TW202547989A - Water-repellent composition, manufacturing method of water-repellent fiber products, and water-repellent fiber products - Google Patents

Abstract

The present invention provides: a water-repellent composition from which it is possible to obtain a water-repellent fiber product which exhibits excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, and texture; a method for producing a water-repellent fiber product using the same; and a water-repellent fiber product using the same. Provided is a water-repellent composition containing an amino-modified silicone, a silicone resin, and an alkyl polysiloxane, wherein: the blending amount of the silicone resin is 1,000-5,000 parts by mass relative to 100 parts by mass of the blending amount of the amino-modified silicone; and the blending amount of the silicone resin is 60-130 parts by mass relative to 100 parts by mass of the total blending amount of both the amino-modified silicone and the alkyl polysiloxane.

Description

Water-repellent composition, manufacturing method of water-repellent fiber products, and water-repellent fiber products

This invention relates to a water-repellent composition, a method for manufacturing water-repellent fiber products, and water-repellent fiber products.

In the past, fluorinated water-repellent agents with fluorine groups have been known, and it is also known that water-repellent properties are imparted to the surface of fiber products by treating them with these fluorinated water-repellent agents. These fluorinated water-repellent agents are generally manufactured by polymerizing or copolymerizing fluoroalkyl monomers. Although fiber products treated with fluorinated water-repellent agents exhibit excellent water-repellent properties, the fluoroalkyl monomers cause environmental problems due to their reluctance to decompose.

Therefore, in recent years, research on fluorine-free (i.e., non-fluorinated) polysiloxane water repellents as proposed in patents 1 and 2 below has been continuously advancing. [Previous Art Documents] [Patent Documents]

[Patent Document 1] Japanese Patent Application Publication No. 2017-226946 [Patent Document 2] International Publication No. 2019/131456

[Technical Problem to be Solved by the Invention] In recent years, water-repellent fiber products have been increasingly used for outdoor applications, and higher requirements are being placed on these products for water pressure resistance and abrasion resistance than in the past. However, the water-repellent agents described in the aforementioned patents 1 and 2 still have room for improvement, particularly in terms of water pressure resistance, abrasion resistance, and such durability.

This invention is made in view of the foregoing circumstances, and its purpose is to provide a water-repellent agent composition, a method for manufacturing water-repellent fiber products using the same, and water-repellent fiber products using the same; the aforementioned water-repellent agent composition yields water-repellent fiber products with excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, and superior texture. [Technical Means]

After conducting in-depth research to solve the above-mentioned problems, the inventor discovered that by combining specific polysiloxanes, polysiloxanes, and alkyl polysiloxanes, and adjusting the mass ratio of the amount of polysiloxane to the amount of specific polysiloxanes, as well as the mass ratio of the amount of polysiloxane to the total amount of specific polysiloxanes and alkyl polysiloxanes, it is possible to obtain fiber products with high water repellency and durability, water pressure resistance and durability, and abrasion resistance, as well as a soft texture. Based on this insight, the present invention was completed.

One aspect of the present invention provides a water-repellent composition comprising an amino-modified polysiloxane, a polysiloxane resin, and an alkyl polysiloxane; the amount of the polysiloxane resin is 1,000 to 5,000 parts by mass relative to 100 parts by mass of the amino-modified polysiloxane resin, and the amount of the polysiloxane resin is 60 to 130 parts by mass relative to 100 parts by mass of the combined amount of the amino-modified polysiloxane resin and the alkyl polysiloxane resin.

The water-repellent composition according to one aspect of the present invention can provide water-repellent fiber products with excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, and texture.

From the perspectives of water repellency, durable water repellency, texture, and seam slippage, the functional group equivalent of the aforementioned amine-modified polysiloxane can be 100–20,000 g/mol. Here, the functional group equivalent of amine-modified polysiloxane refers to the molecular weight of amine-modified polysiloxane corresponding to 1 mol of nitrogen atoms.

The present invention also provides a method for manufacturing a water-repellent fiber product comprising a step of treating fibers with a treatment liquid containing a water-repellent composition of the present invention as described above, and a water-repellent fiber product having fibers and a water-repellent composition of the present invention as described above attached to the fibers.

According to the manufacturing method of the water-repellent fiber product of this invention, water-repellent fiber products with excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, and superior texture can be stably manufactured. [Effects of the Invention]

According to one aspect of the present invention, a water-repellent agent composition can be provided, which yields water-repellent fiber products with excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, and texture. Furthermore, the water-repellent agent composition of one aspect of the present invention exhibits excellent resistance to agents used in the preceding water-repellent treatment step of fibers using this water-repellent agent composition. Therefore, it offers the advantage that even when the agents used in the preceding step are introduced into the water-repellent treatment bath, the water repellency is not easily reduced (i.e., it has good resistance to introduced agents).

The ideal embodiment of the present invention (hereinafter also referred to as the embodiment) will be described in detail below. However, the present invention is not limited to the following embodiment.

[Water-repellent composition] The water-repellent composition of this embodiment contains water-repellent components including amine-modified polysiloxane (hereinafter sometimes referred to as component (I)), polysiloxane resin (hereinafter sometimes referred to as component (II)) and alkyl polysiloxane (hereinafter sometimes referred to as component (III)).

<Amine-Modified Polysiloxanes> Amine-modified polysiloxanes can be listed as compounds having an organic group containing an amino group and/or an imine group on the side chain and/or at the end of an organopolysiloxane. Such organic groups can be, for example, those represented by -R- _NH2 and those represented by -R-NH-R'- _NH2 . R and R' can be divalent groups such as ethylidene and propylidene. Some or all of the amino and/or imine groups can also be blocked amino and/or imine groups. Blocked amino and/or imine groups are obtained, for example, by treating the amino and/or imine groups with a blocking agent. Blocking agents include, for example, fatty acids with 2 to 22 carbon atoms, acid anhydrides of fatty acids with 2 to 22 carbon atoms, acetyl halides of fatty acids with 2 to 22 carbon atoms, and aliphatic monoisocyanates with 1 to 22 carbon atoms.

From the perspectives of water repellency, durable water repellency, texture, and seam slippage, the functional group equivalent of amine-modified polysiloxane is ideally 100–20,000 g/mol, more ideally 150–12,000 g/mol, and even more ideally 200–4,000 g/mol.

Ideally, amine-modified polysiloxane (PVC) is liquid at 25°C. The ideal kinematic viscosity of PVC 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. When the kinematic viscosity at 25°C is above 10 ^mm² /s, the desired effect of the water-repellent composition can be easily obtained; when it is below 100,000 ^mm² /s, there is a tendency to easily ensure workability and seam slippage. The kinematic viscosity at 25°C refers to the value measured using the method described in JIS K 2283:2000 (Uberlot viscometer). Furthermore, at 25°C, especially in the case of low viscosity, cs (centipoise) is sometimes used as the unit, and the two are essentially the same.

Amine-modified polysiloxanes can be made from commercially available products. Examples of commercially available products include: KF8005, KF-868, KF-864, and KF-393 (all manufactured by Shin-Etsu Chemical Co., Ltd., trade names); XF42-B1989 (manufactured by Momentive Performance Materials Japan Co., Ltd.); and SF-8417 and BY16-853U (both manufactured by Dow Toray Industries, Ltd., trade names).

Amine-modified polysiloxanes can be used alone or in combination with two or more.

Amine-modified polysiloxanes can be neutralized or remain unneutralized, with some or all of the amine and/or imine groups being neutralized. Neutralization can be achieved using organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, methanesulfonic acid, and toluenesulfonic acid; and inorganic acids such as hydrogen chloride, sulfuric acid, and nitric acid.

<Polysilicone Resin> The water-repellent composition of this embodiment contains polysilicone resin. Ideally, the polysilicone resin is an organic polysiloxane containing MQ, MDQ, MT, MTQ, MDT, or MDTQ as constituent components, is solid at 25°C, and has a three-dimensional structure. Furthermore, the polysilicone resin, according to JIS K 6249:2003, section 13, hardness test, measured by a type A hardness tester, ideally has a hardness of 20 or higher, and more ideally 60 or higher. Here, M, D, T and Q represent (R”) _3SiO0.5 unit, (R”) _2SiO unit, R” _SiO1.5 unit and _SiO2 unit, respectively. _R ” represents a monovalent aliphatic hydrocarbon with 1 to 10 carbon atoms, or a monovalent aromatic hydrocarbon with 6 to 15 carbon atoms.

Polysiloxane resins are commonly referred to as MQ resins, MT resins, or MDT resins, and sometimes also include terms such as MDQ, MTQ, or MDTQ.

Polysiloxanes can be obtained alone or in the form of solutions prepared by dissolving them in suitable solvents. The solvent can be an alkyl polysiloxane and/or a solvent other than an alkyl polysiloxane. Examples of solvents other than alkyl polysiloxanes include, for example, n-hexane, isopropanol, dichloromethane, 1,1,1-trichloroethane, and mixtures of these solvents.

Examples of solutions that dissolve polysiloxanes in alkyl polysiloxanes include: KF7312J (a mixture of trimethylsilyl polysiloxane and decamethylcyclopentasiloxane in a 50:50 mass ratio), KF7312F (a mixture of trimethylsilyl polysiloxane and octamethylcyclotetrasiloxane in a 50:50 mass ratio), KF9021L (a mixture of trimethylsilyl polysiloxane and low-viscosity methyl polysiloxane (volatile methyl polysiloxane) in a 50:50 mass ratio), and KF7312L (a mixture of trimethylsilyl polysiloxane and low-viscosity methyl polysiloxane (viscosity ² mm²)). These solutions are available from Shin-Etsu Chemical Industry Co., Ltd. /s) = 50:50 (mass ratio) mixture, etc. Furthermore, as described below, volatile methyl polysiloxanes are not used as the basis for calculating the mass fraction, mass ratio, etc. of "alkyl polysiloxanes" in this embodiment.

Examples of standalone polysiloxane resins include: MQ-1600 Solid Resin (a trimethylsilyl polysiloxane) and MQ-1640 Flake Resin (a mixture of trimethylsilyl polysiloxane and polypropylsilsesquioxane) commercially available from Dow Toray Industries, Ltd. These commercially available products contain trimethylsilyl polysiloxane and may contain MQ, MDQ, MT, MTQ, MDT, or MDTQ.

From the perspectives of water repellency, water pressure resistance, abrasion resistance, and texture, in the water repellent composition of this embodiment, the amount of polysiloxane resin is ideally 1,000–5,000 parts by weight relative to 100 parts by weight of amino-modified polysiloxane, more ideally 1,200–4,000 parts by weight, and even more ideally 1,500–3,500 parts by weight. If the resin content is below the lower limit, the overall water repellency, liquid repellency, water resistance, abrasion resistance, and resistance to infiltration will decrease. Furthermore, if the resin content exceeds the upper limit, in addition to the aforementioned performance reduction, the texture of the fibers treated with the composition may also be significantly deteriorated. Moreover, from the above perspective, relative to the total amount of 100 parts by mass of amino-modified polysiloxane and alkyl polysiloxane, the amount of polysiloxane resin is ideally 60 to 130 parts by mass, more ideally 65 to 125 parts by mass, and even more ideally 90 to 120 parts by mass.

<Alkyl polysiloxane> The water-repellent composition of this embodiment contains alkyl polysiloxane as a water-repellent component. This alkyl polysiloxane can achieve a kinematic viscosity exceeding ² mm²/s at 25°C, thereby distinguishing it from alkyl polysiloxanes used as solvents (e.g., solvents for polysiloxane resins). That is, in one embodiment, the alkyl polysiloxane of this embodiment has a kinematic viscosity exceeding 2 ^mm² /s at 25°C, and the alkyl polysiloxane contained in the water-repellent composition as a solvent has a kinematic viscosity of less than 2 ^mm² /s at 25°C. Based on the viewpoint of non-volatility, the alkyl polysiloxanes of this embodiment can be distinguished from alkyl polysiloxanes that are volatile (i.e., volatile) from the system. Here, the distinction between non-volatile and volatile alkyl polysiloxanes can be made as follows.

Non-volatile alkyl polysiloxanes are liquid or plastic at room temperature (25°C) (meaning their plasticity can be measured according to the method specified in JIS K 6249, and is expressed as the value (unit: mm) after applying a 1 kgf load to a 4.2 g spherical sample at 25°C for 3 minutes). More specifically, non-volatile alkyl polysiloxanes are defined as those whose mass reduction is less than 1% after 1 g of alkyl polysiloxane is spread on a 48 mm diameter glass petri dish and left at 25°C and normal pressure for 24 hours. Furthermore, alkyl polysiloxanes that are chain-like or cyclic and have a degree of polymerization of 10 or higher are considered non-volatile. On the other hand, alkyl or cyclic alkyl polysiloxanes with a degree of polymerization of less than 10 (especially less than 7) are volatile at room temperature and are therefore ideally intended as part of a solvent, rather than as a water-repellent component of the present embodiment. In one embodiment, volatile polysiloxanes with a degree of polymerization of less than 10 (especially less than 7) specifically include dimethyl polysiloxanes and trimer-heptamer cyclodimethyl polysiloxanes (D3, D4, D5, D6, and D7) with a kinematic viscosity of less than ^{2 mm²} /s at 25°C. These are explicitly excluded from the scope of alkyl polysiloxanes as a water-repellent component of the present embodiment.

Alkyl polysiloxanes as water-repellent components are, in one state, compounds in which the side chains and ends of cyclic organopolysiloxanes are saturated hydrocarbon groups, or compounds in which the side chains of cyclic organopolysiloxanes are saturated hydrocarbon groups. Examples of such alkyl polysiloxanes include compounds represented by the following general formula (1):

[Chemistry 1] [In formula (1), ^R13 , ^R14 , ^R15 , ^R16 , ^R17 , and ^R18 each independently represent a monovalent saturated hydrocarbon having 1 to 18 carbon atoms, and v represents the value indicating that the compound represented by formula (1) is nonvolatile.]; and compounds represented by the following general formula (2):

[Chemistry 2] [In formula (2), ^R19 and ^R20 each independently represent monovalent saturated hydrocarbons with 1 to 18 carbon atoms, and w represents the value of non-volatileness of the compound represented by formula (2).]

In the compounds represented by the above general formula (1) used in this embodiment, ^R13 , ^R14 , ^R15 , ^R16 , ^R17 , and ^R18 are each independently a monovalent saturated hydrocarbon having 1 to 18 carbon atoms. From the viewpoint that polysiloxane resins are readily soluble in compounds represented by general formula (1) and that such compounds are readily available, the number of carbon atoms in these saturated hydrocarbons is ideally 1 to 10. The saturated hydrocarbons can be linear or branched. Ideally, the saturated hydrocarbons are linear, and more ideally, linear alkyl groups. Ideally, the saturated hydrocarbons are methyl or ethyl, and more ideally, methyl. The value of v can be appropriately selected so that the compound represented by general formula (1) is non-volatile and its kinematic viscosity exceeds 2 ^mm² /s, for example, within the range of kinematic viscosity described later. From the viewpoint of making the alkyl polysiloxane non-volatile, v is ideally 3 or more or 5 or more. Furthermore, the use of compounds as solvents for polysiloxanes is not excluded: the value of v in formula (1) is not a value representing the non-volatile nature of the compound represented by formula (1) but a value representing the volatile nature of the compound (therefore, a compound with a low degree of polymerization). However, such volatile alkyl polysiloxane is not the same as the "alkyl polysiloxane" used in this embodiment, i.e., the mass part, mass ratio, etc. of the alkyl polysiloxane used as a water-repellent component. The stability of a system can sometimes be improved by using volatile polysiloxanes.

Compounds represented by the above general formula (1) can be listed as, for example, non-volatile dimethyl polysiloxane, diethyl polysiloxane, etc.

In the compounds represented by the above general formula (2) used in this embodiment, ^R19 and ^R20 are each independently monovalent saturated hydrocarbons having 1 to 18 carbon atoms. Ideally, the carbon number of these saturated hydrocarbons is 1 to 10. When the carbon number of the saturated hydrocarbons is within the above range, there is a tendency for polysiloxane resins to be readily soluble in the compounds represented by general formula (2) and to readily obtain the compounds. The saturated hydrocarbons can be linear or branched. Ideally, the saturated hydrocarbons are linear, and more preferably linear alkyl groups. Ideally, the saturated hydrocarbons are methyl or ethyl, and more preferably methyl. w is a value indicating that the compounds represented by general formula (2) are nonvolatile. Ideally, w is in the range of 10 to 1000 or 20 to 1000. Furthermore, the use of the following alkyl polysiloxanes as solvents for polysiloxanes is not excluded: alkyl polysiloxanes whose w is not a non-volatile value but a volatile value (i.e., low degree of polymerization), such as low-polymerization and volatile alkyl polysiloxanes with w in the range of 2 to 10 (especially 4 or 5). Such cyclic and volatile alkyl polysiloxanes tend to readily dissolve polysiloxanes and are readily available, and are suitable for use in this embodiment.

w is a volatile value of the compound represented by general formula (2) and can ideally serve as a solvent for polysiloxanes. Examples of such compounds include decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane. However, as mentioned above, these are not used as specifications for the "alkyl polysiloxane" in this embodiment in terms of mass ratio, etc.

Alkyl polysiloxanes can be used alone or in combination of two or more.

Ideally, the alkyl polysiloxane of this embodiment is liquid at 25°C. The kinematic viscosity of the alkyl polysiloxane at 25°C is ideally greater than 2 ^mm² /s and less than 100,000 ^mm² /s, more ideally greater than 5 ^mm² /s and less than 10,000 ^mm² /s, even more ideally greater than 10 ^mm² /s and less than 1,000 ^mm² /s, even more ideally greater than 10 ^mm² /s and less than 500 ^mm² /s, and particularly ideally greater than 10 ^mm² /s and less than 100 ^mm² /s. When the kinematic viscosity at 25°C is within the above range, the polysiloxane tends to dissolve easily, ensuring workability. In this invention, the kinematic viscosity at 25°C refers to the value measured using the method described in JIS K 2283:2000 (Uberlot viscometer). As mentioned above, alkyl polysiloxanes with a kinematic viscosity of 2 ^mm² /s or less are not specified as the alkyl polysiloxanes of this embodiment for use in mass ratios, etc., but their use as solvents for polysiloxanes in the system is not excluded. As mentioned above, by using volatile cyclic or chain alkyl polysiloxanes, the processability of polysiloxanes and the stability of the system can sometimes be improved.

In the water-repellent composition of this embodiment, the amount of alkyl polysiloxane is 500 to 15,000 parts by mass relative to 100 parts by mass of amino-modified polysiloxane. From the viewpoints of water repellency, texture, and seam slippage, the ideal amount of alkyl polysiloxane is 900 to 6,000 parts by mass relative to 100 parts by mass of amino-modified polysiloxane. Furthermore, as mentioned above, in addition to the aforementioned amount (parts by mass) of alkyl polysiloxane, volatile alkyl polysiloxanes may also be added as solvents, etc.

From the perspectives of texture, water repellency, water pressure resistance, and abrasion resistance, the mass ratio of polysiloxane to alkyl polysiloxane in the water repellent composition of this embodiment [(II):(III)] is ideally 30:70 to 80:20, and more ideally 40:60 to 60:40. Furthermore, as mentioned above, in addition to the above-mentioned mass ratio of alkyl polysiloxane, volatile alkyl polysiloxanes may also be added as solvents, etc.

<Other Ingredients> In addition to the ingredients described above, the water-repellent composition of this embodiment may further contain solvents (alkyl polysiloxanes and other solvents other than those mentioned in the above item <alkyl polysiloxanes>), crosslinking agents (such as polyfunctional isocyanate compounds and other compounds), surfactants, defoamers, organic acids, inorganic acids, alcohols, antibacterial agents, antifungal agents, pH adjusters, colorants, silica, antioxidants, deodorizers, various catalysts, emulsion stabilizers, chelating agents, antistatic agents, and organic modified polysiloxanes other than amine-modified polysiloxanes.

(Crossing Agent) There are no particular limitations on the polyfunctional isocyanate compounds that can be used as crosslinking agents, as long as they have two or more isocyanate groups within their molecules. Commonly known polyisocyanate compounds can be used. Examples of polyfunctional isocyanate compounds include: alkyl diisocyanates, aryl diisocyanates, and cycloalkyl diisocyanates; and modified polyisocyanate compounds such as dimers, trimers, or tetramers of these diisocyanates. The ideal number of carbon atoms in alkyl diisocyanates is 1 to 12.

Examples of diisocyanate compounds include: 2,4- or 2,6-toluene diisocyanate, ethyl diisocyanate, propyl diisocyanate, 4,4-diphenylmethane diisocyanate, terephthalic diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethyl diisocyanate. Hexamethylene-1,6-diisocyanate, phenyl diisocyanate, toluene or naphthalene diisocyanate, 4,4'-methylene-bis(phenyl isocyanate), 2,4'-methylene-bis(phenyl isocyanate), 3,4'-methylene-bis(phenyl isocyanate), 4,4'-epenylethyl-bis(phenyl isocyanate), ω,ω'-diisocyano-1,3-xylene ω,ω’-diisocyanate-1,4-dimethylcyclohexane, ω,ω’-diisocyanate-1,4-xylene, ω,ω’-diisocyanate-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanate-cyclohexane, 4,4’-methylene-bis(cyclohexyl isocyanate), 3-isocyanate-methyl-3,5,5-trimethylcyclohexane α-Diisocyanates, acid-diisocyanate dimers, ω,ω’-diisocyanate diethylbenzene, ω,ω’-diisocyanate dimethyltoluene, ω,ω’-diisocyanate diethyltoluene, bis(2-isocyanate ethyl) fumarate, 1,4-bis(2-isocyanate-propyl-2-yl)benzene, and 1,3-bis(2-isocyanate-propyl-2-yl)benzene.

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

Modified polyisocyanate compounds derived from diisocyanate compounds are not particularly limited as long as they have two or more isocyanate groups. Examples include polyisocyanates with biuret, isocyanurate, carbamate, urea diketone, urethane, and trimer structures; adducts of trihydroxymethylpropane aliphatic isocyanates, etc. Furthermore, polymeric MDI (MDI = diphenylmethane diisocyanate) can also be used as a polyisocyanate compound. Polyisocyanate compounds can be used alone or in combination of two or more.

The isocyanate groups in polyfunctional isocyanate compounds can be untreated or capped with end-capping agents. End-capping agents include: pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole, and others; phenols such as phenol, methylphenol, chlorophenol, isobutylphenol, tributylphenol, isopentylphenol, octylphenol, and nonylphenol; and ε-caprolactam, δ-valerolactam, etc. Lactamines such as γ-butyrolactam; active methylene compounds such as dimethyl malonate, diethyl malonate, acetoacetone, methyl acetoacetate, and ethyl acetoacetate; oximes such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and diphenyl ketone oxime; imidazole compounds such as imidazole and 2-methylimidazolium; and sodium hydrogen sulfite. Among these, pyrazoles and oximes are ideal from the viewpoint of durable water-repellent properties.

Water-dispersible isocyanates can also be used for polyfunctional isocyanate compounds. These are polyisocyanates that introduce hydrophilic groups into the polyisocyanate structure to provide interfacial activity, thereby endowing the polyisocyanates with water dispersibility. In addition, conventional catalysts such as organotin and organozinc can be used to promote the reaction between the amine and isocyanate groups.

From the perspectives of water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, and texture, in the water repellent composition of this embodiment, the amount of polyfunctional isocyanate compound is ideally 10 to 600 parts by mass relative to the total amount of amino-modified polysiloxane and polysiloxane resin combined to 100 parts by mass, and more ideally 30 to 300 parts by mass.

Crosslinking agents other than the aforementioned polyfunctional isocyanate compounds include, for example, melamine resin and glyoxal resin.

Melamine resins can use compounds with a melamine backbone, such as trihydroxymethyl melamine, hexahydroxymethyl melamine, and other polyhydroxymethyl melamines; alkoxymethyl melamine where part or all of the hydroxymethyl group of polyhydroxymethyl melamine is replaced by an alkyl group having 1 to 6 carbon atoms; and alkoxymethyl melamine where part or all of the hydroxymethyl group of polyhydroxymethyl melamine is replaced by an alkoxymethyl group having 2 to 6 carbon atoms. These melamine resins can be monomers or polymers of two or more dimers, or mixtures thereof. Furthermore, substances co-condensed with a portion of melamine and urea, etc., can also be used. Examples of such melamine resins include: BECKAMINE APM, BECKAMINE M-3, BECKAMINE M-3(60), BECKAMINE MA-S, BECKAMINE J-101, and BECKAMINE J-101LF manufactured by DIC Corporation; UNIKA RESIN 380K manufactured by Union Chemical Industries, Ltd.; and RIKEN RESIN MM series manufactured by Riken Kogyo Co., Ltd.

Glyoxal resins can use conventional formulations. Examples of glyoxal resins include 1,3-dimethylglyoxal urea resins, dihydroxymethyldihydroxyvinylurea resins, and dihydroxymethyldihydroxyacrylurea resins. The functional groups of these resins can also be substituted with other functional groups. Examples of glyoxal resins include: BECKAMINE N-80, BECKAMINE NS-11, BECKAMINE LF-K, BECKAMINE NS-19, BECKAMINE LF-55P Conc., BECKAMINE NS-210L, BECKAMINE NS-200, and BECKAMINE NF-3 manufactured by DIC Corporation; UNI RESIN GS-20E manufactured by Union Chemical Industries, Ltd.; and RIKEN RESIN RG series and RIKEN RESIN MS series manufactured by Riken Kogyo Co., Ltd.

From the perspective of promoting the reaction, it is ideal to use catalysts in melamine resins and glyoxal resins. There are no particular restrictions on such catalysts, as long as they are commonly used. Examples include: boron fluoride compounds such as ammonium borofluoride and zinc borofluoride; neutral metal salt catalysts such as magnesium chloride and magnesium sulfate; and inorganic acids such as phosphoric acid, hydrochloric acid, and boric acid. These catalysts can also be used in conjunction as co-catalysts, such as citric acid, tartaric acid, malic acid, maleic acid, and lactic acid. Examples of such catalysts include: CATALYST ACX, CATALYST 376, CATALYST O, CATALYST M, CATALYST G(GT), CATALYST X-110, CATALYST GT-3, and CATALYST NFC-1 manufactured by DIC Corporation; UNIKA CATALYST 3-P and UNIKA CATALYST MC-109 manufactured by Union Chemical Industries, Ltd.; and RIKEN FIXER RC series, RIKEN FIXER MX series, and RIKEN FIXER RZ-5 manufactured by Riken Kogyo Co., Ltd.

(Surfactants) Surfactants may include, for example, polyepoxide adducts, or may be further combined with other surfactants. Other surfactants may include those that maintain a stable temperature range when expanding into an emulsion and adjust the amount of foam produced when preparing a diluted solution with water. Other surfactants may consist of any of the following: nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Other surfactants may be used alone or in combination of two or more.

(Defoamers) There are no specific limitations on defoamers. Examples include: oil-based defoamers such as castor oil, sesame oil, flaxseed oil, and animal and vegetable oils; fatty acid-based defoamers such as stearic acid, oleic acid, and palmitic acid; fatty acid ester-based defoamers such as isoamyl stearate, distearate succinate, ethylene glycol distearate, and butyl stearate; and defoamers such as polyoxyethylene monohydric alcohol, di- and tri-pentylphenoxyethanol, and 3... Defoamers include: alcohol-based defoamers such as heptanol and 2-ethylhexanol; ether-based defoamers such as 3-heptylcellulose, nonylcellulose, and 3-heptylcarbitol; phosphate-based defoamers such as tributyl phosphate and tributyl(butoxyethyl) phosphate; amine-based defoamers such as dipentylamine; amide-based defoamers such as polyalkylene amide and amide polyamine; sulfate-based defoamers such as sodium lauryl sulfate; and mineral oils. Defoamers can be used alone or in combination of two or more.

(Organic acids) There are no particular limitations on organic acids, and examples include: lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, methanesulfonic acid, toluenesulfonic acid, etc. Organic acids can be used alone or in combination of two or more.

(Inorganic acids) There are no particular limitations on inorganic acids; examples include hydrogen chloride, sulfuric acid, and nitric acid. Inorganic acids can be used alone or in combination of two or more.

(Alcohols) There are no particular limitations on alcohols, and examples include: ethanol, isopropanol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, dipropylene glycol, propylene glycol, etc. Alcohols can be used alone or in combination of two or more.

(Antistatic Agents) Antistatic agents that do not easily hinder water repellency are preferred. Examples of antistatic agents include cationic surfactants such as higher alcohol sulfates, sulfated oils, sulfonates, ammonium quaternary salts, and imidazoline-type quaternary salts; nonionic surfactants such as polyethylene glycol-type and polyol ester-type surfactants; and amphoteric surfactants such as imidazoline-type quaternary salts, alanine-type, and betaine-type surfactants. High molecular weight compounds include the aforementioned antistatic polymers and polyalkylamines. Antistatic agents can be used alone or in combination of two or more.

The water-repellent composition of the present embodiment is suitable for use as a fiber processing agent, paper processing agent, leather processing agent, etc.

[Method for manufacturing water-repellent composition] The following will describe the method for manufacturing the water-repellent composition of this embodiment.

The water-repellent composition of this embodiment can be obtained by mixing the above-mentioned amine-modified polysiloxane, polysiloxane resin, and alkyl polysiloxane. The content of each of the above-mentioned components in the water-repellent composition of this embodiment can be set to the above-mentioned ideal proportions.

The water-repellent composition of this embodiment can be a single-agent form, which is a mixture of amino-modified polysiloxane (component (I)), polysiloxane resin (component (II)), and alkyl polysiloxane (component (III)) in advance; it can also be a two-agent form, which is a mixture of two of the above three components and a single-agent form of the other component; or it can be a three-agent form, in which the above three components are each separated. From the viewpoint of ease of handling, the water-repellent composition of this embodiment is physically based on the dispersion (including emulsification and dissolution) of the above three components in an aqueous medium.

When the formulation is a pre-mixed mixture of components (I), (II), and (III), the water-repellent composition of this embodiment can be obtained by: simultaneously dispersing (including emulsifying and dissolving) components (I), (II), and (III) in an aqueous medium; or mixing a dispersion obtained by dispersing at least one of the three components in an aqueous medium with a dispersion obtained by dispersing the other components in an aqueous medium; or mixing the dispersions of components (I), (II), and (III) respectively.

Methods for dispersing the above components in an aqueous medium include, for example, mixing and stirring the components, the aqueous medium, and, if necessary, a dispersant. In the case of mixing and stirring, conventional emulsifying and dispersing machines such as emulsifiers (milders), high-speed mixers, homogenizers, ultrasonic homogenizers, homogenizing mixers, bead mills, pearl mills, DYNO-MILLs, Aspec mills, basket mills, ball mills, nanomizers, altimizers, and star bursters can be used. One of these emulsifying and dispersing machines can be used alone or in combination of two or more.

The ideal aqueous medium is water, or a mixture of water and a water-miscible hydrophilic solvent. Examples of hydrophilic solvents include: methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, hexanediol, glycerol, butylethylene glycol, butyl diethylene glycol, Solfit, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, etc.

From the perspective of dispersion stability, the above-mentioned dispersion ideally contains a surfactant. There are no particular limitations on the type of surfactant, as long as it improves the emulsification and dispersion stability; examples include conventional nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. One type can be used alone, or two or more can be used in combination.

The above-mentioned dispersion can be used directly as a treatment solution in water treatment, or it can be further diluted with an aqueous medium or a hydrophobic organic solvent to prepare a treatment solution. The dispersion can be used directly in its unneutralized (without neutralization) form, or its pH can be adjusted by methods such as neutralizing amine-modified polysiloxane. When pH adjustment is required, the pH of the treatment solution can be adjusted to 5.5–6.5.

[Water-repellent fiber product] This embodiment also provides a water-repellent fiber product having fibers and a water-repellent agent composition of this embodiment attached to the fibers. The manufacturing method of the water-repellent fiber product of this embodiment will be described below.

Water-repellent fiber products can be manufactured by a method comprising the step of treating fibers with a treatment solution containing a water-repellent agent composition of the present invention as described above.

There are no particular restrictions on the materials used for fibers, 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, and polypropylene; and composite and blended fibers of these. Fibers can take any form, such as yarn, cloth, non-woven fabric, or paper. Fibers can also be used to make fiber products.

Methods for treating fibers with a treatment solution containing a water-repellent composition of this embodiment include, for example: a single-step treatment method using a treatment solution containing component (I), component (II), and component (III); a two-step treatment method using a treatment solution containing two of the above three components and a treatment solution containing the third component; and a three-step treatment method using three dispersions, each containing the above three components. When performing a two-step or three-step treatment, the order in which the components are treated can be arbitrary.

The above-mentioned treatment solutions and dispersions can be used directly in their unneutralized (without neutralization) form, or the pH can be adjusted to 5.5–6.5. For example, the following organic acids can be used for pH adjustment: lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, methanesulfonic acid, toluenesulfonic acid, etc.; inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid, etc.; hydroxides such as sodium hydroxide, potassium hydroxide, etc.; carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate, sodium dihydrogen phosphate, etc.; organic amines such as monoethanolamine, diethanolamine, triethanolamine, triethylamine, etc.; and ammonia, etc.

Methods for treating fibers with the aforementioned treatment solutions include, for example, padding, impregnation, spraying, and coating. Furthermore, when the water-repellent component contains water, it is ideal to dry it after it adheres to the fiber to remove the water.

The amount of water-repellent composition attached to the fiber in this embodiment can be adjusted according to the desired degree of water repellency. Ideally, the amount of water-repellent composition should be adjusted to 0.1–5g per 100g of fiber, and more ideally, to 0.1–3g. If the amount of water-repellent composition attached is 0.1g or more, the fiber tends to exhibit full water repellency more easily; if it is less than 5g, the fiber texture tends to be better and more economical.

Furthermore, it is ideal to perform heat treatment after the water-repellent composition of this embodiment is attached to the fiber. There are no particular restrictions on temperature conditions, but from the viewpoint of water repellency, durable water repellency, and texture, it is ideal to perform the heat treatment at 110 to 180°C for 1 to 5 minutes.

The water-repellent fiber products of this embodiment exhibit excellent water repellency and a soft texture, making them suitable for use in clothing and non-clothing applications such as down covers, coats, jackets, windbreakers, blouses, dress shirts, skirts, trousers, gloves, hats, duvet covers, duvet drying covers, curtains, and tents. [Example]

The invention will be further illustrated by the following embodiments, but the invention is not limited by such embodiments.

<Preparation of Amine-Modified Polysiloxane Dispersion> (Preparation Example A1) 30 parts by weight of KF8005 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name), 0.3 parts by weight of antonic acid, and 1 part by weight of ethylene oxide 5-molar adduct of a branched alcohol with 12-14 carbon atoms were mixed. Then, 68.7 parts by weight of water were added to the obtained mixture little by little while mixing, to obtain a dispersion containing 30% by weight of amine-modified polysiloxane.

(Preparation Examples A2-A7) Except for changing the amine-modified polysiloxane from KF8005 to the amine-modified polysiloxane listed in Table 1, the dispersion containing 30% by mass of amine-modified polysiloxane was obtained in the same manner as in Preparation Example A1. Furthermore, KF-868, KF-864, and KF-393 are trade names manufactured by Shin-Etsu Chemical Industry Co., Ltd., SF-8417 and BY16-853U are trade names manufactured by Dow Toray Industries, Ltd., and XF42-B1989 is a trade name manufactured by Mitu Advanced Materials Co., Ltd.

<Physical Properties of Amine-Modified Polysiloxane> The functional group equivalents (unit: g/mol) and kinematic viscosity (unit: ^mm² /s) of the amine-modified polysiloxanes used above are shown in Table 1. Furthermore, the kinematic viscosity at 25°C was measured using the method described in JIS K 2283:2000 (Uberlot viscometer).

[Table 1] Functional group equivalent (g/mol) Kinematic viscosity at 25°C ( ^mm² /s) Preparation Example A1 Preparation Example A2 Preparation Example A3 Preparation Example A4 Preparation Example A5 Preparation Example A6 Preparation Example A7 Preparation Example A8 KF-8005 11000 1200 30 KF-868 8800 90 30 KF-864 3800 1700 30 SF-8417 1800 1200 30 30 XF42-B1989 1500 900 30 KF-393 350 70 30 BY-16-853U 460 13 30 Formic acid 0.3 0.3 0.3 0.3 0.3 0.3 0.3 C12-14 alcohol 5EO adduct 1 1 1 1 1 1 1 1 water 68.7 68.7 68.7 68.7 68.7 68.7 68.7 69.0

(Preparation Example A8) 30 parts by weight of SF-8417 (manufactured by Dow Toray Industries, Inc., trade name) as the amino-modified polysiloxane and 1 part by weight of ethylene oxide 5 molar adduct of branched alcohols with 12 to 14 carbon atoms were mixed. Then, 69.0 parts by weight of water were added to the obtained mixture little by little while mixing, to obtain a dispersion containing 30% by weight of amino-modified polysiloxane.

<Preparation of Alkyl Polysiloxane Dispersion> (Preparation Example B) One part by mass of a 5-molar adduct of a branched-chain alcohol with 12-14 carbon atoms was mixed with 30 parts by mass of dimethyl polysiloxane (kinematic viscosity of 100 ^mm² /s at 25°C, manufactured by Dow Toray Industries, Inc.) as the alkyl polysiloxane. Then, 69 parts by mass of water were added little by little while mixing to obtain a dispersion containing 30% by mass of alkyl polysiloxane.

<Preparation of Polysiloxane Resin Dispersion> (Preparation Example C1) Mix 25 parts by weight of volatile dimethyl polysiloxane (kinematic viscosity at 25°C of 1 ^mm² /s, manufactured by Dow Toray Industries, Inc.) as a solvent into 25 parts by weight of MQ-1600 (a trimethylsilyl polysiloxane, manufactured by Dow Toray Industries, Inc.) as a solvent until the polysiloxane resin dissolves. Then, further mix 5 parts by weight of 5 molar adduct of a branched-chain alcohol with 10 carbon atoms and 1 part by weight of ARQUAD T-28 (stearyltrimethylammonium chloride). Next, while mixing in small amounts, add 44 parts by weight of water to obtain a dispersion containing 25% by weight of polysiloxane resin.

(Preparation Examples C2, C5 to C9) Except for changing the polysiloxane resin from MQ-1600 to the polysiloxane resin listed in Table 2, the dispersion containing 25% by mass of polysiloxane resin was obtained in the same manner as in Preparation Example C1.

(Preparation Examples C3 and C4) Except for changing the polysiloxane resin from MQ-1600 to the mixture of polysiloxane resin and alkyl polysiloxane (as solvent) listed in Table 2, the dispersion containing 25% by mass of polysiloxane resin was obtained in the same manner as in Preparation Example C1. Furthermore, the values of "non-volatile components" in Table 2 are those recorded in the product catalog for MQ-1600, KF-9021L, and KF7312L, while the others are expressed as 100% based on the product catalog's description of the powder form.

The above examples of polysiloxane resin preparation are summarized in Table 2.

<Preparation of Dispersions of Polyfunctional Isocyanates> (Preparation Example D1: Dispersion of Methyl Ethyl Ketone Oxime-Capped Compound of the Reaction Product of Trihydroxymethylpropane and Toluene Diisocyanate) First, prepare Pollene AD (75% by mass of the reaction product of trihydroxymethylpropane and toluene diisocyanate (mass ratio of 2,4 isomer to 2,6 isomer is 80:20), solvent: ethyl acetate; manufactured by SAPICI, trade name) as the reaction product of trihydroxymethylpropane and toluene diisocyanate.

The reaction product of trihydroxymethylpropane and toluene diisocyanate prepared above, 1 mole (308.4 g), was heated to 60-70°C. Then, 3 moles (261.4 g) of methyl ethyl ketone oxime were slowly added, and the reaction was allowed to proceed until the isocyanate content, as confirmed by infrared spectrophotometry, was zero at 60-70°C. 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 compound.

180 parts by weight of the above-obtained composition and 20 parts by weight of ethylene oxide 30 molar adduct of triphenylphenylphenol 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 of methyl ethyl ketone oxime-terminated product containing 40% by weight of the reaction product of trimethylolpropane and toluene diisocyanate.

(Preparation Example D2: Dispersion of methyl ethyl ketone oxime-terminated compound of hexamethylene diisocyanate isocyanurate type) Add 1 mol (504.6 g) of DURANATE THA-100 (isocyanurate type of hexamethylene diisocyanate, NCO functional group: 3, content 100% by mass, manufactured by Asahi Kasei Chemicals, trade name) and methyl isobutyl ketone to a reaction vessel and heat to 60–70°C. Then, slowly add 3 mol (261.4 g) of methyl ethyl ketone oxime, reacting until the isocyanate content, confirmed by infrared spectrophotometer at 60–70°C, is zero, thereby obtaining a colorless, transparent, viscous liquid composition containing 98.7% by mass of methyl ethyl ketone oxime-terminated polyisocyanate compound.

180 parts by weight of the above-obtained composition, 20 parts by weight of methyl ethyl ketone as an organic solvent, and 20 parts by weight of ethylene oxide 30 molar 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 of isocyanurate-type methyl ethyl ketone oxime-terminated compound containing 40% by weight of hexamethylene diisocyanate.

<Preparation of Water-Repellent Fiber Products> (Example 1) The following components were diluted with water to obtain a treatment bath containing 0.13% by mass of the amino-modified polysiloxane dispersion obtained in Preparation Example A1, 3.16% by mass of the alkyl polysiloxane dispersion obtained in Preparation Example B, 4.05% by mass of the polysiloxane resin dispersion obtained in Preparation Example C1, 0.50% by mass of NICEPOLE FE-26 (antistatic agent, manufactured by Nichih Chemical Co., Ltd., trade name) and 0.50% by mass of TEXPORT BG-290 (penetrating agent, manufactured by Nichih Chemical Co., Ltd., trade name). Using this treatment bath, 100% polyester fabric that has already been dyed is subjected to a pressing dyeing treatment at 15–40°C (pick-up rate of 60% by mass), followed by heat treatment at 180°C for 1 minute to obtain water-repellent fiber products. Furthermore, the table shows the mass ratio of the amount of polysiloxane resin to the amount of amino-modified polysiloxane, and the mass ratio of the amount of polysiloxane resin to the total amount of amino-modified polysiloxane and alkyl polysiloxane.

(Examples 2-35, Comparative Examples 1-7) Except that the amino-modified polysiloxane dispersion shown in Table 1 was used instead of the amino-modified polysiloxane dispersion obtained in Preparation Example A1, and the proportions (mass%) of the alkyl polysiloxane dispersion shown in Preparation Example B and the polysiloxane resin dispersions shown in Preparation Examples C1-C9 in Table 2 were changed as shown in Tables 3-7, water-repellent fiber products were obtained in the same manner as in Example 1. For the water-repellent fiber products obtained above, the following methods were used to determine their water repellency, liquid repellency, water pressure resistance, abrasion resistance, durable water repellency (i.e., water repellency after washing), durable liquid repellency (i.e., liquid repellency after washing), durable water pressure resistance (i.e., water pressure resistance after washing), durable abrasion resistance (i.e., abrasion resistance after washing), texture, carry-in resistance, and seam slippage. The results are shown in Tables 3-7.

(Evaluation of Water Repellency of Fiber Products) The test was conducted according to the spraying method of JIS L 1092 (2009), with the spray water temperature set at 20°C. Results were evaluated visually according to the following grades. Slightly better properties were marked with a "+", and properties between grades 4 and 5 were rated "4-5". Water Repellency: State 5: No surface wetness 4: Slightly wet surface 3: Partially wet surface 2: Wet surface 1: Overall wet surface 0: Completely wet on both sides

(Evaluation of the water-repellency of fiber products) For the above-mentioned water-repellency fiber products, the water repellency after air drying was evaluated by washing 20 times (L-20) according to the C4M method 1930 of JIS L 1930 (2014) and the water repellency was evaluated in the same way as the above-mentioned water repellency evaluation method.

(Evaluation of liquid repellency and durable liquid repellency of fiber products) The test was conducted according to the spraying method of JIS L 1092 (2009), with the spray water temperature set at 20°C. Results were evaluated visually according to the following grades. Slightly better properties were marked with a "+", and properties falling between grade 4 and grade 5 were rated "4-5". Liquid repellency: State 5: Liquid repellency angle to water droplets on fabric is 45° or higher 4: Liquid repellency angle to water droplets on fabric is less than 45° 3: Water droplets are not repelled, but flow in a straight line 2: Water droplets flow in a serpentine manner 1: The surface is generally wet 0: Both sides are completely wet In addition, the durable liquid repellency is evaluated by washing 20 times (L-20) according to the C4M method of JIS L 1930 (2014) and then air-drying.

(Water Pressure Resistance and Durability Evaluation of Fiber Products) The water pressure resistance of fiber products was determined by applying pressure to a 210mm × 210mm test piece cut from the fiber product using a WP-100K high-pressure water pressure testing machine (manufactured by Taeyong Scientific Instruments) at an acceleration of 60cmAq/min, and measuring the water pressure when 3 drops of water leaked from the test piece. In addition, the durability water pressure resistance was determined by washing the sample 20 times (L-20) according to the C4M method of JIS L 1930 (2014), followed by air drying, and then measuring the water pressure resistance after drying.

(Evaluation of Abrasion Resistance and Durability of Fiber Products) The water repellency of Martindale after abrasion (condition load: 9 kPa, number of cycles: 1000) was evaluated according to the aforementioned (Evaluation of Water Repellency of Fiber Products). In addition, the durability and abrasion resistance were evaluated after washing 20 times (L-20) and air drying according to the C4M method of JIS L 1930 (2014), and then the water repellency of Martindale after abrasion (condition load: 9 kPa, number of cycles: 1000) was evaluated according to the aforementioned (Evaluation of Water Repellency of Fiber Products). The Martindale abrasion test is evaluated according to ISO 12947.2-1998: Testing the abrasion resistance and balling resistance of fabrics by the Martindale method – Part 2: Determination of sample breakage.

(Evaluation of the resistance to introduction of fiber products) Treatment baths were prepared with dissolved DISPATEX K (anionic polymer, water, manufactured by Nichih Chemical Co., Ltd.) 200 ppm, NICCA SUNSOLT 1200K (anionic polymer, nonionic surfactant, water, manufactured by Nichih Chemical Co., Ltd.) 200 ppm, and sodium sulfate 200 ppm as described in the examples and comparative examples. Using this treatment bath, fiber products were pressure-dyed at 15–40°C, followed by heat treatment at 180°C for 1 minute to obtain water-repellent fiber products. The water repellency of the obtained water-repellent fiber products was evaluated according to the aforementioned (Evaluation of the water repellency of fiber products).

(Evaluation of the Texture of Fiber Products) The water-repellent fiber products mentioned above are evaluated based on their feel using a 5-point scale as shown below. 1: Hard ~ 5: Soft

(Seam slip resistance of fiber products) The suture slip resistance of the above-mentioned water-repellent fiber products was determined according to JIS L 1096:2010, section 8.23, 8.23.1, method b) B. A smaller value indicates better suture slip resistance; values below 4 mm are considered good.

[Table 2] Manufacturing Company content Non-volatile components Preparation Example C1 Preparation Example C2 Preparation Example C3 Preparation Example C4 Preparation Example C5 Preparation Example C6 Preparation Example C7 Preparation Example C8 Preparation Example C9 DOWSIL MQ-1600 Dow Chemicals Toray Polysiloxane resin 100% 25 DOWSIL MQ-1640 Dow Chemicals Toray Polysiloxane resin 100% 25 KF-9021L Shin-Etsu Chemical Industry Polysiloxane resin + low viscosity dimethyl polysiloxane 50% 50 KF-7312L Shin-Etsu Chemical Industry Dimethyl polysiloxane resin with a kinematic viscosity of 2 ^mm² /s at +25°C 50% 50 KMP-706 Shin-Etsu Chemical Industry Polysiloxane resin 100% 25 X-52-854 Shin-Etsu Chemical Industry Polysiloxane resin 100% 25 X-52-1621 Shin-Etsu Chemical Industry Polysiloxane resin 100% 25 KMP-605 Shin-Etsu Chemical Industry Polysilicon oxide composite powder 100% 25 KMP-402 Shin-Etsu Chemical Industry Polysiloxane rubber powder 100% 25 Dimethyl polysiloxane (1 ^mm² /s) 25 25 25 25 25 25 25 C10 alcohol 7EO adduct 5 5 5 5 5 5 5 5 5 ARQUAD T-28 1 1 1 1 1 1 1 1 1 water 44 44 44 44 44 44 44 44 44

[Table 3] Implementation Example 1 Implementation Example 2 Implementation Example 3 Implementation Example 4 Implementation Example 5 Implementation Example 6 Implementation Example 7 Implementation Example 8 Mixed (by weight) Amine-modified polysiloxane 30% by weight dispersion Preparation Example A1 0.13 Preparation Example A2 0.13 Preparation Example A3 0.13 Preparation Example A4 0.13 Preparation Example A5 0.13 Preparation Example A6 0.13 Preparation Example A7 0.13 Preparation Example A8 0.13 Alkyl polysiloxane 30% by weight dispersion Preparation Example B 3.16 3.16 3.16 3.16 3.16 3.16 3.16 3.16 Polysiloxane resin 25% by weight dispersion Preparation Example C1 4.05 4.05 4.05 4.05 4.05 4.05 4.05 4.05 Antistatic agent NICEPOLE FE-26 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Expansion agent TEXPORT BG-290 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 water 91.66 91.66 91.66 91.66 91.66 91.66 91.66 91.66 SiR/AmSi 2596/100 2596/100 2596/100 2596/100 2596/100 2596/100 2596/100 2596/100 SiR/AmSi+DmSi 103/100 103/100 103/100 103/100 103/100 103/100 103/100 103/100 Evaluation Initial water repellency L-0 5 5 5 5 5 5 5 5 Durable water repellency L-20 4 4 4 4 4 4 4 4 initial repellency L-0 5 5 5 5 5 5 5 5 Durable liquid repellency L-20 4 4 4 4 4 4 4 4 Introducing resistance/DISPATEX K L-0 5 5 5 5 5 5 5 5 Introducing resistance/NICCA SUNSOLT 1200K L-0 5 5 5 5 5 5 5 5 Introducing resistance/Glazide L-0 5 5 5 5 5 5 5 5 Initial water pressure resistance L-0 520 490 500 510 490 500 490 520 Durable and water-pressure resistant L-20 500 500 500 500 490 500 500 500 Initial wear resistance L-0 5 5 5 5 5 5 5 5 Durability and wear resistance L-20 4- 4- 4- 4- 4- 4- 4- 4- texture 4 4 4 4 4 4 4 4 Seam slippage 1.7 1.8 1.8 1.7 1.8 1.8 1.8 1.7

[Table 4] Implementation Example 9 Implementation Example 10 Implementation Example 11 Implementation Example 12 Implementation Example 13 Implementation Example 14 Implementation Example 15 Implementation Example 16 Mixed (by weight) Amine-modified polysiloxane 30% by weight dispersion Preparation Example A1 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 Alkyl polysiloxane 30% by weight dispersion Preparation Example B 3.16 3.16 3.16 3.16 3.16 3.16 3.16 3.16 Polysiloxane resin 25% by weight dispersion Preparation Example C1 Preparation Example C2 4.05 Preparation Example C3 4.05 Preparation Example C4 4.05 Preparation Example C5 4.05 Preparation Example C6 4.05 Preparation Example C7 4.05 Preparation Example C8 4.05 Preparation Example C9 4.05 Antistatic agent NICEPOLE FE-26 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Expansion agent TEXPORT BG-290 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 water 91.66 91.66 91.66 91.66 91.66 91.66 91.66 91.66 SiR/AmSi 2596/100 2596/100 2596/100 2596/100 2596/100 2596/100 2596/100 2596/100 SiR/AmSi+DmSi 103/100 103/100 103/100 103/100 103/100 103/100 103/100 103/100 Evaluation Initial water repellency L-0 5 5 5 5 5 5 5 5 Durable water repellency L-20 4 4 4 4 4 4 4 4 initial repellency L-0 5 5 5 5 5 5 5 5 Durable liquid repellency L-20 4 4 4 4 4 4 4 4 Introducing resistance/DISPATEX K L-0 5 5 5 5 5 5 5 5 Introducing resistance/NICCA SUNSOLT 1200K L-0 5 5 5 5 5 5 5 5 Introducing resistance/Glazide L-0 5 5 5 5 5 5 5 5 Initial water pressure resistance L-0 490 500 510 490 500 490 520 490 Durable and water-pressure resistant L-20 500 500 500 490 500 500 500 500 Initial wear resistance L-0 5 5 5 5 5 5 5 5 Durability and wear resistance L-20 4- 4- 4- 4- 4- 4- 4- 4- texture 4 4 4 4 4 4 4 4 Seam slippage 1.8 1.8 1.7 1.8 1.8 1.8 1.7 1.8

[Table 5] Implementation Example 17 Implementation Example 18 Implementation Example 19 Implementation Example 20 Implementation Example 21 Implementation Example 22 Implementation Example 23 Implementation Example 24 Implementation Example 25 Implementation Example 26 Mixing (parts by weight) Amine-modified polysiloxane 30% by weight dispersion Preparation Example A1 0.22 0.13 0.17 0.13 0.13 0.08 0.15 0.13 0.13 0.13 Alkyl polysiloxane 30% by weight dispersion Preparation Example B 3.07 3.08 2.91 3.92 3.19 1.97 1.90 3.16 3.16 3.16 Polysiloxane resin 25% by weight dispersion Preparation Example C1 4.05 4.15 4.33 3.18 4.00 2.53 2.54 4.05 4.05 4.05 40% by weight dispersion of polyfunctional isocyanate compounds Preparation Example D1 0.50 2.50 5.00 Antistatic agent NICEPOLE FE-26 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Expansion agent TEXPORT BG-290 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 water 91.66 91.65 91.58 91.77 91.67 94.41 95.41 91.16 89.16 86.66 SiR/AmSi 1550/100 2723/100 2075/100 1973/100 2486/100 2514/100 1389/100 2596/100 2596/100 2596/100 SiR/AmSi+DmSi 103/100 108/100 117/100 65/100 100/100 103/100 103/100 103/100 103/100 103/100 Evaluation Initial water repellency L-0 5 5 5 5 5 5 5 5 5 5 Durable water repellency L-20 4 4 4 4 4 4 4 5 5 5 initial repellency L-0 5 5 5 5 5 5 5 5 5 5 Durable liquid repellency L-20 4 4 4 4 4 4 4 5 5 5 Introducing resistance/DISPATEX K L-0 5 5 5 5 5 5 5 5 5 5 Introducing resistance/NICCA SUNSOLT 1200K L-0 5 5 5 5 5 5 5 5 5 5 Introducing resistance/Glazide L-0 5 5 5 5 5 5 5 5 5 5 Initial water pressure resistance L-0 500 510 490 500 490 520 520 490 500 510 Durable and water-pressure resistant L-20 500 500 490 500 500 500 500 500 500 500 Initial wear resistance L-0 5 5 5 5 5 5 5 5 5 5 Durability and wear resistance L-20 4- 4- 4- 4- 4- 4- 4- 4-5 4-5 4-5 texture 4 4 4 4 4 4 4 4 4 4 Seam slippage 1.8 1.7 1.8 1.8 1.8 1.7 1.7 1.8 1.8 1.7

[Table 6] Implementation Example 27 Implementation Example 28 Implementation Example 29 Implementation Example 30 Implementation Example 31 Implementation Example 32 Implementation Example 33 Implementation Example 34 Implementation Example 35 Mixing (parts by weight) Amine-modified polysiloxane 30% by weight dispersion Preparation Example A1 0.13 0.13 0.13 0.05 0.08 0.28 0.08 0.32 0.19 Alkyl polysiloxane 30% by weight dispersion Preparation Example B 3.16 3.16 3.16 1.80 3.21 3.01 3.45 2.61 3.15 Polysiloxane resin 25% by weight dispersion Preparation Example C1 4.05 4.05 4.05 1.52 4.05 4.05 3.76 4.53 4.10 40% by weight dispersion of polyfunctional isocyanate compounds Preparation Example D2 0.50 2.50 5.00 Antistatic agent NICEPOLE FE-26 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Expansion agent TEXPORT BG-290 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 water 91.16 89.16 86.66 95.63 91.66 91.66 91.71 91.55 92.56 SiR/AmSi 2596/100 2596/100 2596/100 2514/100 4043/100 1224/100 3932/100 1195/100 1798/100 SiR/AmSi+DmSi 103/100 103/100 103/100 103/100 103/100 103/100 89/100 129/100 102/100 Evaluation Initial water repellency L-0 5 5 5 5 5 5 5 5 5 Durable water repellency L-20 5 5 5 5 4 5 3 5 5 initial repellency L-0 5 5 5 5 4-5 5 5 5 5 Durable liquid repellency L-20 5 5 5 4 3 3 3 5 5 Introducing resistance/DISPATEX K L-0 5 5 5 5 5 5 5 5 5 Introducing resistance/NICCA SUNSOLT 1200K L-0 5 5 5 5 5 5 5 5 5 Introducing resistance/Glazide L-0 5 5 5 5 5 5 5 5 5 Initial water pressure resistance L-0 490 500 490 480 480 490 470 460 460 Durable and water-pressure resistant L-20 490 500 500 460 470 480 470 450 460 Initial wear resistance L-0 5 5 5 5 5 5 5 5 5 Durability and wear resistance L-20 4-5 4-5 4-5 3-4 3-4 3-4 3-4 3-4 3-4 texture 4 4 4 4 4 4 4-5 4 4 Seam slippage 1.8 1.8 1.8 1.8 1.8 1.7 1.8 1.7 1.7

[Table 7] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Mixing (parts by weight) Amine-modified polysiloxane 30% by weight dispersion Preparation Example A1 0.05 0.57 0.04 0.03 0.45 0.17 0.03 Alkyl polysiloxane 30% by weight dispersion Preparation Example B 3.24 2.72 3.25 3.81 2.33 4.88 4.98 Polysiloxane resin 25% by weight dispersion Preparation Example C1 4.05 4.05 4.05 3.39 2.80 1.95 1.98 Antistatic agent NICEPOLE FE-26 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Expansion agent TEXPORT BG-290 0.50 0.50 0.50 0.50 0.50 0.50 0.50 water 91.66 91.66 91.66 91.77 95.65 94.80 94.80 SiR/AmSi 7154/100 592/100 8455/100 11143/100 519/100 956/100 5500/100 SiR/AmSi+DmSi 103/100 103/100 103/100 74/100 84/100 32/100 33/100 Evaluation Initial water repellency L-0 5 5 5 5 5 5 5 Durable water repellency L-20 3 3 3 3 3 4 3 initial repellency L-0 3 3 3 3 3 3-4 3 Durable liquid repellency L-20 2-3 2-3 2-3 2-3 2-3 3 2-3 Introducing resistance/DISPATEX K L-0 4 3-4 3 3 3 4 3 Introducing resistance/NICCA SUNSOLT 1200K L-0 3 2 2 2 2 3 2 Introducing resistance/Glazide L-0 4 3 2 2 2 3 2 Initial water pressure resistance L-0 430 440 430 430 360 330 320 Durable and water-pressure resistant L-20 380 400 350 340 340 350 340 Initial wear resistance L-0 3 4 3 3 3 3 3 Durability and wear resistance L-20 2-3 3-4 2-3 2-3 3 2-3 2-3 texture 2 4 2 1 4 4 2 Seam slippage 1.8 2.0 1.8 1.8 3.0 2.5 1.8

It has been confirmed that the water-repellent fiber products treated with the water-repellent composition of Examples 1-35 possess excellent water repellency, durable water repellency, liquid repellency, durable liquid repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, texture, and resistance to infiltration. [Industrial Applicability]

According to the present invention, a water-repellent composition can be provided for water-repellent fiber products with excellent water repellency, durable water repellency, water pressure resistance, durable water pressure resistance, abrasion resistance, durable abrasion resistance, texture and resistance to water ingress.

Claims (4)

A water-repellent composition comprising an amino-modified polysiloxane, a polysiloxane resin, and an alkyl polysiloxane; the amount of the polysiloxane resin is 1,000 to 5,000 parts by mass relative to 100 parts by mass of the amino-modified polysiloxane resin, and the amount of the polysiloxane resin is in the range of 60 to 130 parts by mass relative to 100 parts by mass of the combined amount of the amino-modified polysiloxane and the alkyl polysiloxane. The water-repellent composition as described in claim 1, wherein the functional group equivalent of the amine-modified polysiloxane is 100 to 20,000 g/mol. A method for manufacturing a water-repellent fiber product, comprising the step of treating the fiber with a treatment solution containing a water-repellent composition as described in claim 1 or 2. A water-repellent fiber product comprising fibers and a water-repellent agent as described in claim 1 or 2 attached to the fibers.