Methods for manufacturing non-fluorinated water-repellent agent compositions and water-repellent fiber products

Abstract

This invention discloses a non-fluorinated water-repellent composition that can improve the water-repellent properties of various articles during actual use. The non-fluorinated water-repellent composition of this invention contains: (A) a non-fluorinated water-repellent component, which is selected from at least one of the group consisting of acrylic compounds, polysiloxane compounds, wax compounds, carbamate compounds, and dendritic polymer compounds; and (B) an alicyclic polyisocyanate.

Description

[Technical Field]

[0001] This case discloses a non-fluorine water-repellent agent composition and a method for manufacturing a water-repellent fiber product. [Previous Technology]

[0002] Fluorinated water-repellent agents, such as those containing fluorinated compounds, are manufactured by polymerizing monomers with fluoroalkyl groups. Articles treated with such fluorinated water-repellent agents exhibit excellent water-repellent properties. However, there are concerns about the environmental burden caused by monomers with fluoroalkyl groups. Therefore, the international community has shifted towards pursuing non-fluorinated water-repellent agents that exhibit excellent water-repellent properties. For example, Patent Document 1 discloses a water-based water-repellent treatment agent containing a non-fluorinated water-repellent component and a crosslinking component that can react with the aforementioned water-repellent component, and is formed from a mixed emulsion containing the aforementioned water-repellent component and the aforementioned crosslinking component in one particle. Furthermore, Patent Document 2 discloses a water-repellent composition containing an amino-modified polysiloxane, a polysiloxane resin, and a polyfunctional isocyanate compound. [Prior Art Documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2017 / 199726 [Patent Document 2] Japanese Patent Application Publication No. 2017-226946 [Summary of the Invention]

[0004] [Technical Problem to be Solved by the Invention] Various water-repellent articles experience surface wear due to friction and other factors during actual use, easily reducing their water-repellent properties. In the prior art, there is still room for improvement regarding the water-repellent properties (wear-resistant water repellency) of such articles during actual use. [Technical Means]

[0005] As a means to solve the above-mentioned problems, this case discloses the following plurality of embodiments. < Embodiment 1> A non-fluorinated water-repellent composition comprising: (A) a non-fluorinated water-repellent component selected from at least one of acrylic compounds, polysiloxane compounds, wax compounds, carbamate compounds, and dendritic polymer compounds; and (B) an alicyclic polyisocyanate. < Embodiment 2> The non-fluorinated water-repellent composition of Embodiment 1, wherein (B) the alicyclic polyisocyanate is at least one of isophorone diisocyanate and hydrogenated MDI (methylene bis(cyclohexyl isocyanate)). < Embodiment 3> The non-fluorinated water-repellent composition of Embodiment 1 or 2, wherein (B) the alicyclic polyisocyanate is a trimer. <Sample 4> A non-fluorinated water-repellent composition of any of Samples 1-3, wherein, in addition to (B) alicyclic polyisocyanates, it also contains at least one of aliphatic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates. <Sample 5> A method for manufacturing a water-repellent fiber article, comprising the step of treating fibers with a treatment solution containing a non-fluorinated water-repellent composition of any of Samples 1-4. [Effects of the Invention]

[0006] Various articles are treated with the non-fluorine water-repellent composition of the present invention, thereby imparting excellent water-repellent properties to the articles. For example, the articles can become excellent in addition to initial water repellency and wash-resistant water repellency, as well as water repellency (abrasion-resistant water repellency) during actual use.

Implementation Method

[0008] 1. Non-fluorinated water-repellent composition The following describes an embodiment of a non-fluorinated water-repellent composition, but the non-fluorinated water-repellent composition of the present invention is not limited to this type. An embodiment of the non-fluorinated water-repellent composition contains: (A) a non-fluorinated water-repellent component, which is selected from at least one of the group consisting of acrylic compounds, polysiloxane compounds, wax compounds, carbamate compounds, and dendritic polymer compounds; and (B) an alicyclic polyisocyanate.

[0009] 1.1 (A) Non-fluorine-based water-repellent component A non-fluorine-based water-repellent agent composition of one embodiment contains at least one selected from the group consisting of acrylic compounds, polysiloxane compounds, wax compounds, urethane compounds, and dendritic polymer compounds as the (A) non-fluorine-based water-repellent component. The (A) non-fluorine-based compound can be at least one of acrylic compounds and polysiloxane compounds, or can be at least one of wax compounds, urethane compounds, and dendritic polymer compounds. In particular, when the (A) non-fluorine-based compound is at least one of acrylic compounds and polysiloxane compounds, more excellent performance can be expected.

[0010] 1.1.1 Acrylic compound The acrylic compound has, for example, a structural unit derived from a (meth)acrylate monomer represented by the following general formula (A1) (hereinafter also referred to as the "(A1) component"). The acrylic compound can further have a structural unit derived from a compound represented by the following general formula (A2) (hereinafter also referred to as the "(A2) component"). In this case, in the present application, "(meth)acrylate" means "acrylate" or the corresponding "methacrylate", and the same applies to "(meth)acrylic acid", "(meth)acrylamide", etc.

[0011] [Chemical formula 1] [In formula (A1), R1 is hydrogen or methyl; R2 is a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. ]

[0012] [Chemical formula 2] [In formula (A2), R11 is hydrogen or methyl; R12 is a divalent hydrocarbon group having 1 to 6 carbon atoms; Z is an ester group or an amide group; W is a group represented by -CO-R13 (R13 is 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 (W1). 【0OO13】[Chemical formula 3]

[0014] The above (A1) component has a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. This hydrocarbon group can be linear or branched, can be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and further can have an alicyclic or aromatic cyclic structure. Among these, from the viewpoint of water repellency, a linear one is ideal, and a linear alkyl group is more ideal. In this case, the water repellency will be more excellent. When the monovalent hydrocarbon group having 12 to 30 carbon atoms has a substituent, examples of the substituent include one or more of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloyloxy group, etc. In the above general formula (A-1), R2 is preferably an unsubstituted hydrocarbon group.

[0015] The ideal number of carbons in the aforementioned hydrocarbon group is 12 to 24, and more ideally 12 to 22. When the number of carbons is within this range, the water repellency and texture will be particularly excellent. The hydrocarbon group is particularly ideally a straight-chain alkyl group with 18 to 22 carbons.

[0016] The above-mentioned (A1) component may be, for example, selected from at least one of (meth)stearyl acrylate, (meth)cetyl acrylate, (meth)lauryl acrylate, (meth)myristyl acrylate, (meth)pentadecanyl acrylate, (meth)heptadecyl acrylate, (meth)nonadecanyl acrylate, (meth)ecicoacrylate, (meth)tidecyl acrylate and (meth)tidecyl acrylate.

[0017] The above-mentioned component (A1) may have at least one functional group selected from the group consisting of hydroxyl, amino, carboxyl, epoxy, and isocyanate groups that can react with a crosslinking agent. In this case, the durable water repellency can be further improved. The isocyanate group may also form a capped isocyanate group protected by a capping agent. In addition, if the above-mentioned component (A1) has an amino group, the texture can be further improved.

[0018] The above (A1) component is ideally a monofunctional (meth)acrylate monomer having a polymerizable unsaturated group within one molecule.

[0019] The above (A1) ingredient can be used alone or in combination of two or more.

[0020] In the above formula (A2), R12 can be straight-chain or branched, can be saturated hydrocarbon group or unsaturated hydrocarbon group, and further, can have an alicyclic ring structure.

[0021] In the above formula (A2), when Z is an ester group, R12 is ideally a hydrocarbon group with 2 to 4 carbon atoms, and W is ideally a group represented by -NH-CO-NH2 or a group represented by the above formula (W1). When Z is an amino group, R12 is ideally a hydrocarbon group with 2 to 4 carbon atoms, W is ideally a group represented by -CO-R13, and R13 is ideally 1 to 2 carbon atoms.

[0022] The above-mentioned (A2) component is not particularly limited, and examples include: diacetone acrylamide, 2-methacrylate [2-(2-dioxo-2-imidazolidine)ethyl] ester, and N-[2-(2-dioxo-2-imidazolidine-3-yl)ethyl]methacrylamide. Among these, from the viewpoint of durable water repellency, the above-mentioned (A2) component is ideally diacetone acrylamide or 2-methacrylate [2-(2-dioxo-2-imidazolidine)ethyl] ester.

[0023] The above (A2) ingredient can be used alone or in combination of two or more.

[0024] The ratio of constituent units derived from component (A1) to constituent units derived from component (A2) in acrylic compounds is the mass ratio of the (A1) component to the (A2) component. Ideally, (A1) / (A2) is 100 / 0 to 70 / 30, more ideally 99.9 / 0.1 to 70 / 30, even more ideally 99.8 / 0.2 to 80 / 20, and particularly ideally 99.7 / 0.3 to 90 / 10. If (A1) / (A2) is within the above range, the durable water repellency and water-repellent properties are better.

[0025] The total mass of the (A1) component and the (A2) component combined is ideally 60 to 100% by mass, more ideally 70 to 99% by mass, and even more ideally 80 to 98% by mass, relative to the total amount of monomer components constituting acrylic compounds.

[0026] From the viewpoint of peel strength, acrylic compounds ideally contain, in addition to component (A1) and, depending on the case, component (A2), at least one of vinyl chloride and vinylidene chloride monomer (A3) (hereinafter also referred to as "(A3) component") as monomer components.

[0027] (A3) From the point of view of maintaining the texture of fiber products, the ideal component is vinyl chloride.

[0028] From the viewpoint of water repellency, durable water repellency, and peel strength, the mass of the formulated component (A3) is ideally 10 parts by mass or more, and more ideally 20 parts by mass or more, relative to the total mass of the formulated component (A1) and component (A2) of 100 parts by mass. From the viewpoint of water repellency, durable water repellency, and texture, the mass of the formulated component (A3) is ideally 100 parts by mass or less, and more ideally 75 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less, relative to the total mass of the formulated component (A1) and component (A2) of 100 parts by mass.

[0029] From the viewpoint that acrylic compounds can improve their emulsification stability in the composition during and after emulsification polymerization or dispersion polymerization, it is ideal that, in addition to component (A1) and component (A2) as appropriate, they also contain a reactive emulsifier (A4) as a monomer component, selected from at least one of the following compounds with HLB of 7 to 18 and represented by the following general formula (A4-1), compounds with HLB of 7 to 18 and represented by the following general formula (A4-2), and compounds with HLB of 7 to 18 that are formed by adding an epoxide with 2 to 4 carbons to an oil having hydroxyl and polymerizable unsaturated groups (A4-3).

[0030] 〔Chemical 4〕[In formula (A4-1), R3 is hydrogen or methyl; X is a straight-chain or branched alkyl group having 1 to 6 carbon atoms; Y1 is a divalent group containing an alkoxy group having 2 to 4 carbon atoms.]

[0031] 〔Chemical 5〕[In formula (A4-2), R4 is a monovalent unsaturated hydrocarbon group with 13-17 carbon atoms and a polymerizable unsaturated group; Y2 is a divalent group containing an alkoxy group with 2-4 carbon atoms.]

[0032] In this case, "reactive emulsifier" refers to an emulsifying dispersant with free radical reactivity, that is, a surfactant having one or more polymerizable unsaturated groups in its molecule, and which can copolymerize with monomers such as (meth)acrylates.

[0033] In addition, "HLB" refers to the HLB value calculated by the Griffin method, which treats the ethoxy group as a hydrophilic group and all others as lipophilic groups.

[0034] The HLB values ​​of the compounds (A4-1) to (A4-3) above are 7 to 18. From the viewpoint of emulsification stability (hereinafter referred to as emulsification stability) of acrylic compounds in emulsification polymerization or dispersion polymerization and in the composition after polymerization, the ideal value is 9 to 15. Furthermore, from the viewpoint of storage stability of the water-repellent composition, it is more ideal to use two or more reactive emulsifiers (A4) having different HLB values ​​within the above range.

[0035] In the above general formula (A4-1), R3 is hydrogen or methyl, and methyl is more ideal from the viewpoint of copolymerization with component (A1) and / or component (A2). X is a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and straight-chain alkyl group having 2 to 3 carbon atoms is more ideal from the viewpoint of emulsification stability of acrylic compounds. Y1 is a divalent group containing an alkoxy group having 2 to 4 carbon atoms. The type, combination, and number of addition groups of the alkoxy groups in Y1 can be suitably selected within the range of the above HLB. Furthermore, in the case of two or more alkoxy groups, they may have a block addition structure or a random addition structure.

[0036] The compound represented by the above general formula (A4-1) is ideally represented by the compound represented by the following general formula (A4-1-1).

[0037] 〔Chemical 6〕[In formula (A4-1-1), R3 is hydrogen or methyl; X is a straight-chain or branched alkyl group having 1 to 6 carbon atoms; AlO is an alkoxy group having 2 to 4 carbon atoms; m can be suitably selected within the range of the above HLB, specifically, ideally an integer from 1 to 80. When m is 2 or more, the m AlOs can be the same or different.]

[0038] In the compound represented by the above general formula (A4-1-1), R3 is hydrogen or methyl, and methyl is more ideal from the viewpoint of copolymerization with component (A1) and / or component (A2). X is a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and straight-chain alkyl group having 2 to 3 carbon atoms is more ideal from the viewpoint of emulsification stability of acrylic compounds. A1O is an alkoxy group having 2 to 4 carbon atoms. The type and combination of A1O, and the value of m, can be suitably selected within the above HLB range. From the viewpoint of emulsification stability of acrylic compounds, m is ideally an integer from 1 to 80, and more ideally an integer from 1 to 60. When m is 2 or more, the m A1Os can be the same or different. Furthermore, in the case of two or more A1Os, they can have a block addition structure or a random addition structure.

[0039] The reactive emulsifier represented by the above general formula (A4-1-1) can be obtained by conventional methods and is not particularly limited. In addition, it can be easily obtained from commercially available products, such as "LATEMUL PD-420", "LATEMUL PD-430", and "LATEMUL PD-450" manufactured by Kao Corporation.

[0040] In the above general formula (A4-2), R4 is a monovalent unsaturated hydrocarbon group with 13 to 17 carbon atoms and a polymerizable unsaturated group. Examples of such unsaturated hydrocarbon groups include: tridepenyl, tridecadienyl, tetradecadienyl, tetradecadienyl, pentadecenyl, pentadecadienyl, pentadectrienyl, heptadecadienyl, heptadecadienyl, and heptadecatrienyl. From the viewpoint of emulsification stability of acrylic compounds, R4 is more ideally a monovalent unsaturated hydrocarbon group with 14 to 16 carbon atoms.

[0041] Y2 is a divalent group containing an alkoxy group having 2 to 4 carbon atoms. The type, combination, and number of addition groups of the alkoxy groups in Y2 can be suitably selected within the range of the above-mentioned HLB. Furthermore, in the case of two or more alkoxy groups, they may have a block addition structure or a random addition structure. From the viewpoint of the emulsification stability of acrylic compounds, alkoxy groups are more ideally ethoxy groups.

[0042] The compound represented by the above general formula (A4-2) is ideally represented by the compound represented by the following general formula (A4-2-1).

[0043] 〔Chemical 7〕[In formula (A4-2-1), R4 is a monovalent unsaturated hydrocarbon group with 13 to 17 carbon atoms having a polymerizable unsaturated group; A2O is an alkoxy group with 2 to 4 carbon atoms; n can be suitably selected within the range of the above HLB, specifically, ideally an integer from 1 to 50. When n is 2 or more, the n A2Os can be the same or different.]

[0044] R4 in the compound represented by the above general formula (A4-2-1) can be listed as being the same as R4 in the above general formula (A4-2).

[0045] A2O is an alkoxy group with 2 to 4 carbon atoms. From the viewpoint of emulsification stability of acrylic compounds, the type and combination of A2O, as well as the value of n, can be suitably selected within the aforementioned HLB range. From the viewpoint of emulsification stability of acrylic compounds, A2O is more ideally an ethoxy group; n is ideally an integer from 1 to 50, more ideally an integer from 5 to 20, and even more ideally an integer from 8 to 14. When n is 2 or more, the n A2Os can be the same or different. Furthermore, in the case of two or more A2Os, they can have block addition structures or random addition structures.

[0046] The reactive emulsifier represented by the above general formula (A4-2-1) can be synthesized, for example, by adding an epoxide to a corresponding phenol having an unsaturated hydrocarbon group, but is not limited thereto. For example, it can be synthesized by adding a specified amount of epoxide to a phenol under pressure at 120~170°C using an alkaline catalyst such as sodium hydroxide or potassium hydroxide.

[0047] The phenols with unsaturated hydrocarbon groups mentioned above include not only industrially manufactured pure products or mixtures, but also those that exist as pure products or mixtures extracted and refined from plants, etc. Examples include: 3-[8(Z),11(Z),14-pentadecantrienyl]phenol, 3-[8(Z),11(Z)-pentadecanadienyl]phenol, 3-[8(Z)-pentadecanyl]phenol, 3-[11(Z)-pentadecanyl]phenol, etc., extracted from cashew nut shells, etc., and collectively referred to as cardanol.

[0048] Compound (A4-3) is a compound with an HLB of 7-18 and formed by adding an epoxide with 2-4 carbon atoms to an oil containing hydroxyl groups and polymerizable unsaturated groups. Examples of oils containing hydroxyl groups and polymerizable unsaturated groups include: mono- or diglycerides of fatty acids containing hydroxyunsaturated fatty acids (palmitoic acid, oleic acid, linolenic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.); and triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid (ricinoleic acid, trans-ricinoleic acid, 2-hydroxytetraenoic acid, etc.). From the viewpoint of emulsifying stability of acrylic compounds, an epoxide adduct of a triglyceride containing at least one hydroxyunsaturated fatty acid is ideal; an epoxide adduct of castor oil (containing ricinoleic acid triglycerides) with 2-4 carbon atoms is more ideal; and an ethylene oxide adduct of castor oil is even more ideal. Furthermore, the molar number of the epoxide addition can be suitably selected within the aforementioned HLB range. From the viewpoint of emulsification stability of acrylic compounds, 20-50 molars is more ideal, and 25-45 molars is even more ideal. In addition, in cases where there are two or more epoxides, they may have block addition structures or random addition structures.

[0049] Compound (A4-3) can be synthesized, for example, by adding an epoxide to an oil containing a hydroxyl group and a polymerizable unsaturated group, but is not limited thereto. For example, it can be synthesized by adding a specified amount of epoxide to a triglyceride of a fatty acid containing ricinoleic acid, i.e., castor oil, using an alkaline catalyst such as sodium hydroxide or potassium hydroxide, under pressure and at 120-170°C.

[0050] From the viewpoint of improving water repellency and emulsification stability of acrylic compounds in emulsion polymerization or dispersion polymerization and in the post-polymerization composition, the composition ratio of the monomers of the above (A4) components in the acrylic compound is ideally 0.5 to 20% by mass, more ideally 1 to 15% by mass, and even more ideally 3 to 10% by mass, relative to the total amount of monomer components constituting the acrylic compound.

[0051] Acrylic compounds, from the viewpoint of improving durable water repellency, may contain, in addition to component (A1) and component (A2) as appropriate, at least one second (meth)acrylate monomer (A5) (hereinafter also referred to as "A5 component") selected from the group consisting of monomers represented by general formula (A5-1), monomers represented by general formula (A5-2), monomers represented by general formula (A5-3), and monomers represented by general formula (A5-4) as monomer components.

[0052] 〔Chemical 8〕[In formula (A5-1), R5 is hydrogen or methyl; R6 is a monovalent chain hydrocarbon group with 1 to 11 carbon atoms having at least one functional group selected from the group consisting of hydroxyl, amino, carboxyl, epoxy, isocyanate, and (meth)acryloxy. However, the number of (meth)acryloxy groups in the molecule is 2 or less.]

[0053] 〔Chemical 9〕[In formula (A5-2), R7 is hydrogen or methyl; R8 is a monovalent cyclic hydrocarbon group with 1 to 11 carbon atoms that may have substituents.]

[0054] 〔Chemical 10〕[In formula (A5-3), R9 is an unsubstituted monovalent chain hydrocarbon group with 1 to 4 carbon atoms.]

[0055] 〔Chemical 11〕[In formula (A5-4), R10 is hydrogen or methyl; p is an integer greater than or equal to 2; S is a (p+1) valence organic group; T is a monovalent organic group with polymerizable unsaturated groups.]

[0056] The monomer described above (A5-1) is a (meth)acrylate monomer having a monovalent chain hydrocarbon group with 1 to 11 carbon atoms in the ester portion, having a functional group selected from at least one of the groups consisting of hydroxyl, amino, carboxyl, epoxy, isocyanate, and (meth)acrylic acid. From the viewpoint of being able to react with a crosslinking agent, the monovalent chain hydrocarbon group with 1 to 11 carbon atoms is ideally having a functional group selected from at least one of the groups consisting of hydroxyl, amino, carboxyl, epoxy, and isocyanate. When an acrylic compound containing a monomer with (A5-1) having such a group that can react with a crosslinking agent is used to treat a fiber product, the durable water repellency can be improved while maintaining the texture of the resulting fiber product. The isocyanate group can also be a capped isocyanate group protected by a capping agent.

[0057] The aforementioned chain hydrocarbon group may be straight-chain or branched, and may be saturated or unsaturated hydrocarbon groups. In addition to the aforementioned functional groups, the chain hydrocarbon group may also have substituents. From the viewpoint of improving water repellency, it is ideal to be straight-chain and / or saturated hydrocarbon groups.

[0058] Specifically, monomers of (A5-1) include: 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloxymethyl)ethyl isocyanate. These monomers can be used alone or in combination of two or more. From the viewpoint of improving durable water repellency, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloxymethyl)ethyl isocyanate are ideal. Furthermore, from the viewpoint of improving texture, dimethylaminoethyl (meth)acrylate is ideal.

[0059] From the viewpoint of water repellency, the mass of the formulated (A5-1) component is ideally 3 parts by mass or more, and more ideally 5 parts by mass or more, relative to the total mass of the (A1) component and the (A2) component (100 parts by mass). From the viewpoint of water repellency, the mass of the formulated (A5-1) component is ideally 30 parts by mass or less, and more ideally 25 parts by mass or less, relative to the total mass of the (A1) component and the (A2) component (100 parts by mass).

[0060] The monomers described above (A5-2) are (meth)acrylate monomers having a monovalent cyclic hydrocarbon group with 1 to 11 carbon atoms in the ester portion. Examples of cyclic hydrocarbon groups include isobornyl, cyclohexyl, and dicyclopentanyl. These cyclic hydrocarbon groups may also have substituents such as alkyl groups. However, when the substituent is a hydrocarbon group, the hydrocarbon group whose total number of carbon atoms in the substituent and the cyclic hydrocarbon group is 11 or less is selected. Furthermore, from the viewpoint of improving durable water repellency, these cyclic hydrocarbon groups are ideally directly bonded to the ester bond. The cyclic hydrocarbon group can be alicyclic or aromatic; in the case of an alicyclic group, it can be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specific monomers include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. These monomers can be used alone or in combination of two or more. From the perspective of improving durable water repellency, isoborneol methacrylate and cyclohexyl methacrylate are ideal, with isoborneol methacrylate being even more ideal.

[0061] From the viewpoint of water repellency, the mass of the formulated component (A5-2) is ideally 3 parts by mass or more, and more ideally 5 parts by mass or more, relative to the total mass of the formulated component (A1) and component (A2) of 100 parts by mass. From the viewpoint of water repellency, the mass of the formulated component (A5-2) is ideally 30 parts by mass or less, and more ideally 25 parts by mass or less, relative to the total mass of the formulated component (A1) and component (A2) of 100 parts by mass.

[0062] The monomers described above (A5-3) are methacrylate monomers formed by directly bonding unsubstituted monovalent chain hydrocarbon groups with 1 to 4 carbon atoms to the ester bond of the ester moiety. Ideally, the chain hydrocarbon groups with 1 to 4 carbon atoms are straight-chain hydrocarbon groups with 1 to 2 carbon atoms or branched hydrocarbon groups with 3 to 4 carbon atoms. Examples of chain hydrocarbon groups with 1 to 4 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tributyl, etc. Specific compounds include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tributyl methacrylate. These monomers can be used alone or in combination of two or more. From the viewpoint of improving water repellency, methyl methacrylate, isopropyl methacrylate, and tributyl methacrylate are ideal, with methyl methacrylate being more ideal.

[0063] From the viewpoint of water repellency, the mass of the formulated (A5-3) component is ideally 3 parts by mass or more, and more ideally 5 parts by mass or more, relative to the total mass of the (A1) component and the (A2) component (100 parts by mass). From the viewpoint of water repellency, the mass of the formulated (A5-3) component is ideally 30 parts by mass or less, and more ideally 25 parts by mass or less, relative to the total mass of the (A1) component and the (A2) component (100 parts by mass).

[0064] The monomer in (A5-4) above is a (meth)acrylate monomer having three or more polymerizable unsaturated groups within a molecule. Ideally, it is a polyfunctional (meth)acrylate monomer having three or more (meth)acryloxy groups within a molecule, where T in the above general formula (A5-4) is a (meth)acryloxy group. In formula (A5-4), the p Ts can be the same or different. Specific compounds may be listed as follows: ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, neopentyltetroxide triacrylate, neopentyltetroxide trimethacrylate, dinepentyltetroxide hexaacrylate, dinepentyltetroxide hexamethacrylate, etc. These monomers can be used alone or in combination of two or more. From the perspective of improving water repellency and durability, tetramethylolpropane tetraacrylate and ethoxyisocyanurate triacrylate are more ideal.

[0065] From the viewpoint of water repellency, the mass of the formulated component (A5-4) is ideally 3 parts by mass or more, and more ideally 5 parts by mass or more, relative to the total mass of the formulated component (A1) and component (A2) of 100 parts by mass. From the viewpoint of water repellency, the mass of the formulated component (A5-4) is ideally 30 parts by mass or less, and more ideally 25 parts by mass or less, relative to the total mass of the formulated component (A1) and component (A2) of 100 parts by mass.

[0066] In terms of water repellency and texture, the total composition ratio of the monomers of the above (A5) component in the acrylic compound is ideally 1 to 30% by mass, more ideally 3 to 25% by mass, and even more ideally 5 to 20% by mass, relative to the total amount of monomer components constituting the acrylic compound.

[0067] From the viewpoint of water repellency, the mass of the formulated component (A5) is ideally 3 parts by mass or more, and more ideally 5 parts by mass or more, relative to the total mass of the formulated components (A1 and A2) of 100 parts by mass. From the viewpoint of water repellency, the mass of the formulated component (A5) is ideally 30 parts by mass or less, and more ideally 25 parts by mass or less, relative to the total mass of the formulated components (A1 and A2) of 100 parts by mass.

[0068] In addition to component (A1) and component (A2) as appropriate, acrylic compounds may also contain monofunctional monomers (A6) that can copolymerize with such monomers (hereinafter also referred to as "(A6) component") to the extent that the effects of the present invention are not impaired.

[0069] Component (A6) may include, for example: (meth)acrylic acid morpholine, (meth)acrylates with hydrocarbon groups other than those in (A1), (A2), and (A5) above, (meth)acrylic acid, fumarate, maleate, fumaric acid, maleic acid, (meth)acrylamide, N-hydroxymethylacrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other ethylene monomers other than those in component (A3) that do not contain fluorine. Furthermore, (meth)acrylates with hydrocarbon groups other than those in components (A1), (A2), and (A5) may have substituents such as vinyl, hydroxyl, amino, epoxy, isocyanate, or terminal isocyanate groups on the hydrocarbon group, or substituents other than quaternary ammonium groups that can react with crosslinking agents, or ether bonds, ester bonds, amide bonds, or carbamate bonds. Examples of (meth)acrylates other than components (A1), (A2), and (A5) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol di(meth)acrylate. Among these, (meth)acrylic acid morpholine is more ideal from the viewpoint of improving the peel strength of the resulting fibrous product against the coating.

[0070] From the viewpoint of water repellency, the mass of the formulated (A6) component is ideally 3 parts by mass or more, and more ideally 5 parts by mass or more, relative to the total mass of the formulated (A1) component and (A2) component (100 parts by mass). From the viewpoint of water repellency, the mass of the aforementioned (A6) monomer is ideally 40 parts by mass or less, and more ideally 35 parts by mass or less, relative to the total mass of the formulated (A1) component and (A2) component (100 parts by mass).

[0071] In terms of improving durable water repellency, acrylic compounds ideally have at least one functional group selected from the group consisting of hydroxyl, amino, carboxyl, epoxy, and isocyanate groups that can react with crosslinking agents. Isocyanate groups can also form capped isocyanate groups protected by capping agents. Furthermore, in terms of improving texture, acrylic compounds ideally have amino groups.

[0072] The ideal weight-average molecular weight of acrylic compounds is 30,000 or higher. If the weight-average molecular weight is 30,000 or higher, the water-repellent properties tend to be further enhanced. Furthermore, the ideal weight-average molecular weight of acrylic compounds is 50,000 or higher. In this case, the water-repellent properties can be more fully utilized. The ideal upper limit for the weight-average molecular weight of acrylic compounds is around 5 million.

[0073] The weight average molecular weight of acrylic compounds refers to the value obtained by measuring the molecular weight using a GPC (gel permeation chromatography) apparatus (Tosoh Corporation's GPC "HLC-8020") at a column temperature of 40°C and a flow rate of 1.0 ml / min, using tetrahydrofuran as the dissolution solution, and converting it to standard polystyrene. Furthermore, the column used is composed of three Tosoh Corporation-manufactured products: TSK-GELG5000HHR, G4000HHR, and G3000HHR, connected together.

[0074] The ideal melt viscosity of acrylic compounds at 105°C is 1000 Pa·s or less. When the melt viscosity at 105°C is 1000 Pa·s or less, it tends to maintain a good texture. Furthermore, when the melt viscosity of acrylic compounds is 1000 Pa·s or less, the precipitation or sedimentation of acrylic compounds can be suppressed when they are emulsified or dispersed to form a water-repellent composition, thus tending to maintain good storage stability of the water-repellent composition. Moreover, the ideal melt viscosity at 105°C is 500 Pa·s or less. In this case, while maintaining sufficient water repellency, the texture will also be even better.

[0075] "Melt viscosity at 105°C" refers to the viscosity measured when 1g of a non-fluorinated polymer is placed in a cylinder with a mold (10mm in length and 1mm in diameter) using an overhead flow tester (e.g., Shimadzu CFT-500), and the mixture is kept at 105°C for 6 minutes, and then a load of 100kg･f / cm2 is applied by a plunger.

[0076] 1.1.2 Polysiloxane Compounds Polysiloxane compounds are, for example, at least one of polysiloxane resins and polysiloxane oils. From a water-repellent point of view, polysiloxane resins are ideal among these polysiloxane compounds. One polysiloxane compound may be used alone or in combination of two or more.

[0077] The polysiloxane may be an organopolysiloxane containing MQ, MDQ, MT, MTQ, MDT, or MDTQ as constituent components, which is solid at 25°C and has a three-dimensional structure. Here, M, D, T, and Q represent (R'')3SiO0.5 units, (R'')2SiO units, R''SiO1.5 units, and SiO2 units, respectively. R'' represents a monovalent aliphatic hydrocarbon group with 1 to 10 carbon atoms, or a monovalent aromatic hydrocarbon group with 6 to 15 carbon atoms.

[0078] Polysiloxane resin is commonly referred to as MQ resin, MT resin or MDT resin, and sometimes also has a part indicating MDQ, MTQ or MDTQ.

[0079] Polysiloxanes can also be obtained in the form of a solution formed by dissolving them in a suitable solvent. Examples of solvents include, for example, relatively low molecular weight methyl polysiloxanes, decamethylcyclopentasiloxanes, octamethylcyclotetrasiloxanes, n-hexane, isopropanol, dichloromethane, 1,1,1-trichloroethane, and mixtures of these solvents.

[0080] Solutions of polysiloxane resins, for example, include KF7312J (a mixture of trimethylsilyl polysiloxane and decamethylcyclopentasiloxane = 50:50), KF7312F (a mixture of trimethylsilyl polysiloxane and octamethylcyclotetrasiloxane), KF9021L (a mixture of trimethylsilyl polysiloxane and low-viscosity methyl polysiloxane = 50:50), and KF7312L (a mixture of trimethylsilyl polysiloxane and low-viscosity methyl polysiloxane = 50:50), which are commercially available from Shin-Etsu Chemical Co., Ltd.

[0081] Examples of standalone polysiloxanes include: MQ-1600 solid Resin (a trimethylsilyl polysiloxane) and MQ-1640 Flake Resin (a trimethylsilyl polysiloxane and polypropyl silsesquioxane) commercially available from Toray Dow Corning (Co., Ltd.). These commercially available products contain trimethylsilyl polysiloxane and also contain MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0082] Polysiloxane, which is a linear organic polysiloxane, may also have organic groups in at least one of the side chains and the end of the organic polysiloxane. This type of polysiloxane oil can use the same types as hydrophobic polysiloxane oil and functionalized polysiloxane oil, such as: linear polysiloxane oils like dimethyl polysiloxane oil, methylphenyl polysiloxane oil, and methylhydrogen polysiloxane oil; modified polysiloxane oils like amine-modified polysiloxane oil, epoxy-modified polysiloxane oil, methanol-modified polysiloxane oil, mercapto-modified polysiloxane oil, carboxyl-modified polysiloxane oil, polyether-modified polysiloxane oil, alkyl-modified polysiloxane oil, aralkyl-modified polysiloxane oil, alkylaralkyl-modified polysiloxane oil, higher fatty acid ester-modified polysiloxane oil, and higher aliphatic amide-modified polysiloxane oil, etc.

[0083] Amine-modified polysiloxane oils may be listed as compounds in which at least one of the side chains and terminals of an organopolysiloxane has an organic group containing an amino group and / or an imine group. Such organic groups may include: organic groups represented by -R-NH2, organic groups represented by -R-NH-R'-NH2. R and R' may include: divalent groups such as ethylidene and propylidene. Some or all of the amino group and / or imine group may be blocked amino groups and / or imine groups. Blocked amino groups and / or imine groups may be obtained, for example, by treating the amino group and / or imine group with a blocking agent. Blocking agents may include, for example: fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, amide halides of fatty acids having 2 to 22 carbon atoms, aliphatic monoisocyanates having 1 to 22 carbon atoms, etc.

[0084] The functional group equivalent of amine-modified polysiloxane oil, from the viewpoint of water repellency, is ideally 100~20000 g / mol, more ideally 150~12000 g / mol, and even more ideally 200~4000 g / mol.

[0085] Ideally, amine-modified polysiloxane oil is liquid at 25°C. The ideal kinematic viscosity of amine-modified polysiloxane oil at 25°C is 10~100,000 mm² / s, more ideally 10~30,000 mm² / s, and even more ideally 10~5,000 mm² / s. If the kinematic viscosity at 25°C is greater than 100,000 mm² / s, there is a tendency for excessively high viscosity and poor workability. The kinematic viscosity at 25°C refers to the value measured using the method described in JIS K 2283:2000 (Ubelod viscometer).

[0086] Amine-modified polysiloxane oils are also readily available in commercially available form. Commercially available products include, for example: KF8005, KF-868, KF-864, KF-393, and KF-8021 (all manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade names); TSF-4709 and XF42-B1989 (manufactured by Momentive Performance Materials Japan LLC, trade names); BY16-872, SF-8417, BY16-853U, and BY16-892 (all manufactured by Toray Industries and Dow Corning, Ltd., trade names); KF-8010 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.); and WACKER (registered trademark) FINISH WR 301 (manufactured by Wacker Asahikasei Silicone Co., Ltd.), etc.

[0087] In addition, polysiloxane oils other than amino-modified polysiloxane oils are also readily available in commercially available forms. Examples of commercially available products include: KF-101 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: epoxy-modified polysiloxane oil), X-22-3701E (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: carboxyl-modified polysiloxane oil), SF8428 (manufactured by Toray Industries & Dow Corning Co., Ltd., trade name: methanol-modified polysiloxane oil), KF-9901 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: methyl hydrogen polysiloxane oil), X-22-715 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: methyl hydrogen polysiloxane oil), and others. (Shin-Etsu Chemical Co., Ltd., trade name: Advanced fatty acid ester modified polysiloxane oil), KF-96-3000cp (Shin-Etsu Chemical Co., Ltd., trade name: Dimethyl polysiloxane oil), SF8416 (Toray & Dow Corning Co., Ltd., trade name: Alkyl modified polysiloxane oil), SH203 (Toray & Dow Corning Co., Ltd., trade name: Alkyl aralkyl modified polysiloxane oil), SF8410 (Toray & Dow Corning Co., Ltd., trade name: Polyether modified polysiloxane oil), etc.

[0088] The polysiloxane compound may also be an organically modified polysiloxane represented by the following general formula (1). Furthermore, in the following general formula (1), each structural unit may be block or random, or may be arranged alternately.

[0089] 〔Chemical 12〕[In formula (1), R20, R21 and R22 are each independently hydrogen atom, methyl, ethyl or alkoxy group with 1 to 4 carbon atoms; R23 is a hydrocarbon group with 8 to 40 carbon atoms having an aromatic ring or an alkyl group with 8 to 40 carbon atoms; R30, R31, R32, R33, R34 and R35 are each independently hydrogen atom, methyl, ethyl, alkoxy group with 1 to 4 carbon atoms, hydrocarbon group with 8 to 40 carbon atoms having an aromatic ring or an alkyl group with 3 to 22 carbon atoms; a is an integer of 0 or more, b is an integer of 1 or more, (a+b) is 10 to 200, when a is 2 or more, the multiple R20 and R21 can be the same or different, when b is 2 or more, the multiple R22 and R23 can be the same or different.]

[0090] In organically modified polysiloxanes, the alkoxy groups with 1 to 4 carbon atoms can be linear or branched. Examples of alkoxy groups with 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy. From the viewpoint of ease of industrial manufacture and availability, R20, R21, and R22 are ideally composed of hydrogen atoms or methyl groups, and more ideally, each is composed of a methyl group.

[0091] The hydrocarbon groups having 8 to 40 carbon atoms in the above-mentioned aromatic rings can be exemplified by, for example, aralkyl groups having 8 to 40 carbon atoms, groups represented by the following general formula (2) or (3), etc.

[0092] 〔Chemical 13〕[In formula (2), R40 is an alkyl group with 2 to 6 carbon atoms; R41 is a single bond or an alkyl group with 1 to 4 carbon atoms; c is an integer from 0 to 3. In the case where c is 2 or 3, the multiple R41s can be the same or different.]

[0093] The above-mentioned alkyl groups may be linear or branched.

[0094] 〔Chemical 14〕[In formula (3), R42 is an alkyl group with 2 to 6 carbon atoms; R43 is a single bond or an alkyl group with 1 to 4 carbon atoms; d is an integer from 0 to 3. In the case where d is 2 or 3, the multiple R43s can be the same or different.]

[0095] The above-mentioned alkyl groups may be linear or branched.

[0096] Examples of the aralkyl groups having 8 to 40 carbon atoms include phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, and naphthylethyl. Among these, phenylethyl and phenylpropyl are ideal from the viewpoint of being easy to manufacture and obtain industrially.

[0097] In the group represented by the above general formula (2), from the viewpoint of being easy to manufacture and obtain industrially, R40 is ideally an alkyl group with 2 to 4 carbons, and c is ideally 0 or 1, more ideally 0.

[0098] In the group represented by the above general formula (3), from the viewpoint of being easy to manufacture and obtain industrially, R42 is ideally an alkyl group with 2 to 4 carbons, and d is ideally 0 or 1, more ideally 0.

[0099] The hydrocarbon group having 8 to 40 carbons with an aromatic ring is preferably an aralkyl group having 8 to 40 carbons and a group represented by the general formula (2) above, from the viewpoint that it is easy to manufacture and obtain industrially; from the viewpoint that it can improve water repellency, it is more preferably an aralkyl group having 8 to 40 carbons.

[0100] The aforementioned alkyl groups with 8 to 40 carbon atoms can be linear or branched. Examples of alkyl groups with 8 to 40 carbon atoms include: octyl, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, stearyl, dodecyl, hexadecyl, octadecyl, tridecyl, and tridecyl. From the viewpoint of improving water repellency, alkyl groups with 12 to 36 carbon atoms are ideal, and alkyl groups with 16 to 34 carbon atoms are even more ideal. Furthermore, the fewer carbon atoms in the alkyl group, the better the chalk mark tends to be. In addition, the more carbon atoms in the alkyl group, the better the water repellency tends to be. Furthermore, if the number of carbon atoms exceeds 40, the stability of the dispersion tends to decrease. Moreover, in the case of fewer than 8 carbon atoms, the water repellency tends to become poor.

[0101] In the organically modified polysiloxane, R30, R31, R32, R33, R34, and R35 are each independently a hydrogen atom, methyl, ethyl, alkoxy group with 1 to 4 carbon atoms, hydrocarbon group with 8 to 40 carbon atoms having an aromatic ring, or alkyl group with 3 to 22 carbon atoms. From the viewpoint of ease of industrial manufacture and availability, it is ideal for R30, R31, R32, R33, R34, and R35 to be independently a hydrogen atom, methyl, ethyl, or alkoxy group with 1 to 4 carbon atoms, with methyl being the most ideal.

[0102] In organic modified polysiloxane, a is an integer greater than or equal to 0. From the perspective of ease of industrial manufacturing, availability, and superior peel strength, a is ideally below 40, and even more ideally below 30.

[0103] In organically modified polysiloxane, (a+b) is 10~200. From the viewpoint of ease of industrial manufacture and availability, (a+b) is ideally 20~100, and more ideally 40~60. If (a+b) is within the above range, the manufacture and handling of polysiloxane itself tend to become easier.

[0104] Organically modified polysiloxanes can be synthesized by conventional methods. Organically modified polysiloxanes can be obtained, for example, by hydrosilylation of a polysiloxane having a SiH group with an aromatic compound having a vinyl group and / or an α-olefin.

[0105] Examples of the polysiloxanes having SiH groups mentioned above include methylhydrosiloxanes with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxanes and methylhydrosiloxanes. Among these, methylhydrosiloxanes are ideal from the viewpoint of being easy to manufacture and readily available in industry.

[0106] The above-mentioned aromatic compounds having vinyl groups are compounds that are the source of the hydrocarbon groups having 8 to 40 carbon atoms in the aromatic ring of R23 in the above general formula (1). Examples of aromatic compounds having vinyl groups include: styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-isopropylphenylphenyl ether, allyl-o-phenylphenyl ether, allyl-tris(phenylethyl)-phenyl ether, allyl-tris(2-phenylpropyl)phenyl ether, etc.

[0107] The above-mentioned α-olefins are compounds that are the source of the alkyl group with 8 to 40 carbons in R23 of the above general formula (1). Examples of α-olefins include: 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexadecene (C26), 1-octadecene (C28), 1-triaconene (C30), 1-tridodecene (C32), etc., which are α-olefins with 8 to 40 carbons.

[0108] The above-mentioned hydrosiliconization reaction can also be carried out in the following manner: as needed, in the presence of a catalyst, the above-mentioned polysiloxane having SiH groups reacts with the above-mentioned aromatic compound having vinyl groups and the above-mentioned α-olefin in stages or in one step.

[0109] The amount of SiH-based polysiloxane, vinyl-based aromatic compound and α-olefin used in the hydrosiliconization reaction can be appropriately selected based on the SiH equivalent of the SiH-based polysiloxane or the number average molecular weight, etc.

[0110] Catalysts used in the hydrosiliconization reaction can be listed as compounds of platinum, palladium, etc., among which platinum compounds are ideal. Platinum compounds can be listed as, for example, platinum(IV) chloride.

[0111] The reaction conditions for the hydrogenation of silicon are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10~200℃, ideally 50~150℃. The reaction time is, for example, 3~12 hours when the reaction temperature is 50~150℃.

[0112] Furthermore, the hydrosiliconization reaction is ideally carried out in an inert gas environment. Examples of inert gases include nitrogen and argon. Although the reaction will proceed without a solvent, a solvent may also be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0113] Regarding the water-repellent agent composition, from the viewpoint of water repellency and white powder stains, it is ideal to use both the aforementioned acrylic compound and the aforementioned polysiloxane compound. The mass ratio of the acrylic compound (α) and the polysiloxane compound (β) is not particularly limited. For example, when the polysiloxane compound (β) is a polysiloxane resin, if the total mass of the acrylic compound (α) and the polysiloxane compound (β) is 100 parts by mass, the polysiloxane compound (β) may account for 1 to 99 parts by mass. Ideally, it is 5 to 98 parts by mass, more ideally 10 to 97 parts by mass, and even more ideally 15 to 95 parts by mass. By using a proportion of polysiloxane compound (β) within this range, the water repellency and bonded appearance after wear will become excellent. Alternatively, when the polysiloxane compound (β) is an organically modified polysiloxane, and the total mass of the acrylic compound (α) and the polysiloxane compound (β) is 100 parts by mass, the polysiloxane compound (β) can account for 10 to 90 parts by mass. Ideally, it should be 10 to 80 parts by mass, more ideally 15 to 70 parts by mass, and even more ideally 20 to 60 parts by mass. By using a proportion of polysiloxane compound (β) within this range, the water repellency will be excellent, and white powder spots will be less likely to form.

[0114] 1.1.3 Wax compounds Wax compounds, for example, are selected from at least one of paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, animal and plant wax and mineral wax, with paraffin wax being ideal from the viewpoint of water repellency, durable water repellency and texture.

[0115] Wax compounds, for example, may be one or both of n-alkanes and n-olefins. From the viewpoint of water repellency, durable water repellency and texture, n-alkanes are ideal wax compounds.

[0116] n-Alkanes, for example, are selected from at least one of trisane, tetrasane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, triacontane, trisane, dodecane, trisane, tetradecane, pentadecane, and hexadecane. From the viewpoint of water repellency, durable water repellency, and texture, triacontane, trisane, and dodecane are ideal n-alkanes.

[0117] The n-olefin may be, for example, selected from at least one of 1-eicosene, 1-docosahexene, 1-docosatriene, 1-docosathotene, 1-docosapentaene, 1-docosahexaene, 1-heptadecene, 1-docosacapene, docosahexadecene, triacontene, triacontene, tridodecene, triacontene, tritetradecene, trivinadecanene, and trihexadecene. Ideally, from the viewpoint of water repellency, durable water repellency, and texture, the n-olefin is at least one of triacontene, tridodecene, and tridodecene.

[0118] There is no particular limitation on the number of carbons in wax compounds, which can be 20 to 60. From the point of view of water repellency, durable water repellency and texture, the ideal number is 25 to 45.

[0119] There is no particular limitation on the weight average molecular weight of wax compounds, which can be 300~850. From the point of view of water repellency, durable water repellency and texture, the ideal value is 300~700.

[0120] The melting point of wax compounds, from the viewpoint of good water repellency and durable water repellency, especially good water repellency and durable water repellency for cotton, is ideally 35~90℃, more ideally 40~85℃, even more ideally 45~80℃, and even more ideally 50~75℃. The melting point of wax compounds refers to the value determined by the same method as JIS K2235-1991.

[0121] There are no particular limitations on the penetration of wax compounds; for example, it can be below 30. From the viewpoint of water repellency and durable water repellency, it is ideal to be below 20, more ideal to be below 15, and even more ideal to be below 10. There are no particular limitations on the penetration of wax compounds; for example, it can be above 0.1 or above 1. The penetration of wax compounds refers to the value measured using the same method as JIS K2235-1991.

[0122] 1.1.4 Carbamate Compounds Carbamate compounds are, for example, reaction products of aliphatic polyisocyanate derivatives, long-chain active hydrogen compounds, cationic active hydrogen compounds, and acid compounds. More specifically, they may be reaction products of the following substances: (U1) aliphatic polyisocyanate derivatives with an average isocyanate group number of 2 or more, (U2) long-chain active hydrogen compounds having both a hydrocarbon group with 12 to 30 carbon atoms and an active hydrogen group, (U3) cationic active hydrogen compounds having both an active hydrogen group and a cationic group, and (U4) acid compounds that form a salt with a cationic group. Here, the concentration of the aforementioned hydrocarbon group may be 30% to 85%. Furthermore, the aforementioned aliphatic polyisocyanate derivatives may include isocyanurate derivatives of aliphatic polyisocyanates. Further, in the aforementioned cationic active hydrogen compounds, the aforementioned cationic group may be a tertiary amino group, the aforementioned active hydrogen group may be a hydroxyl group, and the aforementioned cationic active hydrogen compounds may have two or more hydroxyl groups in each molecule. When the carbamate compound is a reaction product obtained using a long-chain active hydrogen compound and the concentration of the hydrocarbon group is in a specified ratio, the water repellency tends to be excellent. Furthermore, when the carbamate compound is a reaction product obtained using a cationic active hydrogen compound, for example, its affinity with fibers is enhanced, thereby easily improving wash durability.

[0123] Examples of aliphatic polyisocyanates constituting aliphatic polyisocyanate derivatives (U1) include: hexamethylene diisocyanate (hexane diisocyanate) (HDI), pentamethylene diisocyanate (pentane diisocyanate) (PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2- or 2,3- or 1,3-butanediisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and other aliphatic diisocyanates. Furthermore, in this case, "aliphatic polyisocyanate" includes the concept of alicyclic polyisocyanates.

[0124] Alicyclic polyisocyanates, such as: 3-isocyanomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4′- or 2,4′- or 2,2′-methylene bis(cyclohexyl isocyanate) or mixtures thereof (H12MDI), 1,3- or 1,4-bis(isocyanomethyl)cyclohexane or mixtures thereof (H6XDI), bis(isocyanomethyl)norbornene (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc., alicyclic diisocyanates.

[0125] Aliphatic polyisocyanates, preferably one or both of hexamethylene diisocyanate and 1,3-bis(isocyanomethyl)cyclohexane (hereinafter referred to as bis(isocyanomethyl)cyclohexane), more preferably hexamethylene diisocyanate.

[0126] Aliphatic polyisocyanate derivatives may include, for example: polymers of the above-mentioned aliphatic polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), urethane derivatives (e.g., urethane derivatives generated by reacting the above-mentioned aliphatic polyisocyanates with monohydric or dihydric alcohols, etc.), and polyol derivatives (e.g., polyol derivatives (alcohol adducts, ideally trimethylolpropane adducts) generated by reacting the above-mentioned aliphatic polyisocyanates with trihydric alcohols (e.g., trimethylolpropane, etc.). Examples of derivatives include: biuret derivatives (e.g., biuret derivatives generated by the reaction of the above-mentioned aliphatic polyisocyanates with water or amines), urea derivatives (e.g., urea derivatives generated by the reaction of the above-mentioned aliphatic polyisocyanates with diamines), oxadiazinetrione derivatives (e.g., oxadiazinetrione generated by the reaction of the above-mentioned aliphatic polyisocyanates with carbon dioxide), carbodiimide derivatives (carbodiimide derivatives generated by the decarbonation condensation reaction of the above-mentioned aliphatic polyisocyanates), uretdione derivatives, and urethonimine derivatives.

[0127] Aliphatic polyisocyanate derivatives, preferably at least one of isocyanurate derivatives, trimethylolpropane adducts, urethane derivatives, and biuret derivatives, more preferably isocyanurate derivatives. If the aliphatic polyisocyanate derivative contains isocyanurate derivatives, the texture becomes better.

[0128] An aliphatic polyisocyanate derivative, more preferably at least one of the following: isocyanurate derivative of hexamethylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, urethane derivative of hexamethylene diisocyanate, biuret derivative of hexamethylene diisocyanate, and isocyanurate derivative of bis(isocyanomethyl)cyclohexane, more preferably an isocyanurate derivative of hexamethylene diisocyanate.

[0129] Aliphatic polyisocyanate derivatives may be used alone or in combination of two or more. Ideal examples include: using an isocyanurate derivative of hexamethylene diisocyanate alone; and using an isocyanurate derivative of hexamethylene diisocyanate with at least one of the following groups: an isocyanurate derivative of bis(isocyanomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, a urethane derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate. In this case, relative to the total amount of at least 100 parts by mass of the isocyanurate derivative of hexamethylene diisocyanate and at least one selected from the group consisting of isocyanurate derivatives of bis(isocyanomethyl)cyclohexane, trimethylolpropane adduct of hexamethylene diisocyanate, urethane derivative of hexamethylene diisocyanate, and biuret derivative of hexamethylene diisocyanate, the proportion of the isocyanurate derivative of hexamethylene diisocyanate is, for example, 60 parts by mass or more, ideally 70 parts by mass or more, and, for example, 85 parts by mass or less; furthermore, the proportion of at least one selected from the group consisting of isocyanurate derivatives of bis(isocyanomethyl)cyclohexane, trimethylolpropane adduct of hexamethylene diisocyanate, urethane derivative of hexamethylene diisocyanate, and biuret derivative of hexamethylene diisocyanate is, for example, 15 parts by mass or more, and, for example, 40 parts by mass or less, ideally 30 parts by mass or less.

[0130] Aliphatic polyisocyanate derivatives can be manufactured by conventional methods.

[0131] The average isocyanate group number of the aliphatic polyisocyanate derivative is 2 or more, ideally 2.5, more ideally 2.9, and, for example, 3.8 or less. As long as the above-mentioned average isocyanate group number is above the above-mentioned lower limit, the water repellency can be further improved. Furthermore, the average isocyanate group number is calculated by the following formula (1) using the isocyanate group concentration A, the solid component concentration B, and the number average molecular weight C of the aliphatic polyisocyanate derivative determined by gel permeation chromatography using the following apparatus and conditions. In addition, when two or more aliphatic polyisocyanate derivatives are used, the above-mentioned average isocyanate group number is calculated by the weight ratio of the aliphatic polyisocyanate derivatives and their average isocyanate functional group number.

[0132] Average number of isocyanate functional groups = A / B×C / 42.02 (1) (where A represents the isocyanate group concentration of the aliphatic polyisocyanate derivative, B represents the concentration of solid components, and C represents the number average molecular weight.)

[0133] (Determination conditions for number average molecular weight) Apparatus: HLC-8220GPC (Tosoh) Column: TSKgel G1000HXL, TSKgel G2000HXL, and TSKgel G3000HXL (Tosoh) connected in series Detector: Differential refractometer Injection volume: 100 μL Dissolution solution: Tetrahydrofuran Flow rate: 0.8 mL / min Temperature: 40℃ Calibration range: Standard polyethylene oxide (Tosoh, trade name: TSK standard polyethylene oxide) in the range of 106~22450

[0134] Long-chain active hydrogen compounds are those that have both hydrocarbon groups with 12 to 30 carbon atoms and active hydrogen groups that react with aliphatic polyisocyanate derivatives.

[0135] A hydrocarbon group having 12 to 30 carbon atoms, such as a straight-chain or branched saturated hydrocarbon group having 12 to 30 carbon atoms (e.g., alkyl group), or a straight-chain or branched unsaturated hydrocarbon group having 12 to 30 carbon atoms (e.g., alkenyl group).

[0136] Active hydrogen group, for example, may be hydroxyl group.

[0137] Such a long-chain active hydrogen compound having both hydrocarbon groups and active hydrogen groups may be, for example, at least one of the following: an active hydrogen compound containing straight-chain saturated hydrocarbon groups, an active hydrogen compound containing branched saturated hydrocarbon groups, an active hydrogen compound containing straight-chain unsaturated hydrocarbon groups, and an active hydrogen compound containing branched unsaturated hydrocarbon groups.

[0138] Active hydrogen compounds containing straight-chain saturated hydrocarbon groups are active hydrogen compounds containing straight-chain saturated hydrocarbon groups with 12 to 30 carbon atoms. Examples include: n-tetrazol, n-tetradecanool, n-pentadecanol, n-hexadecanool, n-heptadecanool, n-octadecanool (stearyl alcohol), n-nonadecanol, eicosyl alcohol, etc., which contain straight-chain saturated hydrocarbon groups; for example: sorbitan tristearate, etc., which contain straight-chain saturated hydrocarbon groups, etc.

[0139] Active hydrogen compounds containing branched saturated hydrocarbon groups are active hydrogen compounds containing branched saturated hydrocarbon groups with 12 to 30 carbon atoms. Examples include isomycinol, isocetyl alcohol, isostearyl alcohol, isoetiol, and other alcohols containing branched saturated hydrocarbon groups.

[0140] Active hydrogen compounds containing straight-chain unsaturated hydrocarbon groups are active hydrogen compounds containing straight-chain unsaturated hydrocarbon groups with 12 to 30 carbon atoms. Examples include: tetradecenol, hexadecenol, oleyl alcohol, eicosenool, docosenool, tetradecenol, hexadecenol, octadecenol, and other alcohols containing straight-chain unsaturated hydrocarbon groups.

[0141] Active hydrogen compounds containing branched unsaturated hydrocarbon groups are active hydrogen compounds containing branched unsaturated hydrocarbon groups with 12 to 30 carbon atoms, such as phytol.

[0142] Long-chain active hydrogen compounds, ideally one or both of which contain a straight-chain saturated hydrocarbon group and a straight-chain unsaturated hydrocarbon group. Long-chain active hydrogen compounds may be used alone or in combination with two or more.

[0143] When using a long-chain active hydrogen compound alone, it is ideal to use an active hydrogen compound containing a straight-chain saturated hydrocarbon group alone, more ideally to use an alcohol containing a straight-chain saturated hydrocarbon group alone, and even more ideally to use stearyl alcohol alone. When using two or more long-chain active hydrogen compounds, it is ideal to use an active hydrogen compound containing a straight-chain saturated hydrocarbon group and an active hydrogen compound containing a straight-chain unsaturated hydrocarbon group together, more ideally to use an alcohol containing a straight-chain saturated hydrocarbon group and an alcohol containing a straight-chain unsaturated hydrocarbon group together, or to use an alcohol containing a straight-chain saturated hydrocarbon group, a sorbitan anhydride ester containing a straight-chain saturated hydrocarbon group, and an alcohol containing a straight-chain unsaturated hydrocarbon group together.

[0144] When using alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups, the proportion of alcohols containing straight-chain saturated hydrocarbon groups relative to 100 parts by mass of the total amount of alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups is, for example, 40 parts by mass or more, ideally 55 parts by mass or more, and more ideally 70 parts by mass or more. Furthermore, relative to 100 parts by mass of the total amount of alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups, the proportion of alcohols containing straight-chain unsaturated hydrocarbon groups is, for example, 60 parts by mass or less, ideally 45 parts by mass or less, and more ideally 30 parts by mass or less. As long as the proportion of alcohols containing straight-chain saturated hydrocarbon groups is above the above-mentioned lower limit, the crystallinity of the hydrocarbon groups can be improved, and as a result, the water-repellent property can be improved.

[0145] In the case of using alcohols containing straight-chain saturated hydrocarbon groups, sorbitan anhydrides containing straight-chain saturated hydrocarbon groups, and alcohols containing straight-chain unsaturated hydrocarbon groups, the proportion of alcohols containing straight-chain saturated hydrocarbon groups is, for example, 30 parts by mass or more, and, for example, 60 parts by mass or less, relative to 100 parts by mass of the total amount of alcohols containing straight-chain saturated hydrocarbon groups, sorbitan anhydrides containing straight-chain saturated hydrocarbon groups, and alcohols containing straight-chain unsaturated hydrocarbon groups. Furthermore, the proportion of sorbitan anhydrides containing straight-chain saturated hydrocarbon groups is, for example, 20 parts by mass or more, and, for example, 50 parts by mass or less, relative to 100 parts by mass of the total amount of alcohols containing straight-chain saturated hydrocarbon groups, sorbitan anhydrides containing straight-chain saturated hydrocarbon groups, and alcohols containing straight-chain unsaturated hydrocarbon groups. Furthermore, relative to the total amount of 100 parts by mass of alcohols containing straight-chain saturated hydrocarbon groups, sorbitan anhydrides containing straight-chain saturated hydrocarbon groups, and alcohols containing straight-chain unsaturated hydrocarbon groups, the proportion of alcohols containing straight-chain unsaturated hydrocarbon groups is, for example, 10 parts by mass or more, and, for example, 20 parts by mass or less.

[0146] In cases where two or more long-chain active hydrogen compounds are used together, it is even more ideal to use alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups together, and it is particularly ideal to use stearyl alcohol and oleyl alcohol together.

[0147] Cationic active hydrogen compounds possess both active hydrogen groups and cationic groups. Cationic active hydrogen compounds can be used alone or in combination with two or more groups.

[0148] The active hydrogen group, as described above, is an active hydrogen group that reacts with aliphatic polyisocyanate derivatives, such as a hydroxyl group. Ideally, each molecule of a cationic active hydrogen compound has two or more hydroxyl groups. Furthermore, the cationic group can be, for example, a tertiary amino group. That is, ideally, each molecule of a cationic active hydrogen compound has both two or more hydroxyl groups as active hydrogen groups and a tertiary amino group as a cationic group. More ideally, each molecule of a cationic active hydrogen compound has both two hydroxyl groups as active hydrogen groups and a tertiary amino group as a cationic group. According to such a cationic active hydrogen compound, good dispersibility in water can be imparted, and since cationic groups with affinity for fibers can be introduced, wash durability can be improved.

[0149] Such cationic active hydrogen compounds can be exemplified by, for example, alkyl diethanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and N-methyldipropanolamine, with N-methyldiethanolamine being an ideal example.

[0150] An acid compound is a compound that forms a salt with a cationic group. Examples of acid compounds include one or both of organic and inorganic acids. Examples of organic acids include acetic acid, lactic acid, tartaric acid, or malic acid, with acetic acid or lactic acid being ideal, and acetic acid being more ideal. Examples of inorganic acids include hydrochloric acid, sulfuric acid, or phosphoric acid, with hydrochloric acid being ideal. Ideally, the acid compound should be an organic acid. When an acid compound contains organic acids, heat treatment causes the acid to volatilize, thereby reducing its ionicity and improving its water resistance, thus enhancing its water repellency. Furthermore, heat treatment causes the acid to volatilize, making it easier for cationic groups to adsorb onto the fibers, thereby improving wash durability. Acid compounds can be used alone or in combination of two or more.

[0151] An aminocarbamate compound as a reaction product can be obtained by reacting the above-mentioned aliphatic polyisocyanate derivative, long-chain active hydrogen compound, cationic active hydrogen compound, and acid compound. When reacting the aliphatic polyisocyanate derivative, long-chain active hydrogen compound, cationic active hydrogen compound, and acid compound, firstly, the long-chain active hydrogen compound is incorporated into the aliphatic polyisocyanate derivative, and the aliphatic polyisocyanate derivative reacts with the long-chain active hydrogen compound. At this time, the long-chain active hydrogen compound, for example, in the case where the average number of isocyanate groups in the isocyanurate derivative of the aliphatic polyisocyanate is 3, is ideally incorporated in the following manner: two isocyanate groups in the isocyanurate derivative of the aliphatic polyisocyanate are modified into hydrocarbon groups with 12 to 30 carbon atoms by the long-chain active hydrogen compound, and one isocyanate group remains in the isocyanurate derivative of the aliphatic polyisocyanate, and no unreacted isocyanurate derivative of the aliphatic polyisocyanate remains. Specifically, a long-chain active hydrogen compound is incorporated into an aliphatic polyisocyanate derivative such that the equivalence ratio of isocyanate groups to active hydrogen groups (isocyanate groups / active hydrogen groups) is, for example, 1.2 or more, ideally 1.5 or more, and for example, 2.0 or less. In this manner, the molecule-terminus of the reaction product of the aliphatic polyisocyanate derivative and the long-chain active hydrogen compound (hereinafter referred to as the first intermediate reaction product) consists of a hydrocarbon group and an isocyanate group having 12 to 30 carbon atoms.

[0152] The above reaction was carried out under a nitrogen atmosphere. Furthermore, the reaction conditions were a reaction temperature of, for example, 70°C to 120°C, and a reaction time of 1 hour to 6 hours. The reaction was carried out until the isocyanate concentration of the first intermediate reaction product reached a specified calculated value. The isocyanate concentration could be determined using a potentiometric titration apparatus according to JIS K-1556 via the n-dibutylamine method.

[0153] In addition, in the above reaction, a familiar solvent (solvent) such as methyl ethyl ketone can also be used in a suitable proportion.

[0154] Next, a cationic active hydrogen compound is incorporated into the reaction solution containing the first intermediate reaction product, and the first intermediate reaction product is reacted with the cationic active hydrogen compound. At this time, the cationic active hydrogen compound is incorporated into the first intermediate reaction product in such a way that the equivalence ratio (isocyanate group / active hydrogen group) of the isocyanate group to the active hydrogen group of the cationic active hydrogen compound is, for example, 0.95 or more and, for example, 1.05 or less.

[0155] The above reaction is carried out under a nitrogen atmosphere. Furthermore, the reaction conditions are a reaction temperature of, for example, 70°C to 120°C, and a reaction time of 0.5 hours to 4 hours. Furthermore, the above reaction is carried out until the first intermediate reaction product and the cationic active hydrogen compound have completely reacted. In addition, a familiar solvent such as methyl ethyl ketone can be used in the above reaction in a suitable proportion. This yields a reaction product of the first intermediate reaction product and the cationic active hydrogen compound (hereinafter referred to as the second intermediate reaction product). The second intermediate reaction product has a hydrocarbon group with 12 to 30 carbon atoms and a cationic group.

[0156] Next, an acid compound is incorporated into the second intermediate reaction product. The proportion of the acid compound relative to 1 mol of the cationic group of the cationic active hydrogen compound is, for example, 0.5 mol or more, ideally 3 mol or more, and, for example, 10 mol or less, ideally 4 mol or less. Thereby, the acid compound and the cationic group of the second intermediate reaction product form a salt, thereby obtaining a reaction product (i.e., a carbamate compound) containing an aliphatic polyisocyanate derivative, a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound. The above-mentioned reaction product has a hydrocarbon group having 12 to 30 carbon atoms and a cationic group. Furthermore, because the above-mentioned reaction product has a hydrocarbon group having 12 to 30 carbon atoms, it can self-disperse (self-emulsify) in water without the use of a dispersant (emulsifier). In other words, the above-mentioned reaction product can undergo internal emulsification.

[0157] Next, while maintaining the temperature of this reaction solution at, for example, 50°C to 100°C, water is added to the reaction solution and emulsification is performed. Then, the solvent is removed from the reaction solution. This yields an aqueous dispersion containing the above-described reaction product (i.e., a carbamate compound). The solid content concentration of the aqueous dispersion is, for example, 10% by mass or more, and, for example, 30% by mass or less.

[0158] Since such a urethane compound is a reaction product obtained using a long-chain active hydrogen compound, it has excellent water repellency, and also excellent oil repellency, oil resistance, and antifouling properties. In addition, since such a urethane compound is a reaction product obtained using a cationic active hydrogen compound, the affinity with fibers will be improved, and as a result, the washing durability for fibers is excellent.

[0159] In such a urethane compound, the concentration of the hydrocarbon group is 30% or more and 85% or less, preferably 50%. As long as the concentration of the hydrocarbon group is above the above lower limit, the water repellency can be improved. In addition, as long as the concentration of the hydrocarbon group is below the above upper limit, the stability of the urethane compound can be improved. Also, the concentration of the above hydrocarbon group can be calculated from the amounts of the above respective components put in.

[0160] Also, in the above description, first, an aliphatic polyisocyanate derivative is reacted with a long-chain active hydrogen compound to obtain a reaction solution containing a first intermediate reaction product, then the first intermediate reaction product is reacted with a cationic active hydrogen compound to obtain a reaction solution containing a second intermediate reaction product, and then the second intermediate reaction product is reacted with an acid compound. However, the order of the reactions is not particularly limited. For example, after reacting an aliphatic polyisocyanate derivative with a cationic active hydrogen compound, a long-chain active hydrogen compound and an acid compound may be reacted. In addition, an aliphatic polyisocyanate derivative, a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound may be mixed at once and these may be reacted.

[0161] 1.1.5 Dendritic polymer-based compound A dendritic polymer-based compound may, for example, be a dendritic polymer compound having a radial and regularly branched structure from the center. A dendritic polymer compound can be used which has a linear or branched hydrocarbon group having 1 or more carbon atoms at the terminal branch part to obtain water repellency.

[0162] A dendritic polymer compound may, for example, be the "apolymerextender" disclosed in International Publication No. 2014 / 160906. For example, a compound obtained by reacting at least one isocyanate group-containing compound selected from isocyanates, diisocyanates, polyisocyanates or mixtures thereof with at least one isocyanate-reactive compound selected from the following formula (Ia), (Ib) or (Ic) can be used.

[0163] [Chemical formula 15]

[0164] In the above formula, R50 is independently -H, R51, -C(O)R51, -(CH2CH2O)n(CH(CH3)CH2O)mR52, or -(CH2CH2O)n(CH(CH3)CH2O)mC(O)R51; n is independently 0 to 20, m is independently 0 to 20, and m+n exceeds 0. In addition, R51 is independently an alkyl group with 5 to 29 carbon atoms that may contain one or more unsaturated bonds in a straight or branched chain; R52 is independently -H, or an alkyl group with 6 to 30 carbon atoms that may contain one or more unsaturated bonds in a straight or branched chain.

[0165] Also, in formula (Ia), at least one of R50 or R52 is -H.

[0166] In the above formula, R53 is independently -H, -R51, -C(O)R51, -(CH2CH2O(CH(CH3)CH2O)mR52, or -(CH2CH2O(CH(CH3)CH2OC(O)R51); R54 is independently -H, or a straight-chain or branched alkyl group with 6 to 30 carbon atoms that may contain one or more unsaturated bonds, -(CH2CH2O)n'(CH(CH3)CH2O)m'R52, or -(CH2CH2O(CH(CH3)CH2OC(O)R51, n' is independently 0 to 20, m' is independently 0 to 20, and m+n exceeds 0.

[0167] Also, in formula (Ib), at least one of R52, R53 or R54 is -H.

[0168] In the above formula, R55 is -H, -C(O)R51, or -CH2C[CH2OR50]3.

[0169] Also, in formula (Ic), at least one of R55 or R50 is -H.

[0170] There are no particular limitations on compounds containing isocyanate groups, and examples include: aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and their dimers and trimers modified polyisocyanates. Commercially available products such as "DESMODURN-100" (manufactured by Bayer Corporation, trade name), "DURANATE THA-100" (manufactured by Asahi Kasei Corporation, trade name), and "DURANATE 24A-100" (manufactured by Asahi Kasei Corporation, trade name) can be used. Furthermore, the reaction can be carried out at, for example, 80°C for more than 1 hour.

[0171] 1.2 Polyisocyanates Examples of polyisocyanates include: polyisocyanate monomers, polyisocyanate derivatives, etc. A polyisocyanate refers to an isocyanate compound having a plurality of isocyanate groups in the same molecule. Similarly, a diisocyanate compound refers to an isocyanate compound having two isocyanate groups in the same molecule. These polyisocyanates may be used alone or in combination of two or more.

[0172] There are no particular limitations on the polyisocyanate monomers, but examples include: aromatic polyisocyanates, aromatic aliphatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, etc. These polyisocyanate monomers may be used alone or in combination of two or more.

[0173] There is no particular limitation on the polyisocyanate derivatives, and examples include: polymers of polyisocyanate monomers (e.g., dimers, trimers (e.g., isocyanurate modified products, iminodiazine dione modified products), pentamers, heptamers, etc.), urea carbamate modified products (e.g., urea carbamate modified products formed by further adding the isocyanate group of the polyisocyanate monomer to the carbamate group formed by the reaction of the above-mentioned polyisocyanate monomers with the low molecular weight polyols described below), adducts (e.g., adducts formed by the reaction of polyisocyanate monomers with the low molecular weight polyols described below, etc.). Polyisocyanate derivatives include: biuret-modified products (e.g., biuret-modified products generated by reacting the above-mentioned polyisocyanate monomers with water or amines), urea-modified products (e.g., urea-modified products generated by further adding an isocyanate group to a polyisocyanate monomer formed by reacting the above-mentioned polyisocyanate monomers with diamines), dioxazinetrione-modified products (e.g., dioxazinetrione generated by reacting the above-mentioned polyisocyanate monomers with carbon dioxide gas), carbodiimide-modified products (carbodiimide-modified products generated by the decarbonation condensation reaction of the above-mentioned polyisocyanate monomers), urea diketone-modified products, and urea ketone imide-modified products. Furthermore, polyisocyanate derivatives may also include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI), etc. These polyisocyanate derivatives may be used alone or in combination of two or more.

[0174] 1.2.1 (B) Alicyclic Polyisocyanates—The non-fluorinated water-repellent composition of the embodiment contains an alicyclic polyisocyanate as the polyisocyanate. The alicyclic polyisocyanate may be, for example, selected from: 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylene bis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate, the trans form of these), (A) At least one of the following: trans-isocyanate, trans-, cis-isocyanate, cis-, cis-isocyanate, or mixtures thereof (H12MDI, hydrogenated MDI); methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate); norbornene diisocyanate (various isomers or mixtures thereof) (NBDI); bis(isocyanomethyl)cyclohexane (1,3- or 1,4-bis(isocyanomethyl)cyclohexane or mixtures thereof) (H6XDI, hydrogenated XDI). (B) Alicyclic polyisocyanates, from the viewpoint of excellent water repellency after wear, excellent Bondism, and excellent durable water repellency, are ideally at least one of isophorone diisocyanate (IPDI), hydrogenated MDI, and hydrogenated XDI, more ideally at least one of isophorone diisocyanate (IPDI) and hydrogenated MDI, and even more ideally isophorone diisocyanate (IPDI).

[0175] From the viewpoint of abrasion resistance and water repellency, alicyclic polyisocyanates are ideally polymers of the aforementioned monomers. In particular, when alicyclic polyisocyanates are trimers, abrasion resistance and water repellency are easily further improved. More specifically, when alicyclic polyisocyanates are trimers, both initial Bondism and abrasion resistance Bondism are further improved.

[0176] The polyisocyanate may consist solely of the above-mentioned alicyclic isocyanates, or it may be a combination of alicyclic isocyanates and other polyisocyanates. Alternatively, the alicyclic isocyanate may be reacted with other isocyanates.

[0177] 1.2.2 A non-fluorinated water-repellent composition of an embodiment other than alicyclic polyisocyanates, which may contain aliphatic polyisocyanates in addition to (B) alicyclic polyisocyanates. Aliphatic polyisocyanates may be, for example, selected from at least one of: trimethylene diisocyanate, 1,2-propanediisocyanate, succinate (tetramethylene diisocyanate, 1,2-succinate, 2,3-succinate, 1,3-succinate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, methyl 2,6-diisocyanate-hexanoate, lysine diisocyanate, dimer diisocyanate, etc. Particularly desirable is 1,6-hexamethylene diisocyanate (HDI).

[0178] One embodiment of the non-fluorinated water-repellent composition may contain, in addition to (B) alicyclic polyisocyanates, also aromatic polyisocyanates. The aromatic polyisocyanate may be, for example, selected from: toluene diisocyanate (2,4- or 2,6-toluene diisocyanate or mixtures thereof) (TDI), phenyl diisocyanate (m- or p-phenyl diisocyanate or mixtures thereof), 4,4'-biphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, etc. When the non-fluorinated water-repellent composition contains aromatic polyisocyanates in addition to (B) alicyclic polyisocyanates, there is a tendency for improved initial water pressure resistance and durable water pressure resistance.

[0179] One embodiment of the non-fluorinated water-repellent composition may contain, in addition to (B) alicyclic polyisocyanates, aromatic aliphatic polyisocyanates. The aromatic aliphatic polyisocyanate may be, for example, selected from at least one of: phenyl dimethyl diisocyanate (1,3- or 1,4-phenyl dimethyl diisocyanate or a mixture thereof) (XDI), tetramethylphenyl dimethyl diisocyanate (1,3- or 1,4-tetramethylphenyl dimethyl diisocyanate or a mixture thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, etc.

[0180] As described above, an embodiment of the non-fluorinated water-repellent composition may contain at least one of aliphatic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates, in addition to (B) aliphatic polyisocyanates. When an embodiment of the non-fluorinated water-repellent composition contains other polyisocyanates besides (B) aliphatic polyisocyanates, the mass ratio of the aliphatic polyisocyanate to other polyisocyanates (aliphatic polyisocyanate / other polyisocyanates) may be 99 / 1 to 1 / 99, 95 / 5 to 5 / 95, 90 / 10 to 10 / 90, or 85 / 15 to 25 / 75. In particular, when aliphatic polyisocyanates and aliphatic polyisocyanates are contained in this ratio, the water repellency of the initial Bondism, the worn Bondism, and the worn water-repellent properties will be further improved.

[0181] 1.2.3 Capped Polyisocyanates The above-mentioned polyisocyanates can also be capped by a capping agent. Capped polyisocyanates can be obtained by reacting the above-mentioned polyisocyanates with a capping agent. A single capping agent or two or more capping agents can be used alone or in combination.

[0182] The capping agent may be, for example, a compound having one or more active hydrogen atoms in its molecule. The capping agent may be, for example, at least one selected from: alcohol compounds, alkylphenol compounds, phenol compounds, active methylene compounds, thiol compounds, acetylamine compounds, acetylimide compounds, imidazole compounds, imidazoline compounds, triazole compounds, carbamate compounds, urea compounds, oxime compounds, amine compounds, acetylimide compounds, imine compounds, pyrazole compounds, and bisulfites. Ideally, the compound is selected from at least one of acetylamine compounds, active methylene compounds, oxime compounds, and pyrazole compounds. For example, it is ideally selected from at least one of ε-caprolactam, acetoacetone, diethyl malonate, methyl ethyl ketone oxime, cyclohexanone oxime, 3-methylpyrazole, and 3,5-dimethylpyrazole. From the viewpoint of wash durability and water repellency, it is more ideal to select one or both of dimethylpyrazole and dimalonate.

[0183] 1.2.4 Self-emulsifying property The aforementioned polyisocyanates may or may not possess self-emulsifying properties. From the viewpoint of initial water pressure resistance, those without self-emulsifying properties are more desirable than those with self-emulsifying properties. Examples of self-emulsifying polyisocyanates include those with a portion containing a nonionic hydrophilic group, a cationic hydrophilic group, or an anionic hydrophilic group. From the viewpoint of water repellency, it is ideal to use polyisocyanates containing a nonionic hydrophilic group with an oxyethyl group. To impart self-emulsifying hydrophilic compounds that react with polyisocyanates, examples include: polyoxyalkylene monoalkyl ethers such as polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol-polypropylene glycol monomethyl ether, and polyethylene glycol-polyethylene glycol monobutyl ether; polyethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol; block copolymers and random copolymers of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; random copolymers or block copolymers of ethylene oxide and propylene oxide, or ethylene oxide and butane oxide; polyoxyalkylene monoamines and polyoxyalkylene diamines; etc., with polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether being ideally used. The aforementioned nonionic hydrophilic compounds can be used alone or in combination of two or more. By introducing these compounds at a concentration of approximately 1 to 50 mol% relative to the isocyanate groups, polyisocyanates can be endowed with self-emulsifying properties.

[0184] 1.3 (C) Other components The non-fluorinated water-repellent composition may contain the above-mentioned non-fluorinated water-repellent components and alicyclic polyisocyanates, and may also contain other components. For example, an embodiment of the non-fluorinated water-repellent composition may also contain an aqueous medium and an emulsifier.

[0185] One embodiment of the non-fluorinated water-repellent composition may also contain an aqueous medium. The aqueous medium may be water or a mixture of water and an organic solvent. The amount of organic solvent relative to the aqueous medium may, for example, be 0.1% to 30% by mass or 0.1% to 10% by mass. Ideally, the aqueous medium is composed solely of water. With the non-fluorinated water-repellent composition as a whole, the amount of aqueous medium may be 30 to 99% by mass or 50 to 90% by mass.

[0186] One embodiment of the non-fluorinated water-repellent composition may also contain an emulsifier to improve the dispersibility of the composition in aqueous media. The emulsifier may be at least one selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Ideally, the emulsifier is a nonionic surfactant used alone, or a combination of a nonionic surfactant and a cationic surfactant. In the combination of nonionic and cationic surfactants, the mass ratio of the nonionic surfactant to the cationic surfactant may, for example, be 99.5:0.5 to 50:50, or 99:1 to 90:10.

[0187] Nonionic surfactants may include, for example: polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyglycerol fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkylalkanolamide, acetylenide glycol, ethoxyethylene adduct of acetylenide glycol, polyethylene glycol-polypropylene glycol block copolymers, etc. Anionic surfactants include, for example, sulfates of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfates, polyoxyethylene alkylphenyl ether sulfates, vinyl sulfosuccinate, and polyoxyethylene alkyl ether phosphates. Cationic surfactants include amine salts, amide amine salts, quaternary ammonium salts, and imidazoline onion salts. Specific examples are not particularly limited, but can include: alkylamine salts, polyoxyethylene alkylamine salts, alkyl amide amine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline and other amine salt type surfactants; alkyl trimethylammonium salts, dialkyl dimethylammonium salts, alkyl dimethyl benzylammonium salts, alkyl pyridinium onion salts, alkyl isoquinoline onion salts, chlorobenzophenone and other quaternary ammonium salt type surfactants, etc. Amphoteric surfactants include: alkyl amine oxides, alanine oxides, imidazoline betaines, amide betaines, and acetate betaines, among others. More specifically, examples include: long-chain amine oxides, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethylamino acetate betaine, and fatty acid amide propyl dimethylamino acetate betaine. There are no particular restrictions on the amount of these surfactants used; ideally, in the solid components of emulsions, it is 1-20% by mass, and more ideally, 1.5-10% by mass.

[0188] The hydrophilicity-lipophilicity balance (HLB) value of the above-mentioned emulsifier is not particularly limited. The average HLB of the nonionic emulsifier in the composition of a non-fluorinated water-repellent agent of an embodiment is ideally 6.0~16.0, 6.5~15.5, 7.0~15.0, or 7.5~14.5. If the HLB is outside this range, there is a tendency for a decrease in initial Bondism, Bondism after wear, and initial water pressure resistance. Furthermore, the HLB of the emulsifier is a value obtained by the Griffin method using the following formula: HLB=20×[(molecular weight of hydrophilic groups contained in the surfactant) / (molecular weight of the surfactant)]; the value recorded in Reference 1 (Guide to Surfactants, 3rd edition, May 1, 1998); or the value recorded in Reference 2 (The HLB SYSTEM, 1989.7 ICI Americas Inc). For a specific surfactant, the HLB value is determined using the Griffin method. In cases where the Griffin method cannot be used, the value described in Reference 1 (or Reference 2) is adopted. If the HLB value is not described in Reference 1, the value described in Reference 2 is adopted. In mixtures containing two or more emulsifiers, the HLB of the mixture can be calculated using a weighted average of the HLB values ​​of each individual emulsifier.

[0189] 1.4 Ratio of Non-Fluorine Water-Repellent Components to Polyisocyanates When the composition of a non-fluorine water-repellent agent is an aqueous emulsion, the ideal ratio of the non-fluorine water-repellent component to the crosslinking component (polyisocyanate) in the solid components of this composition is 20-90% by mass for the non-fluorine water-repellent component and 10-80% by mass for the crosslinking component. More ideally, the non-fluorine water-repellent component is 30-85% by mass and the crosslinking component is 15-70% by mass; even more ideally, the non-fluorine water-repellent component is 40-80% by mass and the crosslinking component is 20-60% by mass; particularly ideally, the non-fluorine water-repellent component is 55-80% by mass and the crosslinking component is 20-45% by mass. By adjusting the ratio of the non-fluorine water-repellent component and the crosslinking component, excellent wash-resistant water-repellent properties can be ensured without compromising water repellency. There are no particular limitations on the proportion of solid components in the aqueous emulsion, but an ideal ratio is 20-60% by mass. There are no particular restrictions on the particle size in aqueous emulsions, but ideally the average particle size is less than 10 μm, further ideally less than 1 μm, and especially ideally 50–500 nm. If the average particle size is too large, the stability of the emulsion tends to decrease. Furthermore, this average particle size refers to the particle size (median particle size) measured using a laser diffraction / scattering particle size distribution measuring device, with a cumulative percentage (volume basis) of 50%.

[0190] 2. Method for Manufacturing Non-Fluorine Water-Repellent Composition An example of a method for manufacturing the non-fluorine water-repellent composition of the present invention will be described below. As described above, the non-fluorine water-repellent composition can be obtained by mixing a non-fluorine water-repellent component with a polyisocyanate. The ratio of the non-fluorine water-repellent component to the polyisocyanate in the non-fluorine water-repellent composition can be the ideal ratio described above.

[0191] The non-fluorinated water-repellent composition may be, for example, a formulation in which a non-fluorinated water-repellent component and a polyisocyanate are premixed, or it may be a formulation containing at least one of the above-mentioned components and a formulation containing the other components. From the viewpoint of ease of operation, the non-fluorinated water-repellent composition is physically designed such that each component is dispersed (including emulsified and dissolved) in an aqueous medium.

[0192] A non-fluorinated water-repellent formulation containing one of the components can be obtained, for example, by dispersing (including emulsifying and dissolving) the components simultaneously in an aqueous medium, or by mixing a dispersion obtained by dispersing at least one of the components in an aqueous medium with a dispersion obtained by dispersing the other components in an aqueous medium.

[0193] Methods for dispersing the above-mentioned components in an aqueous medium include, for example, mixing and stirring the components, the aqueous medium, and a dispersant as needed. For mixing and stirring, conventionally known emulsifying and dispersing machines such as emulsifiers, high-speed mixers, homogenizers, ultrasonic homogenizers, homogenizing mixers, bead mills, pearl mills, DYNO-MILL, Aspec Mills, basket mills, ball mills, nanomizers, Altimizers, and Star Bursts can be used. One of these emulsifying and dispersing machines can be used alone, or two or more can be used in combination.

[0194] The types of aqueous media and emulsifiers (surfactants) are as described above.

[0195] The non-fluorinated water-repellent composition prepared as a dispersion as described above can be used directly as a treatment solution, or it can be further diluted with an aqueous medium or a hydrophobic organic solvent to prepare a treatment solution.

[0196] The non-fluorinated water-repellent composition of the present invention can be manufactured, for example, by the following steps: (I) reacting a polyisocyanate, a hydrophilic compound that can react with the isocyanate group of the polyisocyanate, and a capping agent that can react with the isocyanate group of the polyisocyanate until the NCO content is 0%, thereby obtaining a capped isocyanate. (II) adding a non-fluorinated water-repellent component and water to the liquid containing the capped isocyanate obtained in (I) and mixing, thereby obtaining an emulsion. (III) removing the organic solvent from the emulsion obtained in (II) as appropriate, thereby obtaining an aqueous emulsion.

[0197] In step (I) above, the polyisocyanate can be any of those described above, and the hydrophilic compound that can react with the isocyanate group can be a polyethylene glycol monoalkyl ether, etc. The reaction of the polyisocyanate with the hydrophilic compound and the capping agent can be carried out using conventional methods, and can be carried out regardless of the presence of a solvent. When using a solvent, a solvent that is inert to the isocyanate group must be used. During the capping reaction, organometallic salts such as tin, zinc, and lead, metal alkoxides, and tertiary amines can also be used as catalysts. The capping reaction can usually be carried out at -20 to 150°C, but ideally at 0 to 100°C. If the temperature exceeds 150°C, side reactions may occur; on the other hand, if the temperature is too low, the reaction rate will be slowed down, which is unfavorable. The capped isocyanate can be capped with the above-mentioned capping agent at a rate of 50 mol% or more of the isocyanate group, ideally at a rate of 75 mol% or more, and particularly ideally at a rate of 90 mol% or more.

[0198] Furthermore, ideally, a hydrophilic compound is introduced at a concentration of 1-50 mol% relative to the isocyanate groups. By introducing a hydrophilic compound into a portion of the isocyanate groups, the capped isocyanate exhibits self-emulsifying properties, allowing the preparation of a water-repellent agent containing water-repellent and cross-linking components in a single particle without the use of surfactants or with a small amount of surfactants. The reaction in step (I) is ideally carried out until the NCO content is 0%. The NCO content can be determined, for example, by conventional methods such as the method described in section 5.10 of JISK 6806:2003 regarding NCO content; 0% is simply the degree to which virtually all NCO groups have disappeared, which, in conventional determination methods, is below the detection limit or considered to be equivalent to it.

[0199] Examples of solvents for the above reaction system include: acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, n-butyl acetate, cellosolve acetate, toluene, etc. One of these solvents may be used alone, or two or more may be used in combination.

[0200] In step (II) above, the water-repellent component may be the one described above. Alternatively, an organic solvent may be added together with the water-repellent component. Ideally, water should be added only after confirming that the reaction solution (containing the capped isocyanate) from step (I) is uniformly mixed with the water-repellent component and the organic solvent. The emulsion can be obtained by adding water dropwise while stirring.

[0201] In step (III) above, the method for removing organic solvent from the emulsion may be a conventional method, such as vacuum distillation.

[0202] Furthermore, the non-fluorinated water-repellent composition of the present invention can also be obtained by a method for manufacturing a water-repellent treatment agent comprising the following steps: (a) reacting a polyisocyanate and a capping agent capable of reacting with the isocyanate group of the polyisocyanate until the NCO content is 0%, thereby obtaining a capped isocyanate; (b) adding a water-repellent component, a surfactant and water to the liquid containing the capped isocyanate obtained in step (a) and mixing them, thereby obtaining an emulsion; and (c) removing the organic solvent from the emulsion obtained in step (b) as appropriate, thereby obtaining an aqueous emulsion.

[0203] The polyisocyanate and capping agent used in step (a) above are as described above. Furthermore, the NCO content can be determined, for example, by conventional methods such as the method described in section 5.10 of JIS K 6806:2003 regarding NCO content; 0% is simply defined as the degree to which virtually all NCO groups have disappeared, and in conventional methods, this is below the detection limit or considered to be an equivalent range. The solvent used in the reaction system is not particularly limited as long as it allows the reaction to proceed uniformly within the reaction system; for example, the same solvent as in step (I) above can be used.

[0204] In step (b) above, the water-repellent component and surfactant can be those described above. They can also be added together with the water-repellent component to an organic solvent. The surfactant can be added by dropping or other methods if it is pre-dissolved or dispersed in water. Alternatively, it can be pre-dissolved or dispersed together with the water-repellent component in an organic solvent. Conventional emulsification equipment can be used for mixing, such as a homogenizer, homogenizer, colloid mill, or line mixer. This manufacturing method uses a surfactant to forcibly emulsify the mixed solution of the water-repellent component and the crosslinking component. Therefore, in the emulsion, each particle contains both the water-repellent component and the crosslinking component, forming a mixed emulsion.

[0205] In step (c) above, the method for removing organic solvent from the emulsion can be a conventional method, such as vacuum distillation.

[0206] 2. Method for manufacturing water-repellent fiber articles. According to the non-fluorinated water-repellent composition of the present invention, water repellency (abrasion-resistant water repellency) can be imparted to fiber articles during actual use, for example. The following examples illustrate the application of the non-fluorinated water-repellent composition of the present invention to fiber articles; however, the non-fluorinated water-repellent composition of the present invention may also impart excellent abrasion-resistant water repellency to various articles other than fiber articles.

[0207] A method for manufacturing a water-repellent fiber article according to an embodiment includes the step of treating fibers with a treatment solution containing the non-fluorine water-repellent agent composition of the present invention. Through this step, a water-repellent fiber article can be obtained.

[0208] There are no particular restrictions on the raw materials of the fiber, including: natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as nylon, polyester, polyurethane, polypropylene, and acrylic, as well as composite fibers and blended fibers. There are no particular restrictions on the form of the fiber, not limited to raw material forms such as short fibers, long fibers, fiber bundles, and yarns, but also including any form such as textiles, woven fabrics, fillings, non-woven fabrics, paper, sheets, and films. Fibers can also be fiber products.

[0209] Examples of the above-mentioned methods for treating fibers with a treatment solution include: impregnation, spraying, coating, etc. In addition, if the non-fluorinated water-repellent agent composition contains water, it is ideal to dry it after it adheres to the fiber to remove the water.

[0210] The amount of non-fluorinated water-repellent agent adhering to the fiber can be adjusted appropriately according to the desired degree of water repellency. Ideally, the amount of non-fluorinated water-repellent agent adhering to 100g of fiber should be adjusted to 0.1~5g, and more ideally to 0.1~3g. If the amount of non-fluorinated water-repellent agent adhering to the fiber is too small, the fiber may not be able to exert sufficient water repellency; if it is too large, the fiber may become rough and stiff, and it may also become economically disadvantageous.

[0211] The above-described treatment using the treatment solution can be carried out by either a continuous method or a batch method. In the continuous method, firstly, the water-repellent agent composition is diluted in water to prepare the treatment solution. Next, the work to be treated (fiber products) is continuously fed into an impregnation device filled with the treatment solution, so that the processing solution impregnates the work to be treated, and then the unwanted processing solution is removed. The impregnation device is not particularly limited, and ideally it can be a dyeing press, a roller-type applicator, a gravure coating machine-type applicator, a spray applicator, a foam applicator, a coating applicator, etc., with a dyeing press type being particularly ideal. Next, an operation is performed to remove the water remaining in the work to be treated using a dryer. The dryer is not particularly limited, but ideally it can be a hot air dryer, a tenter frame, or a spreading dryer. This continuous method is ideally used when the work to be treated is a fabric such as textiles. On the other hand, the batch method consists of, for example, a step of immersing the work to be treated in the processing solution and a step of removing the water remaining in the treated work to be treated. This batch method is ideally suited for cases where the treated material is not in the form of fabric, such as loose wool, wool tops, cotton slivers, skeins, fiber bundles, or yarns, or for woven fabrics where continuous methods are not suitable. In the impregnation step, machines such as cotton dyeing machines, yarn dyeing machines, liquid dyeing machines, industrial washing machines, and warp beam dyeing machines can be used. For the water removal operation, warm air dryers such as yarn dryers, warp beam dryers, drum dryers, and high-frequency dryers can be used. Ideally, the treated material with the water-repellent agent composition is subjected to dry heat treatment. The ideal temperature for dry heat treatment is 100~200℃, and particularly ideally 120~180℃. The ideal time for dry heat treatment is 10 seconds to 3 minutes, and particularly ideally 1~2 minutes. The method of dry heat treatment is not particularly limited; however, for cases where the treated material is in the form of fabric, a tenter frame is ideal.

[0212] Water-repellent fiber products possess excellent abrasion resistance and water repellency, making them suitable for various applications including down covers, coats, blouses, windbreakers, smocks, dress shirts, skirts, trousers, gloves, hats, bedding covers, bedding drying covers, curtains, and tents, as well as non-clothing products. [Example]

[0213] As described above, one embodiment of the technology of the present invention has been explained. However, the technology of the present invention can be modified in various ways beyond the above-described embodiment without departing from its spirit. The technology of the present invention will be described in more detail below while showing embodiments. However, the technology of the present invention is not limited to the following embodiments.

[0214] 1. Preparation of non-fluorine-based water-repellent component 1.1 Preparation of dispersion of acrylic compound (Preparation Example A-1) In an autoclave, put: 15.6 parts by mass of stearyl acrylate, 0.4 parts by mass of diacetone acrylamide, 0.8 parts by mass of NOIGEN XL-100 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7), 0.2 parts by mass of stearyl trimethylammonium sulfate, 10 parts by mass of tripropylene glycol, and 68.8 parts by mass of water, mix and stir at 45 °C to obtain a mixed solution. Ultrasonic waves are irradiated to this mixed solution to emulsify and disperse all monomers. Then, 0.2 parts by mass of azobis(isobutyramidine) dihydrochloride is added to the dispersion, and under a nitrogen atmosphere, while continuously pressing in 4.0 parts by mass of vinyl chloride so that the internal pressure of the autoclave is maintained at 0.3 MPa, radical polymerization is carried out at 60 °C for 6 hours to obtain a dispersion containing 20% by mass of acrylic resin.

[0215] (Preparation Examples A-2 and A-3) According to the amounts put in shown in Table 1 below, a dispersion containing 20% by mass of acrylic resin is obtained by the same process as Preparation Example A-1.

[0216] [Table 1]

[0217] 1.2 Preparation of dispersion of polysiloxane-based compound 1.2.1 Alkyl-modified polysiloxane dispersion (Preparation Example A-4: octadecyl polydimethylsiloxane dispersion) In a flask, put methylhydrogen polysiloxane with a SiH:SiCH3 molar ratio of 5:5 (measured by 1H NMR (nuclear magnetic resonance)), and a mixed solution of ethylene glycol monobutyl ether / toluene of platinum(IV) chloride as a hydrosilylation catalyst, so that the platinum concentration is 5 ppm relative to the reactants in the system. After replacing the inside of the flask with nitrogen, relative to 1 molar equivalent of the reactive group (Si-H) of methylhydrogen polysiloxane, 1 molar equivalent of 1-octadecene is dropwise added to the mixture in the flask. The inside of the kettle is heated to 120 °C, and an addition reaction is carried out for 6 hours to obtain an alkyl-modified polysiloxane in which R20, R21, and R22 in the following formula (1) are CH3, R23 is C18H37, a is 40, b is 40, a:b is 1:1, and R30 to R35 are CH3. The confirmation of the completion of the addition reaction is carried out by performing FT-IR (Fourier transform infrared) spectroscopic analysis on the obtained alkyl-modified polysiloxane and confirming the disappearance of the absorption spectrum of the SiH group derived from methylhydrogen polysiloxane.

[0218] [Chemical Formula 16]

[0219] 20 parts by weight of the obtained alkyl-modified polysiloxane, 1.2 parts by weight of SPAN40 (sorbitan-based nonionic surfactant, HLB=6.7), 1.3 parts by weight of TWEEN 40 (sorbitan-based nonionic surfactant, HLB=15.6), 0.5 parts by weight of NOIGEN XL-40 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., polyoxyethylene branched decyl ether, HLB=10.5), 0.5 parts by weight of NOIGEN XL-60 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., polyoxyethylene branched decyl ether, HLB=12.5), 0.5 parts by weight of stearyltrimethylammonium sulfate, and 10 parts by weight of dipropylene glycol were heated and mixed. Next, water was added in small batches of 66.0 parts by mass to the resulting mixture to obtain a dispersion containing 20% ​​by mass of octadecyl polydimethylsiloxane (average HLB of nonionic surfactant = 11.4).

[0220] (Preparation Example A-5: Hexadecyl polydimethylsiloxane dispersion) A mixed solution of methylhydropolysiloxane (SiH:SiCH3) with a molar ratio of 4:6 (determined by 1H NMR) and ethylene glycol monobutyl ether and toluene as a silanization catalyst was placed in a flask, such that the platinum concentration was 5 ppm relative to the reactants in the system. After nitrogen substitution in the flask, 1 molar equivalent of 1-hexadecene was added dropwise to the mixture in the flask relative to 1 molar equivalent of the reactive group (Si-H) of methylhydropolysiloxane. The reactor was heated to 120°C and subjected to an addition reaction for 6 hours to obtain alkyl-modified polysiloxanes of the above formula (1), where R20, R21, and R22 are CH3, R23 is C26H53, a is 60, b is 90, a:b is 2:3, and R30~R35 are CH3. The completion of the addition reaction was confirmed by FT-IR (Fourier Transform Infrared) spectral analysis of the obtained alkyl-modified polysiloxane and by confirming the disappearance of the absorption spectrum of the SiH group derived from methylhydrogen polysiloxane.

[0221] Using the obtained alkyl-modified polysiloxane, a dispersion containing 20% ​​by mass of hexadecyl polydimethylsiloxane (average HLB of nonionic surfactant = 9.8) was obtained in the same manner as in Modification Example A-4.

[0222] (Preparation Example A-6: Tridecyl polydimethylsiloxane Dispersion) A mixed solution of methylhydropolysiloxane (SiH:SiCH3) with a molar ratio of 3:7 (determined by 1H NMR) and ethylene glycol monobutyl ether and toluene as a silanization catalyst was placed in a flask, so that the platinum concentration was 5 ppm relative to the reactants in the system. After nitrogen substitution in the flask, 1 molar equivalent of 1-tridecylene was added dropwise to the mixture in the flask relative to 1 molar equivalent of the reactive group (Si-H) of methylhydropolysiloxane. The reactor was heated to 120°C and subjected to an addition reaction for 6 hours to obtain alkyl-modified polysiloxanes of the above formula (1), where R20, R21, and R22 are CH3, R23 is C32H65, a is 140, b is 60, a:b is 7.3, and R30~R35 are CH3. The completion of the addition reaction was confirmed by FT-IR (Fourier Transform Infrared) spectral analysis of the obtained alkyl-modified polysiloxane and by confirming the disappearance of the absorption spectrum of the SiH group derived from methylhydrogen polysiloxane.

[0223] Using the obtained alkyl-modified polysiloxane, a dispersion containing 20% ​​by mass of tridimethylsiloxane (average HLB of nonionic surfactant = 8.1) was obtained in the same manner as in Modification Example A-4.

[0224] The composition of modulation examples A-4 to A-6 and the average HLB of nonionic surfactants are summarized in Table 2 below.

[0225] 〔Table 2〕

[0226] 1.2.2 Dispersion of polysiloxane, dimethyl polysiloxane and amino-modified polysiloxane (Preparation Example A-7) In a 300 mL stainless steel container, add 5.8 parts by weight of MQ-1600 (a trimethylsilyl polysiloxane, manufactured by Toray Industries, Dow Corning, Inc., trade name) as polysiloxane and 13.4 parts by weight of KF-96A-100cs (manufactured by Shin-Etsu Silicon Power Co., Ltd.) as dimethyl polysiloxane, and heat and stir until the polysiloxane is uniformly dissolved. Add 0.8 parts by weight of KF-8012 (manufactured by Shin-Etsu Chemical Co., Ltd., a bi-terminated amino-modified polysiloxane with a functional group equivalent of 2200) as amino-modified polysiloxane to the resulting homogeneous solution to obtain a mixture. Next, 1.6 parts by weight of NOIGEN XL-40 were added, and 78.4 parts by weight of mixed water were added in small amounts each time. The mixture was then ultrasonically treated at 60-70°C for 10 minutes using an ultrasonic emulsifier and cooled to room temperature to obtain a dispersion containing 20% ​​by weight of polysiloxane compound (average HLB of nonionic surfactant = 10.5).

[0227] (Modification Example A-8) Except for using the mixing ratio shown in Table 3 below, a dispersion containing 20% ​​by mass of a polysiloxane compound (average HLB of nonionic surfactant = 4.7) was obtained in the same manner as in Modification Example A-7.

[0228] (Modification Example A-9) Except for using the mixing ratio shown in Table 3 below, a dispersion containing 20% ​​by mass of a polysiloxane compound (average HLB of nonionic surfactant = 18.3) was obtained in the same manner as in Modification Example A-7.

[0229] (Modification Example A-10) Except for using the mixing ratio shown in Table 3 below, a dispersion containing 20% ​​by mass of a polysiloxane compound (average HLB of nonionic surfactant = 10.5) was obtained in the same manner as in Modification Example A-7.

[0230] 1.2.3 Dispersion of Amine-Modified Polysiloxane (Preparation Example A-11) Except that WACKER FINISH WR 301 (manufactured by Asahi Kasei Corporation, amine equivalent 3700, solid content 100%) was used as the amine-modified polysiloxane and the mixing ratio shown in Table 3 below was adopted, a dispersion containing 20% ​​by mass of polysiloxane compound (average HLB of nonionic surfactant = 12.0) was obtained in the same manner as in Preparation Example A-7.

[0231] [Table 3] Furthermore, the nonionic surfactants are SPAN 65: HLB 2.1 (manufactured by Croda), NOIGEN XL-160: HLB 16.3 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), and NIKKOL BC-30: HLB 19.5 (manufactured by Nikko Chemical Co., Ltd.). NOIGEN XL-40 is as described above.

[0232] 1.3 Preparation of a dispersion of wax-based compounds (Preparation Example A-12) In a high-pressure reaction vessel, add 20 parts by weight of Paraffin Wax-155 (manufactured by Nippon Seika Co., Ltd., melting point 69°C), 78 parts by weight of water, 1.0 part by weight of sorbitan monostearate (HLB=4.5), and 1.0 part by weight of polyoxyethylene sorbitan monostearate (HLB=14.9) and seal. Then, while stirring, heat the vessel to 110~120°C. Subsequently, while maintaining high pressure in the vessel, perform high-pressure emulsification for 30 minutes to obtain an emulsion containing 20% ​​by weight of paraffin (average HLB of nonionic surfactant = 9.7).

[0233] 1.4 Preparation of Dispersions of Carbamate Compounds 1.4.1 Synthesis of Polyurethane Resin (Synthesis Example U-1) In a reactor equipped with a thermometer, a stirrer, a nitrogen inlet pipe, and a condenser, under a nitrogen atmosphere, 500 parts by weight of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, trade name: TAKENATE 700), 0.25 parts by weight of 2,6-bis(tributyl)-4-methylphenol (also known as butylated hydroxytoluene, BHT, hindered phenolic antioxidant), and 0.25 parts by weight of tetraphenyldipropylene glycol diphosphite (organophosphite, co-catalyst) were mixed. Then, 10.7 parts by weight of 1,3-butanediol were added to this mixture, and nitrogen was introduced into the liquid phase for 1 hour. Subsequently, the mixture was heated to 80°C and reacted for 3 hours, then cooled to 60°C. Subsequently, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate, acting as a catalyst for isocyanurate esterification, were added, and the reaction was carried out for 1.5 hours. Then, 0.04 parts by mass of o-toluenesulfonamide were added relative to 100 parts by mass of HDI. The reaction mixture was then passed through a thin-film distillation apparatus (temperature 150°C, vacuum 93.3 Pa) and distilled until the residual HDI monomer content was below 0.5%, thereby obtaining an aliphatic polyisocyanate derivative (an isocyanurate derivative of hexamethylene diisocyanate). The obtained aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average isocyanate functional group number of 3.0.

[0234] 1.4.2 Preparation of Polyurethane Resin Dispersion (Preparation Example A-13) In a reactor equipped with a stirrer, thermometer, cooler, and nitrogen inlet pipe, 100.08 parts by mass of the aliphatic polyisocyanate derivative of Synthesis Example U-1 (aliphatic polyisocyanate derivative) and 90.03 parts by mass of KALCOL 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound were mixed and reacted at 110°C for 4 hours under nitrogen atmosphere until the concentration of isocyanate groups was 3.67%. Next, the reaction solution was cooled to 80°C, and 9.89 parts by mass of N-methyldiethanolamine as a cationic active hydrogen compound were added, and the reaction was carried out at 80°C for 1 hour. 50 parts by mass of methyl ethyl ketone as a solvent were added, and the reaction was carried out at 80°C until the isocyanate groups could be confirmed to have disappeared by infrared absorption spectroscopy. Next, 57.7 parts by mass of methyl ethyl ketone (MEK) were added to the reaction solution, the temperature was raised to 80°C, and the mixture was stirred until the reaction solution was completely dissolved. The solution was then cooled to 75°C. Subsequently, 18.93 parts by mass of acetic acid, an acidic compound, was added for neutralization. Then, while maintaining the reaction solution at 75°C, 20 parts by mass of NIKKOL Hexaglyn 1-SV (HLB=9.0, manufactured by Nikko Chemical Co., Ltd.) were added and mixed. Then, 800 parts by mass of deionized water heated to 70°C was slowly added for emulsification. Next, MEK was distilled off using an evaporator under reduced pressure at a water bath temperature of 60°C. Finally, the concentration of solids was adjusted to 20% by mass with deionized water to obtain a dispersion containing polyurethane resin (average HLB=9.0 for nonionic surfactants, 20% by mass of solids).

[0235] 1.5. Preparation of a dispersion of dendritic polymer compounds (Preparation Example A-14) 15.3 parts by weight of sorbitan tristearate (hydroxyl value = 77.2 mg KOH / g) and 24.7 parts by weight of 4-methyl-2-pentanone (MIBK) were added to a four-necked round-bottom flask equipped with a top stirrer, thermocouple, and DeanStark / condenser. The solution was refluxed for 1 hour to remove residual moisture. After 1 hour, the solution was cooled to 50°C, 4.0 parts by weight of DESMODUR N-100 were added, followed by the addition of a catalyst, and the solution was heated to 80°C for more than 1 hour to obtain a dendritic polymer solution.

[0236] 52.7 parts by weight of water, 0.7 parts by weight of ARMEEN DM-18D, 2.0 parts by weight of TERGITOL TMN-10, and 0.6 parts by weight of acetic acid were added to a beaker and stirred to prepare a surfactant solution, which was then heated to 60°C. The prepared dendritic polymer solution was cooled to 60°C, and the heated surfactant solution was slowly added to prepare a cloudy emulsion. After homogenization at 41.37 MPa (6000 psi), the solvent was removed by distillation under reduced pressure to obtain a dispersion containing 20% ​​dendritic polymer compounds (average HLB of nonionic surfactant = 14.4, solids content 20% by weight).

[0237] 2. Preparation of Polyisocyanate Dispersion (Preparation Example B-1: DMP-Capped Product of IPDI Monomer) In a reactor equipped with a stirrer, thermometer, cooler, and nitrogen inlet pipe, 150 parts by mass (NCO equivalent: 1.35 mol) of Isophorone Diisocyanate (hereinafter sometimes referred to as IPDI, Tokyo Chemical Industry Co., Ltd., NCO group content: 37.8%, NV: 100%) and 150 parts by mass of diethylene glycol methyl ethyl ether (hereinafter sometimes referred to as MEDG) as solvent were mixed at room temperature. 130 parts by mass (1.35 mol) of dimethylpyrazole (hereinafter sometimes referred to as DMP, Tokyo Chemical Industry Co., Ltd.) as capping agent were added in several portions to maintain the temperature of the reaction solution below 50°C, and the mixture was stirred for 1 hour. Subsequently, Fourier transform infrared (FT-IR) spectroscopy confirmed that the peak originating from the NCO group (around 2260 cm⁻¹) had disappeared, indicating that the group had been capped. Next, 28 parts by weight of NOIGEN XL-100 (HLB=14.7, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) were added, and mixed pure water was added in small amounts each time to obtain a dispersion containing 20% ​​by weight of IPDI monomer and DMP end-capping compound (average HLB=14.7 of nonionic surfactant).

[0238] (Example B-2: DMP-terminated IPDI trimer) Using the same method as Example B-1, 150 parts by mass (NCO equivalent: 0.62 mol) of Vestanet 1890 / 100 (isophorone diisocyanate trimer, manufactured by Evonik, NCO content: 17.3%, NV: 100%) as a polyisocyanate and 59.6 parts by mass (0.62 mol) of dimethylpyrazole (DMP) as a terminator were used to obtain an IPDI trimer DMP-terminated product. Next, 21 parts by mass of NOIGEN XL-40 (HLB=10.5, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) were added, and mixed pure water was added in small amounts each time to obtain a dispersion containing 20% ​​by mass of IPDI trimer DMP-terminated product (average HLB of nonionic surfactant = 10.5).

[0239] (Modification Example B-3: DMP-terminated product of IPDI trimer) Using the same method as Modification Example B-1, 150 parts by mass (NCO equivalent: 0.62 mol) of Vestanet 1890 / 100 (isophorone diisocyanate trimer, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) as a polyisocyanate and 59.6 parts by mass (0.62 mol) of dimethylpyrazole (DMP) as a terminator were used to obtain the IPDI trimer DMP-terminated product. Next, 21.0 parts by weight of NIKKOL SI-10RV (HLB=5.0, manufactured by Nikko Chemical Co., Ltd.) and 2.1 parts by weight of stearyltrimethylammonium hydrochloride were added, and mixed pure water was added in small amounts each time to obtain a dispersion containing 20% ​​by weight of IPDI trimer·DMP end-capped material (average HLB=5.0 of nonionic surfactant).

[0240] (Example B-4: DMP-terminated IPDI trimer) Using the same method as Example B-1, 150 parts by mass (NCO equivalent: 0.62 mol) of Vestanet 1890 / 100 (isophorone diisocyanate trimer, manufactured by Evonik Industries, NCO content: 17.3%, NV: 100%) as a polyisocyanate and 59.6 parts by mass (0.62 mol) of dimethylpyrazole (DMP) as a terminator were used to obtain an IPDI trimer DMP-terminated product. Then, 21 parts by mass of mixed NIKKOL BC-25 (HLB=18.5, manufactured by Nikko Chemical Co., Ltd.) and purified water were added in small batches to obtain a dispersion containing 20% ​​by mass of the IPDI trimer DMP-terminated product (average HLB of nonionic surfactant: 18.5).

[0241] (Modification Example B-5: Diethyl malonate end-capping product of IPDI trimer) Except for using 150 parts by weight (NCO equivalent: 0.62 mol) of Vestanet 1890 / 100 (isophorone diisocyanate trimer, manufactured by Evonik Industries, NCO group content: 17.3%, NV: 100%) as the polyisocyanate and 99.3 parts by weight (0.62 mol) of Diethyl Malonate (DEM, Tokyo Chemical Industry Co., Ltd.) as the end-capping agent, the product was modified in the same manner as in Modification Example B-1. Next, 13.6 parts by weight of NOIGEN XL-100 (HLB=14.7, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) and 11.4 parts by weight of NOIGEN XL-60 (HLB=12.5, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) were added, and mixed pure water was added in small amounts each time to obtain a dispersion containing 20% ​​by weight of IPDI trimer diethyl malonate end-capped material (average HLB of nonionic surfactant = 13.7).

[0242] (Modification Example B-6: MEKO end-capped product of IPDI trimer) Except for using 150 parts by weight (NCO equivalent: 0.62 mol) of Vestanet 1890 / 100 (isophorone diisocyanate trimer, manufactured by Evonik Industries, NCO group content: 17.3%, NV: 100%) as a polyisocyanate and 54.0 parts by weight (0.62 mol) of 2-Butanone Oxime (methyl ethyl ketone oxime, MEKO, Tokyo Chemical Industry Co., Ltd.) as an end-capping agent, the product was modulated in the same manner as in Modification Example B-1. Next, 6.9 parts by weight of NOIGEN XL-100 (HLB=14.7, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) and 13.6 parts by weight of NOIGEN XL-60 (HLB=12.5, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) were added, and mixed pure water was added in small amounts each time to obtain a dispersion containing 20% ​​by weight of IPDI trimer MEKO end-capped material (average HLB of nonionic surfactant = 13.2).

[0243] (Example B-7: Self-emulsifying type of DMP-terminated IPDI trimer) In a reactor equipped with a stirrer, thermometer, cooler, and nitrogen inlet pipe, Vestanat, as a polyisocyanate, was prepared at room temperature. 150 parts by mass of 1890 / 100 (isophorone diisocyanate trimer, manufactured by Evonik Industries, NCO group content: 17.3%, NV: 100%) (NCO equivalent: 0.62 mol) and 150 parts by mass of diethylene glycol methyl ethyl ether (hereinafter sometimes abbreviated as MEDG) as solvent were mixed. Then, 23.7 parts by mass of methoxy PEG#1000 (number average molecular weight 1000: manufactured by Toho Chemical Co., Ltd.), a hydrophilic compound containing active hydrogen groups, was added (OH: 0.024 mol, equivalent ratio: OH / NCO=0.038). The mixture was subjected to an amino-formaldehyde esterification reaction at 90°C until the residual isocyanate content no longer changed, thereby synthesizing a polyisocyanate containing hydrophilic groups. Subsequently, 57.3 parts by mass (0.596 mol) of dimethylpyrazole (DMP) as a capping agent were added in several portions to keep the temperature of the reaction solution below 50°C, and the mixture was stirred for 1 hour. Next, small amounts of mixed pure water were added sequentially to obtain a dispersion containing 20% ​​by mass of IPDI trimer·DMP end-capped material (average HLB of nonionic surfactant: 12.7).

[0244] (Modification Example B-8: DMP end-capping product of hydrogenated MDI monomer) Except for using 167 parts by mass (NCO equivalent: 1.27 mol) of Dicyclohexylmethane 4,4'-Diisocyanate (dicyclohexylmethane-4,4'-diisocyanate, hydrogenated MDI monomer, Tokyo Chemical Industry Co., Ltd., NCO group content: 32.0%, NV: 90%) as a polyisocyanate and 122 parts by mass (1.27 mol) of dimethylpyrazole (DMP) as an end-capping agent, the modification was carried out in the same manner as in Modification Example B-1. Next, 3.3 parts by weight of NOIGEN XL-40 (HLB=10.5, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) and 25.6 parts by weight of NOIGEN XL-60 (HLB=12.5, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) were added, and mixed pure water was added in small amounts each time to obtain a dispersion containing 20% ​​by weight of hydrogenated MDI monomer and DMP end-capped material (average HLB of nonionic surfactant = 12.27).

[0245] (Example B-9: DMP-terminated HDI monomer) Except for using 150 parts by mass (NCO equivalent: 1.78 mol) of Hexamethylene Diisocyanate (Tokyo Kasei Corporation, NCO content: 49.9%, NV: 100%) as the polyisocyanate and 171 parts by mass (1.78 mol) of dimethylpyrazole (DMP) as the terminator, the mixture was prepared in the same manner as in Example B-1. Next, 19.0 parts by mass of NOIGEN XL-40 (HLB=10.5, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) and 12.9 parts by mass of NOIGEN XL-60 (HLB=12.5, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) were added, and mixed purified water was added in small increments to obtain a dispersion containing 20% ​​by mass of HDI monomer and DMP-terminated product (average HLB of nonionic surfactant = 11.3).

[0246] (Modification Example B-10: DMP end-capping product of HDI trimer (biuret type)) Except for using 150 parts by mass (NCO equivalent: 0.839 mol) of DURANATE 24A-100 (biuret type of hexamethylene diisocyanate, Asahi Kasei, NCO content: 23.5%, NV: 100%) as a polyisocyanate and 80.7 parts by mass (0.839 mol) of dimethylpyrazole (DMP) as an end-capping agent, the product was modulated in the same manner as in Modification Example B-1. Next, 19.4 parts by weight of NOIGEN XL-40 (HLB=10.5, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) and 3.7 parts by weight of NOIGEN XL-60 (HLB=12.5, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) were added, and mixed pure water was added in small amounts each time to obtain a dispersion containing 20% ​​by weight of HDI trimer·DMP end-capped material (average HLB of nonionic surfactant = 10.8).

[0247] (Modification Example B-11: DMP end-capping product of HDI trimer (isocyanurate type)) Except for using 150 parts by mass (NCO equivalent: 0.825 mol) of DURANATE TPA-100 (isocyanurate type of hexamethylene diisocyanate, Asahi Kasei, NCO content: 23.1%, NV: 100%) as a polyisocyanate and 79.3 parts by mass (0.825 mol) of dimethylpyrazole (DMP) as an end-capping agent, the modification was carried out in the same manner as in Modification Example B-1. Next, 21.3 parts by weight of NOIGEN XL-40 (HLB=10.5, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) and 1.7 parts by weight of stearyl alcohol 4 molar ethylene oxide adduct (HLB=8.4) were added, and mixed pure water was added in small amounts each time to obtain a dispersion containing 20% ​​by weight of HDI trimer·DMP end-capped product (average HLB=10.3 for nonionic surfactants).

[0248] (Modification Example B-12: MEKO end-capping product of HDI trimer (isocyanurate type)) Except for using 150 parts by mass (NCO equivalent: 0.825 mol) of DURANATE TPA-100 (isocyanurate type of hexamethylene diisocyanate, Asahi Kasei, NCO content: 23.1%, NV: 100%) as a polyisocyanate and 71.87 parts by mass (0.825 mol) of 2-Butanone Oxime (methyl ethyl ketone oxime, MEKO, Tokyo Kasei) as an end-capping agent, the product was modified in the same manner as in Modification Example B-1. Next, 19.3 parts by weight of NOIGEN XL-40 (HLB=10.5, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) and 8.9 parts by weight of stearyl alcohol 4 molar ethylene oxide adduct (HLB=8.4) were added, and mixed pure water was added in small amounts each time to obtain a dispersion containing 20% ​​by weight of HDI trimer MEKO end-capped product (average HLB of nonionic surfactant = 9.84).

[0249] (Modification Example B-13: Self-emulsifying type of DMP-terminated HDI trimer) Trixene Aqua BI-220 (manufactured by Lanxess, 40% solids content) was diluted with pure water to make the solids content 20%.

[0250] (Modification Example B-14: Self-emulsifying type of DMP end-capped product of IPDI / HDI trimer) Dilute Trixene Aqua BI-522 (manufactured by Lanxess, 40% solids content) with pure water to make the solids content 20%.

[0251] (Example B-15: Mixed Emulsion) In a reactor equipped with a stirrer, thermometer, cooler, and nitrogen inlet pipe, 150 parts by mass (NCO equivalent: 0.62 mol) of Vestanet 1890 / 100 (isophorone diisocyanate trimer, manufactured by Evonik Industries, NCO group content: 17.3%, NV: 100%) as a polyisocyanate and 150 parts by mass of diethylene glycol methyl ethyl ether (MEDG) as a solvent were mixed at room temperature. Then, 23.7 parts by mass (OH: 0.024 mol, equivalent ratio: OH / NCO=0.038) of methoxy PEG#1000 (number average molecular weight 1000, manufactured by Toho Chemical Co., Ltd.), a hydrophilic compound containing active hydrogen groups, was added and subjected to an amino-formate reaction at 90°C until the amount of residual isocyanate no longer changed, thereby synthesizing a polyisocyanate containing hydrophilic groups. Subsequently, 57.3 parts by mass (0.596 mol) of dimethylpyrazole (DMP) as a capping agent were added in several portions to maintain the temperature of the reaction solution below 50°C, and the mixture was stirred for 1 hour. Then, 100 parts by mass of acetone and 332.4 parts by mass of WACKER FINISH WR 301 (amine-modified polysiloxane, manufactured by Asahi Kasei Corporation, amine equivalent 3700, 100% solids content) (amine 0.09 mol) were added to this solution to homogenize it. Then, 700 parts by mass of deionized water were slowly added dropwise to emulsify the solution. After emulsification, the solvent was removed under reduced pressure, and 6.0 parts by mass of 90% acetic acid and deionized water were added to obtain an emulsion with a solids content of 20%. The emulsion in Preparation Example B-15 was a mixed emulsion of polysiloxane and capped isocyanate containing water-repellent components in a 59:41 ratio (parts by mass).

[0252] (Example B-16: MEKO-terminated product of trimethylolpropane and toluene diisocyanate (TDI)) As a reaction product of trimethylolpropane and toluene diisocyanate, Pururene AD (containing 75% by mass of the reaction product of trimethylolpropane and toluene diisocyanate (2,4-isomer and 2,6-isomer in a mass ratio of 80:20), solvent: ethyl acetate, manufactured by SAPICI, trade name) was prepared. One mole of the above-prepared reaction product of trimethylolpropane and toluene diisocyanate was heated to 60-70°C. Then, 3 moles of methyl ethyl ketone oxime were slowly added, and the reaction was continued until the isocyanate content, as confirmed by infrared spectrophotometry at 60-70°C, was zero. Ethyl acetate was then added to obtain a colorless, transparent, viscous liquid composition containing 98.7% by mass of methyl ethyl ketone oxime-terminated polyisocyanate. 180 parts by weight of the above-obtained composition and 20 parts by weight of the 30 molar ethylene oxide adduct of tristyrene phenol as a nonionic surfactant were mixed and homogenized. Water was slowly added while stirring, and the mixture was homogenized at 30 MPa to obtain a dispersion containing 20% ​​by weight of the methyl ethyl ketone oxime end-capped product of the reaction between trimethylolpropane and toluene diisocyanate.

[0253] (Example B-17: IPDI trimer) In a reactor equipped with a stirrer, thermometer, cooler, and nitrogen inlet pipe, 150 parts by mass (NCO equivalent: 0.62 mol) of isophorone diisocyanate trimer (IPDI trimer) (Vestanat 1890 / 100, manufactured by Evonik Industries, Inc., NCO content: 17.3%, NV: 100%) as a polyisocyanate and propylene glycol diacetate (DOWANOL (registered trademark) PGDA, Ando Parachemie Co., Ltd.) as a solvent were mixed and the polyisocyanate was completely dissolved to obtain a PGDA solution of IPDI trimer. Next, 4.3 parts by mass of N,N-dimethylcyclohexylamine (Kanto Chemical Co., Ltd.) were mixed into the PGDA solution. 12.8 parts by weight of polyoxyethylene tridecyl ether phosphate (Rhodafac range, manufactured by Rhodia, EO: 7mol) as an emulsifier were added to the mixture, and the mixture was mixed while being appropriately cooled to a temperature below 50°C to obtain a solution containing 40% by weight of IPDI trimer.

[0254] (Modification Example B-18: IPDI trimer / HDI trimer ureate) In the same reactor as Modification Example B-17, at room temperature, 42 parts by weight (NCO equivalent: 0.62 mol) of isophorone diisocyanate trimer (IPDI trimer) (Vestanat 1890 / 100, Evonik, NCO content: 17.3%, NV: 100%) of hexamethylene diisocyanate (HDI) ureate type (DURANATE) were prepared as polyisocyanates. 98 parts by weight of TPA-100 (manufactured by Asahi Kasei Corporation, NCO content: 23.1%, NV: 100%) (NCO equivalent: 0.825 mol) and propylene glycol diacetate (DOWANOL PGDA, Ando Parachemie Co., Ltd.) as a solvent were mixed and the polyisocyanate was completely dissolved to obtain a PGDA solution of IPDI trimer / HDI trimer. Next, 4.0 parts by weight of N,N-dimethylcyclohexylamine (Kanto Chemical Co., Ltd.) were mixed into this solution. Then, 11.9 parts by weight of polyoxyethylene tridecyl ether phosphate (Rhodafac range, manufactured by Rhodia Corporation, EO: 10 mol) as an emulsifier were added, and the mixture was mixed while being appropriately cooled to a temperature below 50°C to obtain a solution containing 70% by weight of IPDI trimer / HDI trimer urea ester.

[0255] (Modification Example B-19: IPDI trimer / HDI trimer biuret) In the same reactor as Modification Example B-17, at room temperature, 42 parts by mass (NCO equivalent: 0.62 mol) of isophorone diisocyanate trimer (IPDI trimer) (Vestanat 1890 / 100, manufactured by Evonik, NCO content: 17.3%, NV: 100%), 98 parts by mass (NCO equivalent: 0.839 mol) of biuret form of hexamethylene diisocyanate (HDI) (DURANATE 24A-100, manufactured by Asahi Kasei, NCO content: 23.5%, NV: 100%), and propylene glycol diacetate (DOWANOL (registered trademark) PGDA, Ando Parachemie Co., Ltd.) as solvent were mixed and the polyisocyanates were completely dissolved to obtain a PGDA solution of IPDI trimer / HDI trimer. Next, 4.0 parts by weight of N,N-dimethylcyclohexylamine (Kanto Chemical Co., Ltd.) were mixed into the solution. Then, 11.9 parts by weight of polyoxyethylene tridecyl ether phosphate (Rhodafac range, manufactured by Rhodia, EO: 10mol) as an emulsifier were added, and the mixture was mixed while being appropriately cooled to a temperature below 50°C to obtain a solution containing 70% by weight of IPDI trimer / HDI trimer biuret.

[0256] The properties of the polyisocyanate dispersions or solutions of each of the preparation examples B-1 to B-19 are summarized in Table 4 below.

[0257] 〔Table 4〕

[0258] 3. Preparation of the comparative mixed emulsion (Preparation Example C-1) In a separable flask, add 15.9 parts by mass of CORONATE L (trimethylolpropane adduct of toluene diisocyanate, manufactured by Tosoh Corporation, NCO%=13.4, 75% solids ethyl acetate solution) and 3.6 parts by mass of acetone and stir. Next, slowly add 4.3 parts by mass of methyl ethyl ketone oxime using a dropping funnel and react at 50-55°C for 1 hour. Then, add 2.7 parts by mass of UNIOX M-2000 (polyethylene glycol monomethyl ether with an average molecular weight of 2000, manufactured by Nippon Oil Corporation, 100% solids), 0.001 parts by mass of diazabicycloundecene, and 4.5 parts by mass of acetone, react at 60°C for 2 hours, and after confirming that the NCO content is 0%, cool to 40°C with water. Add 40.5 parts by mass of WACKER FINISH WR 301 (amine-modified polysiloxane, manufactured by Asahi Kasei WACKER Organosilicon Co., Ltd., amine equivalent 3700, 100% solids) and 24.1 parts by mass of acetone. After confirming that the solution becomes homogeneous, slowly add 110 parts by mass of deionized water and emulsify. After emulsification, remove the solvent under reduced pressure, and add 0.74 parts by mass of 90% acetic acid and 109 parts by mass of deionized water to obtain an emulsion with a total concentration of 20% for both amine-modified polysiloxane and terminal isocyanate. This emulsion is a mixed emulsion of amine-modified polysiloxane and terminal isocyanate containing water-repellent components in a 5:2 (mass ratio). Furthermore, this terminal isocyanate has polyethylene glycol monomethyl ether incorporated into a portion of its structure, exhibiting self-emulsifying properties.

[0259] (Modification Example C-2) Except for changing the amount added, the same operation as in Modification Example C-1 was performed to obtain a mixed emulsion containing water-repellent components in a 5:1 (mass ratio) ratio of amine-modified polysiloxane and capped isocyanate (the total concentration of amine-modified polysiloxane and capped isocyanate is 20%; this capped isocyanate has polyethylene glycol monomethyl ether introduced into a part of its structure, and has self-emulsifying properties.).

[0260] (Preparation Example C-3) 16.3 parts by weight of DURANATE 24A-100 (biuret form of hexamethylene diisocyanate, manufactured by Asahi Kasei Chemicals, NCO%=23.5) and 10 parts by weight of methyl isobutyl ketone (MIBK) were added to a separable flask and stirred. 8.8 parts by weight of 3,5-dimethylpyrazole were added, and the mixture was heated at 50°C and reacted until the isocyanate content was 0%, thereby obtaining a capped isocyanate. Next, 62.9 parts by weight of EMASOL S-30V (sorbitan tristearate, manufactured by Kao Corporation, hydroxyl value 68.6 mgKOH / g) and 75 parts by weight of MIBK were added and melted at 60°C. At 60°C, 2.8 parts by mass of dimethylstearylamine, 1.9 parts by mass of acetic acid (90% aqueous solution), and 1.4 parts by mass of Tergitol TMN-10 (HLB=14.4, polyethylene glycol trimethyl nonyl ether, manufactured by Dow Chemical Company, 90% aqueous solution) were dissolved in 150 parts by mass of deionized water and added dropwise. The temperature was maintained, and emulsification was performed using a high-pressure homogenizer (400 bar). Subsequently, 80 parts by mass of deionized water were added, and MIBK was removed by distillation under reduced pressure. Finally, 163 parts by mass of deionized water were added to obtain an emulsion with a total concentration of 20% (HLB=14.4) of sorbitan tristearate and capped isocyanate. This emulsion is a mixed emulsion of sorbitan tristearate and capped isocyanate containing water-repellent components in a 5:2 (mass ratio). Furthermore, this formulation is a mixed emulsion of water-repellent and cross-linking components emulsified with the nonionic surfactant Tergitol TMN-10 and the cationic surfactant dimethylstearylamine acetate.

[0261] 3. Preparation of the water-repellent composition (Examples 1-39, Comparative Examples 1-10) Using the above-mentioned dispersions containing non-fluorinated water-repellent components, dispersions or solutions containing polyisocyanates, mixed emulsions, and / or pure water, a water-repellent composition (treatment solution) was obtained in the manner shown in Tables 5-8. Furthermore, the numerical values ​​for the relevant components in Tables 5-8 are in "mass %".

[0262] 4. Treatment of fiber products: After impregnating 100% polyester (PET) fabric or 100% nylon (Ny) fabric in a treatment solution, heat-treating at 140°C for 2 minutes, thereby obtaining fiber products for evaluation.

[0263] 5. Evaluation Method 5.1 Evaluation of Initial Water Repellency of Fiber Products The water repellency of the above-mentioned fiber products was evaluated by setting the spray water temperature to 20°C according to the spray method of JIS L1092 (2009). The results were evaluated visually according to the following grades. For slightly better properties, "+" was added after the grade, and for slightly worse properties, "-" was added after the grade. Water Repellency: State 5: No surface wet 4: Surface slightly wet 3: Surface partially wet 2: Surface wet 1: Surface completely wet 0: Surface and back completely wet

[0264] 5.2 Evaluation of the wash durability and water repellency of fiber products The above-mentioned fiber products were washed 20 times (L-20) according to JIS L0217 (1995) method 103, and the water repellency after air drying was evaluated using the same process and grade as above.

[0265] 5.3 Evaluation of the abrasion resistance and water repellency of fiber products 5.3.1 Preparation of abrasion cloth According to the Martindale method of JIS L1096:2010, test pieces made of the above-mentioned fiber products were installed on the sample rack of the Martindale abrasion tester, and the standard friction cloth was installed on the friction table of the abrasion tester. The sample rack was placed on it, and a pressing load of 9 kPa was applied for 1000 cycles to obtain the abrasion cloth for evaluation.

[0266] 5.3.2 Evaluation of the water repellency of the abrasive fabric The water repellency of the above abrasive fabric shall be evaluated using the same process and grade as described above.

[0267] 5.4 Bondisman Rain Test for Initial Fiber Products For 100% polyester (PET) fabrics treated with water repellency as described above, the water repellency, water absorption, and water absorption rate were evaluated after a rain test conducted according to the method described in JIS L1092:2009 7.3 Rain Test (Spray Test) Method A. The rain test duration was 10 minutes. Water repellency was graded from 1 to 5 based on the wet conditions shown in Figure 1. A higher number indicates better performance. A + (-) mark after the grade indicates slightly better (poorer) performance in each property.

[0268] 5.5 Bondisman rain test on abrasive fabric In addition to using the abrasive fabric described above, the Bondisman rain test is conducted in the same manner as described above to evaluate water repellency, water absorption, and water absorption rate.

[0269] 5.6 Water pressure resistance of initial fiber products: For 100% polyester (PET) fabrics that have been treated with water repellency as described above, the water pressure resistance shall be determined according to JIS-L1092:2009 7.1 A method (low water pressure method).

[0270] 5.7 Water pressure resistance after washing The above-mentioned fiber products were washed 20 times (L-20) according to method 103 of JIS L0217 (1995), and then the water pressure resistance was measured in the same manner as above.

[0271] 6. Evaluation Results The evaluation results are shown in Tables 5-8 below.

[0272] 〔Table 5〕

[0273] 〔Table 6〕

[0274] 〔Table 7〕

[0275] 〔Table 8〕

[0276] The results shown in Tables 5-8 indicate the following: (1) When fiber products are treated with a water-repellent composition containing a non-fluorinated water-repellent component and a polyisocyanate, the water repellency of the fiber products after abrasion is significantly better than that of the case where the polyisocyanate does not contain alicyclic groups (Comparative Examples 1-9). This effect can be considered as a unique effect brought about by the combination of non-fluorinated water-repellent component and alicyclic polyisocyanate. (2) The above-mentioned effect brought about by alicyclic polyisocyanate also occurs when the polyisocyanate contains both alicyclic polyisocyanate and other polyisocyanates (Examples 9-16, 18, 19, 33, 34 and 39). (3) Regarding the initial water repellency and wash-durable water repellency of the fiber products, there was no significant difference between the cases where the polyisocyanate did not contain alicyclic groups (Comparative Examples 1-9) and the cases where the polyisocyanate contained alicyclic groups (Examples 1-39). (4) Regarding the performance of the Bondisman rain test, initially, there was no significant difference between the cases where the polyisocyanate did not contain alicyclic groups (Comparative Examples 1-9) and the cases where the polyisocyanate contained alicyclic groups (Examples 1-39); however, after abrasion, the cases where the polyisocyanate contained alicyclic groups (Examples 1-39) were superior to those where the polyisocyanate did not contain alicyclic groups (Comparative Examples 1-9).

[0277] Furthermore, although the above embodiments illustrate the use of non-fluorinated water-repellent compositions to impart water-repellent properties to fiber products, the technology of the present invention is not limited to this type. The non-fluorinated water-repellent compositions of the present invention should be able to impart water-repellent and abrasion-resistant water-repellent properties to various articles other than fiber products, but are particularly suitable for imparting water-repellent and abrasion-resistant water-repellent properties to fiber products, as shown in the above embodiments. [Simplified Explanation of the Diagram]

[0007] [Figure 1] shows the evaluation criteria of the Bundesmann Water Repellency Test.

Claims

1. A non-fluorinated water-repellent composition comprising: (A) a polysiloxane compound as a non-fluorinated water-repellent component; and (B) an alicyclic polyisocyanate; wherein the polysiloxane compound (A) comprises: a polysiloxane resin containing MQ, MDQ, MT, MTQ, MDT or MDTQ as constituent components, and an amine-modified polysiloxane oil.

2. The non-fluorinated water-repellent composition as described in claim 1, wherein, (B) Alicyclic polyisocyanates are at least one of isophorone diisocyanate and hydrogenated MDI (methylene bis(cyclohexyl isocyanate)).

3. The non-fluorinated water-repellent composition as described in claim 1 or 2, wherein, (B) Alicyclic polyisocyanate trimers.

4. The non-fluorinated water-repellent composition as described in claim 1 or 2, wherein, In addition to (B) alicyclic polyisocyanates, it also contains at least one of aliphatic polyisocyanates, aromatic polyisocyanates and aromatic aliphatic polyisocyanates.

5. A method for manufacturing a water-repellent fiber article, comprising the step of treating the fiber with a treatment solution containing a non-fluorinated water-repellent composition as described in claim 1 or 2.

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