinated polymer (α) and silicone resin (β) contained in the water repellent composition applied is preferably adjusted to 0.01 to 10 g, and more preferably adjusted to 0.05 to 5 g, per 100 g of the textile product.

[0170] In addition, after the non-fluorine-based polymer (α) and the silicone resin (β) of this embodiment are attached to the textile product, it is preferable to appropriately perform heat treatment. There is no particular restriction on the temperature conditions, but when the water repellent composition of this embodiment is used, the textile product can exhibit sufficiently good water repellency under mild conditions of 100 to 130°C. The temperature conditions may be high-temperature treatment of 130°C or higher (preferably up to 200°C), and in such a case, it is possible to shorten the treatment time compared to the conventional case using a fluorine-based water repellent. Therefore, according to the water-repellent textile product of this embodiment, the deterioration of the textile product due to heat is suppressed, the texture of the textile product during the water repellent treatment becomes soft, and sufficient water repellency can be imparted to the textile product under mild heat treatment conditions, i.e., low-temperature curing conditions.

[0171] In particular, when it is desired to improve the durable water repellency, it is preferable to subject the textile product to water repellency treatment by a method including the above-mentioned step of treating the textile product with a treatment liquid containing the water repellent composition, and the step of attaching a crosslinking agent, typically a melamine resin, a glyoxal resin, or a compound having one or more isocyanate groups or blocked isocyanate groups, to the textile product and heating it. Furthermore, when it is desired to further improve the durable water repellency, it is preferable that the water repellent composition contains a non-fluorine-based polymer (α) copolymerized with a monomer having a functional group capable of reacting with the above-mentioned crosslinking agent.

[0172] As the melamine resin, a compound having a melamine skeleton can be used, for example, polymethylolmelamine such as trimethylolmelamine and hexamethylolmelamine; alkoxymethylmelamine in which a part or all of the methylol groups of polymethylolmelamine are alkoxymethyl groups having an alkyl group having 1 to 6 carbon atoms; acyloxymethylmelamine in which a part or all of the methylol groups of polymethylolmelamine are acyloxymethyl groups having an acyl group having 2 to 6 carbon atoms. These melamine resins may be either a monomer or a polymer of dimer or more, or a mixture of these may be used. Furthermore, a part of melamine co-condensed with urea or the like can also be used. Examples of such melamine resins include Beckamine APM, Beckamine M-3, Beckamine M-3(60), Beckamine MA-S, Beckamine J-101, and Beckamine J-101LF manufactured by DIC Corporation, Unika Resin 380K manufactured by Union Chemical Industry Co., Ltd., and Riken Resin MM series manufactured by Miki Riken Kogyo Co., Ltd.

[0173] As the glyoxal resin, a conventionally known one can be used. Examples of the glyoxal resin include 1,3-dimethylglyoxal urea resin, dimethylol dihydroxyethylene urea resin, and dimethylol dihydroxypropylene urea resin. The functional groups of these resins may be substituted with other functional groups. Examples of such glyoxal resins include Beckamine N-80, Beckamine NS-11, Beckamine LF-K, Beckamine NS-19, Beckamine LF-55P Conc, Beckamine NS-210L, Beckamine NS-200, and Beckamine NF-3 manufactured by DIC Corporation, Uniresin GS-20E manufactured by Union Chemical Industry Co., Ltd., Riken Resin RG series and Riken Resin MS series manufactured by Miki Riken Kogyo Co., Ltd.

[0174] For melamine resin and glyoxal resin, it is preferable to use a catalyst from the viewpoint of promoting the reaction. Such a catalyst is not particularly limited as long as it is a commonly used catalyst, and examples thereof include borofluoride compounds such as ammonium borofluoride and borofluoridium salt; neutral metal salt catalysts such as magnesium chloride and magnesium sulfate; and inorganic acids such as phosphoric acid, hydrochloric acid, and boric acid. If necessary, these catalysts can be used in combination with organic acids such as citric acid, tartaric acid, malic acid, maleic acid, and lactic acid as a promoter. Examples of such catalysts include Catalyst ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, and Catalyst NFC-1, all manufactured by DIC Corporation; Unika Catalyst 3-P and Unika Catalyst MC-109, all manufactured by Union Chemical Industry Co., Ltd.; and Riken Fixer RC series, Riken Fixer MX series, and Riken Fixer RZ-5, all manufactured by Miki Riken Kogyo Co., Ltd.

[0175] 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, as well as polyfunctional isocyanate compounds can be used.

[0176] The polyfunctional isocyanate compound is not particularly limited as long as it has two or more isocyanate groups in the molecule, and known polyisocyanate compounds can be used. Examples of the polyfunctional isocyanate compound include diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate, and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimers or trimers of these diisocyanate compounds. The carbon number of the alkylene diisocyanate is preferably 1 to 12.

[0177] Examples of the diisocyanate compound include 2,4 or 2,6-tolylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, 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-dimethylbenzyl diisocyanate, 1,2 ... benzene, ω,ω'-diisocyanato-1,4-dimethylcyclohexane, ω,ω'-diisocyanato-1,4-dimethylbenzene, ω,ω'-diisocyanato-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanatocyclohexane, 4,4'-methylene-bis(cyclohexyl isocyanate), 3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate, acid-diisocyanate dimer, ω,ω'-diisocyanatodiethylbenzene, ω,ω'-diisocyanatodimethyltoluene, ω,ω'-diisocyanatodiethyltoluene, fumaric acid bis(2-isocyanatoethyl)ester, 1,4-bis(2-isocyanato-prop-2-yl)benzene, and 1,3-bis(2-isocyanato-prop-2-yl)benzene.

[0178] Examples of triisocyanate compounds include triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, and tris(isocyanatophenyl)-thiophosphate.

[0179] The modified polyisocyanate compound derived from a diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups, and examples thereof include polyisocyanates having a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, an allophanate structure, a trimer structure, etc., and adducts of aliphatic isocyanates of trimethylolpropane, etc. Polymeric MDI (MDI=diphenylmethane diisocyanate) can also be used as a polyfunctional isocyanate compound.

[0180] The polyfunctional isocyanate compounds can be used alone or in combination of two or more.

[0181] The isocyanate group contained in the polyfunctional isocyanate compound may be an isocyanate group as it is, or may be a blocked isocyanate group blocked with a blocking agent. Examples of the blocking agent include pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole, and pyrazole; 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 formaldoxime, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; imidazole compounds such as imidazole and 2-methylimidazole; and sodium bisulfite. Among these, pyrazoles and oximes are preferred from the viewpoint of water repellency.

[0182] As the polyfunctional isocyanate compound, a water-dispersible isocyanate can be used, which is a polyisocyanate that has been given water dispersibility by introducing a hydrophilic group into the polyisocyanate structure to give it a surface active effect. In addition, a known catalyst such as an organotin or organozinc can be used in combination to promote the reaction.

[0183] The crosslinking agents and catalysts may be used alone or in combination of two or more.

[0184] The crosslinking agent can be attached to the treated object by, for example, immersing the treated object (textile product) in a treatment liquid in which the crosslinking agent is dissolved in an organic solvent or emulsified and dispersed in water, and drying the treatment liquid attached to the treated object. The crosslinking agent attached to the treated object can be heated to promote the reaction between the crosslinking agent and the treated object and the non-fluorine-based polymer (α). In order to promote the reaction of the crosslinking agent sufficiently and more effectively improve the washing durability, it is preferable to heat the crosslinking agent at 110 to 180°C for 1 to 5 minutes. The process of attaching the crosslinking agent and heating may be performed simultaneously with the process of treating with the treatment liquid containing the water repellent composition described above. When performing the processes simultaneously, for example, a treatment liquid containing the water repellent composition and the crosslinking agent is attached to the treated object, and after removing the water, the crosslinking agent attached to the treated object is further heated. In consideration of simplification of the water repellent processing process, reduction of the amount of heat, and economic efficiency, it is preferable to perform the process simultaneously with the treatment process of the water repellent composition.

[0185] Moreover, excessive use of the crosslinking agent may impair the feel. The crosslinking agent is preferably used in an amount of 0.1 to 50% by mass, particularly preferably 0.1 to 10% by mass, based on the material to be treated (textile product).

[0186] The water-repellent textile product of the present embodiment thus obtained can exhibit sufficient water repellency even when used outdoors for a long period of time, and since the water-repellent textile product does not use any fluorine-based compounds, it can be made environmentally friendly.

[0187] The water-repellent textile product of the present embodiment can be coated on a predetermined portion. Examples of coating include moisture-permeable waterproofing and windproofing for sports and outdoor use. For example, moisture-permeable waterproofing can be achieved by applying a coating liquid containing a urethane resin, an acrylic resin, or the like, and a medium to one side of the textile product that has been treated for water repellency, and then drying the coating liquid.

[0188] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments.

[0189] For example, in the case of producing the non-fluorinated polymer (α) contained in the water repellent composition of the present invention, the polymerization reaction is carried out by radical polymerization in the above embodiment, but the polymerization reaction may be carried out by photopolymerization in which ionizing radiation such as ultraviolet light, electron beams, or gamma rays is irradiated.

[0190] In addition, in the present invention, a textile product is treated with the water repellent composition to form a water repellent textile product. However, the products to be treated with the water repellent composition are not limited to textile products, and may also be articles of metal, glass, resin, etc.

[0191] In such a case, the method for applying the water repellent composition to the article and the amount of the water repellent applied can be determined arbitrarily depending on the type of the article to be treated, etc. EXAMPLES

[0192] The present invention will be further described below with reference to examples, but the present invention is not limited to these examples in any way.

[0193] <Preparation of polymer dispersion> A mixture having the composition shown in Tables 1 and 2 (in the tables, the numerical values ​​indicate (g)) was polymerized according to the procedure described below to obtain a dispersion of a polymer or a hydrophobic compound.

[0194] (Synthesis Example 1) In an autoclave, 23.4g of stearyl acrylate, 0.6g of diacetone acrylamide, 0.2g of Noigen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7), 1.3g of Noigen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5), 0.5g of Noigen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5), 0.4g of stearyl trimethylmonium sulfate, 12.5g of tripropylene glycol and 54.9g of water were placed and mixed and stirred at 45 ° C. to obtain a mixed solution. The mixed solution was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride was added to the mixed solution, and radical polymerization was carried out at 60°C for 6 hours under a nitrogen atmosphere while continuously injecting 6 g of vinyl chloride so as to maintain the internal pressure of the autoclave at 0.3 MPa, thereby obtaining a non-fluorinated polymer (α) dispersion containing 30.0 mass% of non-fluorinated polymer (α).

[0195] (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 non-fluorinated polymer (α) dispersions containing 30.0 mass % of non-fluorinated polymer (α).

[0196] (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 other non-fluorinated polymer dispersions containing 30.0 mass % of other non-fluorinated polymers.

[0197] (Comparative Synthesis Example 6) In a 1000 mL flask, 240.3 g of 1,4-butanediol, 758.5 ​​g of stearic acid, and 1.2 g of p-toluenesulfonic acid were placed, and a dehydration reaction was carried out for 4 hours at 130 to 200 ° C. under a nitrogen stream to obtain a product. The acid value and hydroxyl value of the obtained product were measured, and the acid value was 0.5 mg KOH / g, and the hydroxyl value was 162.1 mg KOH / g. In a separate container, 574.1 g of the above-mentioned product, 270.5 g of hexamethylene diisocyanate, and 0.9 g of a bismuth catalyst (manufactured by Nitto Kasei Co., Ltd., Neostan U-600) were placed, and the reaction was carried out at 80 ° C. for 3 hours. The reaction was carried out until the NCO% was 8.0. After the reaction, the temperature was lowered to 40 ° C., and then 154.6 g of 3,5-dimethylpyrazole was placed and the reaction was carried out at 40 ° C. for 1 hour to obtain a hydrophobic compound. In a 500mL stainless steel container, 40g of the obtained hydrophobic compound, 50g of methyl ethyl ketone, 5g of Decaglin 1-L (nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku), 5g of Decaglin 1-SV (nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku), and 5g of Arcard T-28 (cationic surfactant, manufactured by Lion Specialty Chemicals) were placed and dissolved by heating to 50°C. Then, 295g of hot water at 80°C was added, and emulsified for 20 minutes while maintaining the temperature at 80°C using an ultrasonic emulsifier US-600E (Nihon Seiki Seisakusho Co., Ltd.). After cooling, a 10% dispersion of the hydrophobic compound was obtained.

[0198] [Table 1]

[0199] [Table 2]

[0200] In addition, it was confirmed by gas chromatography (GC-15APTF, manufactured by Shimadzu Corporation) that 98% or more of the total monomers in each of the polymers in the polymer dispersions obtained in Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 to 5 were polymerized.

[0201] Details of the materials shown in Tables 1 and 2 are as follows: Noigen XL-100 (14.7) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7) Noigen XL-60 (12.5) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5) Noigen XL-40 (10.5) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5)

[0202] <Preparation of Dispersion Containing Silicone Resin> (Preparation Example 1) 20 parts by mass of SF 8416 (alkyl-modified silicone, product name, manufactured by Dow Corning Toray Co., Ltd.) as a silicone resin, 1 part by mass of SPAN60 (sorbitan-based nonionic surfactant, HLB=4.7, manufactured by Kao Corporation), 1 part by mass of TWEEN80 (sorbitan-based nonionic surfactant, HLB=15.0, manufactured by Kao Corporation), and 5 parts by mass of butyl diglycol were mixed. Next, 73.0 parts by mass of water were added little by little to the obtained mixture while mixing, and a dispersion containing 20% ​​by mass of silicone resin (β) was obtained.

[0203] (Preparation Examples 2 to 4) A silicone resin dispersion containing 20% ​​by mass of silicone resin was obtained in the same manner as in Preparation Example 1, except that the following resin was used as the silicone resin. (Preparation Example 2) BY 16-872 (Amino silicone, product name, manufactured by Dow Corning Toray Co., Ltd.) (Preparation Example 3) KF-9901 (Methyl hydrogen silicone, product name, manufactured by Shin-Etsu Chemical Co., Ltd.) (Preparation Example 4) KF-96-3000cs (dimethyl silicone, product name, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0204] (Preparation Example 5) 18.5 parts by mass of KF8005 (amino-modified silicone, product name, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.15 parts by mass of formic acid, and 0.5 parts by mass of an ethylene oxide 5 mole adduct of a branched alcohol having 12 to 14 carbon atoms were mixed. Next, 80.85 parts by mass of water was added little by little to the obtained mixture while being mixed, to obtain a dispersion containing 18.5% by mass of amino-modified silicone.

[0205] 15 parts by mass of MQ-1600 (silicone resin = trimethylsilyl group-containing polysiloxane, product name, manufactured by Dow Corning Toray Co., Ltd.) was added with 15 parts by mass of dimethyl silicone (6cs, product name, manufactured by Dow Corning Toray Co., Ltd.) and mixed until the silicone resin was dissolved to obtain a mixture. 18.5 parts by mass of the obtained mixture was mixed with 0.5 parts by mass of an ethylene oxide 5 mole adduct of a branched alcohol having 12 to 14 carbon atoms. Next, 81 parts by mass of water was added little by little while mixing to obtain a dispersion containing silicone resin and dimethyl silicone in total 18.5% by mass.

[0206] The above amino-modified silicone dispersion and a dispersion containing silicone resin and dimethyl silicone were mixed in a ratio of 100:117 to obtain a 20 mass% silicone resin dispersion containing amino-modified silicone, silicone resin, and dimethyl silicone in a mass ratio of 9.2:5.4:5.4 as silicone resin (β).

[0207] <Preparation of Water Repellent Composition> (Examples 1 to 15, Comparative Examples 1 to 9) A non-fluorinated polymer (α) dispersion, another non-fluorinated polymer dispersion, or a hydrophobic compound dispersion, a silicone resin (β) dispersion, and water were mixed so as to obtain the compositions shown in Tables 3 to 5 (the numerical values ​​in the tables indicate (mass %)), to obtain water repellent compositions, respectively.

[0208] (Water repellency evaluation of textile products) The test was conducted according to the spray method of JIS L 1092 (2009) with the shower water temperature at 20°C. In this test, dyed 100% polyester fabric or polyester (PET) / polyurethane (PU) blend fabric (polyester / polyurethane = 80 / 20) was immersed in the water repellent composition of the examples and comparative examples, dried at 130°C for 2 minutes, and further heat-treated at 170°C for 30 seconds to evaluate the water repellency of the obtained fabric. The results were visually evaluated according to the following grades. In addition, if the characteristics were slightly better, the grade was marked with "+", and if the characteristics were slightly worse, the grade was marked with "-". The results are shown in Tables 3 to 5. Water repellency: Status 5: No adhesion or wetness on the surface 4: Slightly wet surface 3: Shows partial surface wetting 2: Surface wetness 1: Shows wetting over the entire surface 0: Both sides are completely wet

[0209] (Feel evaluation of textile products) The feel was evaluated using dyed 100% polyester fabric that had been immersed in a treatment solution of the water repellent composition of the Examples and Comparative Examples, dried at 130°C for 2 minutes, and further heat-treated at 170°C for 30 seconds. The results were evaluated on a 5-point scale based on handling. The results are shown in Tables 3 to 5. 1: Hard ~ 5: Soft

[0210] (Evaluation of durable water repellency of textile products) The test was conducted according to the spray method of JIS L 1092 (2009) with the shower water temperature at 20°C. A blocked isocyanate-based crosslinking agent (NK Assist NY-50) was added to the water repellent composition of the examples and comparative examples to a concentration of 0.03% by mass to prepare a treatment liquid. Next, a dyed 100% polyester fabric was immersed in the prepared treatment liquid. After the immersion treatment, the fabric was dried at 130°C for 2 minutes and further heat-treated at 170°C for 60 seconds to obtain a fabric (L-0), and the fabric after washing 30 times (L-30) according to the 103 method of JIS L 0217 (1995) was evaluated for water repellency in the same manner as the water repellency evaluation method described above. In addition, the polyester (PET) / polyurethane (PU) blended fabric (polyester / polyurethane = 80 / 20) was evaluated in the same manner as the 100% polyester fabric, except that the heat treatment temperature was changed from 170°C to 160°C. The results are shown in Tables 3 to 5.

[0211] (Peel strength of textile coatings) The test was conducted in accordance with JIS K 6404-5 (1999). In this test, a dyed 100% nylon fabric was immersed in the water repellent composition of the examples and comparative examples, then dried at 130°C for 2 minutes, and further heat-treated at 170°C for 30 seconds to obtain a base fabric. A hot melt adhesive tape ("MELCO tape" manufactured by Sun Chemical Industry Co., Ltd.) was thermally bonded to the obtained base fabric at 150°C for 1 minute using a thermocompression device, and the peel strength between the base fabric and the seam tape was measured using an autograph (AG-IS, manufactured by Shimadzu Corporation). The moving speed of the gripper was 100 mm / min, and the average value of the stress was taken as the peel strength [N / inch]. The results are shown in Tables 3 to 5.

[0212] (Evaluation of repellency of textile products) The test was conducted according to the spray method of JIS L 1092 (2009) with the shower water temperature at 20°C, and the degree of water repellency during spray water repellency was visually confirmed and rated on the following 5-point scale. In this test, dyed polyester / polyurethane blended fabric (polyester / polyurethane = 80 / 20) was immersed in the water repellent composition of the examples and comparative examples, dried at 130°C for 2 minutes, and further heat-treated at 170°C for 30 seconds, and the repellency of the obtained fabric was evaluated. If the characteristics were slightly better, the grade was given "+", and if the characteristics were slightly worse, the grade was given "-". The results are shown in Tables 3 to 5. Repellency: Condition 5: Water that comes into contact with the fabric remains in the form of fine droplets, and the water splashes off the surface of the fabric. 4: Water that comes into contact with the fabric remains in the form of fine droplets and rolls off the surface of the fabric. 3: Water that comes into contact with the fabric remains in the form of large droplets and rolls off the surface of the fabric. 2: Water that comes into contact with the fabric does not remain in droplet form, but falls straight down the surface of the fabric. 1: Water that comes into contact with the fabric does not form droplets but instead snakes its way down

[0213] (Chalk mark evaluation of textile products) The chalk marks were evaluated using dyed 100% polyester fabrics that were immersed in the water repellent compositions of the Examples and Comparative Examples, dried at 130°C for 2 minutes, and then heat-treated at 170°C for 30 seconds. The surface of the treated fabric was scratched with a fingernail and visually evaluated on the following 5-point scale. The results are shown in Tables 3 to 5. 5: Clear claw marks are visible 4: Claw marks are visible 3: Some claw marks are visible 2: Almost no claw marks visible 1: No claw marks at all

[0214] [Table 3]

[0215] [Table 4]

[0216]

Table 5

Claims

1. A non-fluorinated polymer (α) containing a structural unit derived from a (meth)acrylic acid ester monomer (A1) represented by the following general formula (A-1) and a structural unit derived from a compound (A2) represented by the following general formula (A-2), A silicone resin (β), A water repellent composition comprising: 【Chemistry 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.] 【Chemistry 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, and W represents -CO-R １３ (In the formula, R １３ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), ２ or a group represented by the following formula (A-3): 【Chemistry 3】 ］

2. The water repellent composition according to claim 1, wherein the non-fluorinated polymer (α) further contains a structural unit derived from at least one monomer (VC) of vinyl chloride and vinylidene chloride.

3. A water-repellent textile product comprising a textile product having the water repellent composition according to claim 1 or 2 adhered thereto.

4. A method for producing a water-repellent textile product, comprising the step of treating a textile product with a treatment liquid containing the water repellent composition according to claim 1 or 2.

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