Water-repellent agent composition

Abstract

The present disclosure provides a water-repellent agent composition for textile products including synthetic fibers, said water-repellent agent composition comprising a silicone compound that comprises a silicone oil and a silicone resin, wherein: in a GPC chart of the silicone compound, a peak top exists in the region for a molecular weight of not less than 1500; in the silicone compound, components having a molecular weight of not less than 1500 include a silicone oil other than amino-modified silicone; and the amount of the silicone resin is not more than 32 wt% with respect to the silicone compound. A water-repellent agent composition according to the present disclosure can provide good water repellency and good chalk mark properties to a base (particularly textile products).

Description

Water repellent composition

[0001] The present disclosure relates to a water repellent composition.

[0002] BACKGROUND ART Non-fluorine-based water repellents have been developed as water repellents for imparting water repellency to substrates (particularly textile products).

[0003] International Publication No. 2020 / 130002 International Publication No. 2019 / 131456 JP 2017 / 226946

[0004] When a water repellent is used in a textile product, not only water repellency but also chalk mark resistance is required. However, the chalk mark resistance has not been taken into consideration or suggested in the past water repellent agents.

[0005] An object of the present disclosure is to provide a water repellent composition that can impart good water repellency and good chalk mark resistance to a substrate (particularly a textile product).

[0006] The present disclosure includes the following aspects: [Item 1] A water repellent composition for textile products containing synthetic fibers, the water repellent composition comprising a silicone compound consisting of a silicone oil and a silicone resin, wherein a GPC chart of the silicone compound shows a peak top in a region of molecular weight of 1500 or more, and a component of the silicone compound having a molecular weight of 1500 or more comprises a silicone oil other than amino-modified silicone, and the amount of the silicone resin is 32 wt% or less based on the silicone compound. [Item 2] The water repellent composition according to Item 1, which comprises a surfactant. [Item 3] The water repellent composition according to Item 2, wherein the surfactant comprises a nonionic surfactant. [Item 4] The water repellent composition according to any one of Items 1 to 3, wherein the number average molecular weight Mn of the silicone oil is 50,000 or less. [Item 5] The water repellent composition according to any one of Items 1 to 4, wherein the number average molecular weight Mn of the silicone oil is 30,000 or less. [Item 6] The water repellent composition according to any one of Items 1 to 5, wherein the number average molecular weight Mn of the silicone resin is 1,000 or more. [Item 7] The water repellent composition according to any one of Items 1 to 6, wherein the number average molecular weight Mn of the silicone compound is 20,000 or less. [Item 8] The water repellent composition according to any one of Items 1 to 7, which is in the form of an organic solvent solution, an organic solvent dispersion, or an aqueous dispersion. [Item 9] A method for producing a textile product, comprising applying the water repellent composition according to any one of Items 1 to 8 to a textile substrate. [Item 10] A method for producing a textile product, comprising applying a water repellent composition containing -SO ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and １ ) (OX ２ ) (wherein, X １ and X ２[Item 11] A method for producing a textile product according to Item 9, comprising a step of providing one or more functional groups selected from the group consisting of monovalent groups represented by the formula: [wherein each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms]. [Item 12] A textile product to which the silicone oil and the silicone resin in the water repellent composition according to any one of Items 1 to 8 are attached. [Item 13] A method for producing a textile product according to Item 9, comprising a step of providing one or more functional groups selected from the group consisting of monovalent groups represented by the formula: ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

[0007] The water repellent composition of the present disclosure can impart good water repellency and good chalk mark resistance to substrates (particularly textile products).

[0008] <Definition of Terms> As used herein, an "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. Furthermore, an "n-valent organic group" refers to an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C １－２０Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents, if explicitly stated.

[0010] In this specification, when a term (symbol) that may appear multiple times in a chemical structure is defined, that definition applies independently at each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0011] The chemical structures described herein should be understood not to encompass chemical structures that would be recognized by those skilled in the art as chemically impossible or extremely unstable.

[0012] <Water repellent composition> The water repellent composition according to the present disclosure is a water repellent composition for textile products containing synthetic fibers, and the water repellent composition contains a silicone compound consisting of silicone oil and silicone resin, and in a GPC chart of the silicone compound, a peak top is present in a region of molecular weight of 1500 or more, and the component of the silicone compound having a molecular weight of 1500 or more contains silicone oil other than amino-modified silicone, and the amount of silicone resin is 32% by weight or less relative to the silicone compound.

[0013] The water repellent composition according to the present disclosure has the above-described characteristics, and can be adhered to a substrate (particularly a fibrous substrate) to impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and can also function as a water resistance agent, oil resistance agent, water repellent agent, oil repellent agent, and / or stain resistance agent.

[0014] The water repellent composition of the present disclosure has the above characteristics, and thus can have good water repellency and good chalk mark resistance, as well as good texture, peel strength, and / or slip properties.

[0015] The water repellent composition of the present disclosure can have good peel strength and slip properties by using a silicone other than amino-modified silicone. In particular, the peel strength and slip properties can be improved by including a silicone oil other than amino-modified silicone in the silicone compound component having a molecular weight of 1,500 or more.

[0016] The water repellent composition according to the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The water repellent composition according to the present disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds.

[0017] The water repellent composition of the present disclosure is for use in textiles containing synthetic fibers.

[0018] Examples of textile products include clothing, bedding, curtains, rugs, towels, fabrics, threads, masks, etc. The textile products of the present invention also include fibers such as threads. More specifically, textile products are described in the "Treated Products" section of this disclosure.

[0019] Examples of synthetic fibers include polyester fibers such as polyester and polylactic acid, polyacrylonitrile fibers such as acrylic, polyamide fibers such as nylon, polyvinyl chloride fibers such as polyvinyl chloride, polyvinyl alcohol fibers such as vinylon, polyvinylidene chloride fibers such as vinylidene, polyolefin fibers such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer, polyurethane fibers such as polyurethane, polyvinyl chloride / polyvinyl alcohol copolymer fibers such as polycrelal, polyalkylene paraoxybenzoate fibers such as benzoate, and polyfluoroethylene fibers such as polytetrafluoroethylene. Synthetic fibers are preferably polyester fibers and polyamide fibers, more preferably polyester and nylon.

[0020] The textile product may include semi-synthetic fibers obtained by spinning fibers obtained by chemically modifying naturally occurring components. Examples of semi-synthetic fibers include protein-based fibers (milk protein casein fiber, Promix, etc.) and cellulosic fibers (rayon, Polynosic, cupra, acetate, etc.).

[0021] Amount of Silicone Compound The amount of the silicone compound in the water repellent composition may be 0.01% by weight or more, 0.03% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more, and may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less.

[0022] [Silicone Compound] The silicone compound is composed of a silicone oil and a silicone resin. In the present disclosure, the silicone compound refers to a mixture of a silicone oil and a silicone resin. The silicone compound is also referred to as a silicone mixture.

[0023] The silicone compound may include one or more silicone oils, or one or more silicone resins.

[0024] In the GPC chart of the silicone compound, a peak top is present in a region of molecular weight of 1500 or more. The fact that the silicone compound has a peak top in a region of molecular weight of 1500 or more in the GPC chart obtained by GPC measurement can be confirmed by the following analysis.

[0025] The silicone compound was confirmed by gel permeation chromatography (GPC) to have a peak top in the molecular weight region of 1500 or more (polystyrene equivalent). For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh Corporation) was used. Two TSKgel SuperMultipore HZ-M columns were used. An RI detector was used. Standard polystyrene (SRM706a NIST) was used as the standard material. The analytical sample was prepared by dissolving silicone resin in tetrahydrofuran to prepare a 0.1 wt% solution, which was then passed through a 0.5 μm filter. When measuring the average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, and 10 μL of the analytical sample was injected at a flow rate of 0.35 mL / min. Furthermore, components with a molecular weight of 1500 or more were separated from the silicone compound by preparative GPC. Gel permeation chromatography was performed using an Agilent 1260 Infinity II LC system (Agilent). One SHODEX KF-G column and two SHODEX KF-806L columns were used in series. An ELSD detector was used. Polymethyl methacrylate was used as the standard. The analytical sample was prepared by dissolving a silicone compound in tetrahydrofuran to prepare a 0.1 wt% solution, which was then passed through a 0.5 μm filter. When measuring the average molecular weight, the column was maintained at 30°C, tetrahydrofuran was used as the eluent, and 100 μL of the analytical sample was injected at a flow rate of 0.50 mL / min. Components with a molecular weight of 1500 or greater were concentrated, and silicone compound components (Mn>1500) were extracted. Regarding the silicone compound components (Mn>1500), １ H-NMR, 29 By measuring Si-NMR, it is confirmed that the region contains a silicone oil component.

[0026] The number average molecular weight Mn of the silicone compound may be 200 or more, 300 or more, 500 or more, 700 or more, 1000 or more, 1500 or more, 2000 or more, 2500 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, 8000 or more, or 10000 or more, and may be 100000 or less, 80000 or less, 60000 or less, 50000 or less, 40000 or less, 30000 or less, 25000 or less, 20000 or less, 15000 or less, or 10000 or less. The number average molecular weight Mn of the silicone compound is a value obtained by GPC measurement of a mixture of two or more silicones consisting of a silicone resin and a silicone oil.

[0027] Among silicone compounds, components with a molecular weight of 1500 or more include silicone oils other than amino-modified silicones. Components with a molecular weight of 1500 or more refer to components with a molecular weight of 1500 or more per molecule (i.e., silicone resins and / or silicone oils). The presence of silicone resins and / or silicone oils with a molecular weight of 1500 or more can be confirmed by GPC or the like.

[0028] The silicone oil other than the amino-modified silicone in the silicone compound component having a molecular weight of 1500 or more may be the silicone oil described below in [Silicone Oil].

[0029] In one embodiment, the silicone compound component having a molecular weight of 1500 or more may be only silicone oil other than amino-modified silicone.

[0030] In one embodiment, the silicone compound component having a molecular weight of 1,500 or more may be a silicone oil represented by the following general formula (1), and may be preferably dimethylpolysiloxane or diethylpolysiloxane.

[0031] [Unit] The silicone compound is composed of a combination of at least one unit selected from the group consisting of M units, D units, T units, and Q units.

[0032] M unit is (R Ｍ ) ３ SiO ０．５Represents the unit. Ｍ are each independently a hydrocarbon group having 1 to 40 carbon atoms or a reactive group in the silicone compound.

[0033] The ratio of M units contained in the silicone compound of the present disclosure may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more in the molecule, and may be 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0034] The amount of M units relative to the amount of D units, T units, or Q units may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more, and may be 150 mol% or less, 130 mol% or less, 100 mol% or less, 80 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

[0035] D unit is (R Ｄ ) ２ represents a SiO unit. Ｄ are each independently a hydrocarbon group having 1 to 40 carbon atoms or a reactive group in the silicone compound.

[0036] The ratio of D units contained in the silicone compound of the present disclosure may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more in the molecule, and may be 95 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less. The silicone compound of the present disclosure does not necessarily contain D units.

[0037] T unit is R Ｔ SiO １．５ Represents the unit. Ｔ are each independently a hydrocarbon group having 1 to 40 carbon atoms or a reactive group in the silicone compound.

[0038] The proportion of T units contained in the silicone compound of the present disclosure may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more in the molecule, and may be 95 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less. The silicone compound of the present disclosure does not have to contain T units.

[0039] The Q unit is SiO ２ Represents a unit.

[0040] The proportion of Q units contained in the silicone compound of the present disclosure may be 0 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more in the molecule, and may be 95 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less. The silicone compound of the present disclosure does not necessarily contain Q units.

[0041] Examples of hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms and hydrocarbon groups having 6 to 40 carbon atoms.

[0042] Examples of the hydrocarbon group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and other hydrocarbon groups having 1 to 5 carbon atoms (particularly an aliphatic hydrocarbon group, particularly an alkyl group such as a methyl group or an ethyl group, particularly a methyl group).

[0043] The hydrocarbon group having 6 to 40 carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, preferably linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less. Examples of aromatic hydrocarbon groups include a phenyl group.

[0044] Examples of reactive groups include groups having functional groups (e.g., hydroxy groups, amino groups, mercapto groups, epoxy groups, carboxyl groups, halogen-substituted alkyl groups, vinyl groups, (meth)acrylic groups, (meth)acryloyloxy groups, oxyalkylene groups, isocyanate groups, (meth)acrylamide groups, hydrogen atoms directly bonded to silicon atoms, etc.). These functional groups may be directly bonded to the silicon atom, or may be bonded to an organic group directly bonded to the silicon atom. The organic group may be a hydrocarbon group, such as an alkylene group or a divalent aromatic group. The hydrocarbon group may have from 2 to 12 carbon atoms, and the alkylene group preferably has from 2 to 10 carbon atoms. The divalent aromatic group preferably has from 6 to 12 carbon atoms. The reactive group may be a group selected from the group consisting of a hydroxy group, an epoxy ring, a carboxyl group, a (meth)acrylic group, and an amino group, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0045] The silicone compound may be an unmodified silicone (such as polyalkylsiloxane, polyalkylphenylsiloxane, or polydimethylsiloxane) in which the reactive group is not modified, or may be a modified silicone (such as amino-modified, polyether-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogensilicone, carbinol-modified silicone, carboxyl-modified silicone, or mercapto-modified silicone).

[0046] The above description of silicone compounds may be applied independently to silicone resins and silicone oils.

[0047] [Silicone Resin] The water repellent composition of the present disclosure contains a silicone resin. The silicone resin may contain MQ, MDQ, MT, MTQ, MDT, or MDTQ as a constituent component. The silicone resin is preferably an organopolysiloxane having a three-dimensional structure. Here, M, D, T, and Q are each (R″) ３ SiO ０．５ Units, (R'') ２ SiO unit, R''SiO １．５ Units and SiO ２ R″ represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

[0048] The number average molecular weight Mn of the silicone resin may be 200 or more, 300 or more, 500 or more, 700 or more, 1000 or more, 1500 or more, 2000 or more, 2500 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, 8000 or more, or 10000 or more; and may be 100000 or less, 80000 or less, 60000 or less, 50000 or less, 40000 or less, 30000 or less, 25000 or less, 20000 or less, 15000 or less, or 10000 or less.

[0049] The number-average molecular weight Mn of the silicone resin can be obtained by GPC (gel permeation chromatography) (polystyrene equivalent). For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh Corporation) was used. Two TSKgel SuperMultipore HZ-M columns were used. An RI detector was used. Standard polystyrene (SRM706a NIST) was used as the standard. The analytical sample was prepared by dissolving the silicone resin in tetrahydrofuran to prepare a 0.1 wt% solution, which was then passed through a 0.5 μm filter. When measuring the average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, and 10 μL of the analytical sample was injected at a flow rate of 0.35 mL / min.

[0050] The silicone resin preferably has a hardness of 20 or more, more preferably 60 or more, as measured with a type A durometer in accordance with JIS K 6249:2003 13. Hardness Test.

[0051] The silicone resin may be an MQ resin, an MT resin, or an MDT resin, and may have a moiety designated MDQ, MTQ, or MDTQ.

[0052] The molar ratio of M to D, T, or Q (M / D, M / T, or M / Q) may be 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, or 1.0 or more, and may be 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, or 1.1 or less, and may be 0.6 or more and 1.7 or less, preferably 0.8 or more and 1.5 or less.

[0053] The silicone resin may also be obtained as a solution in which the silicone resin is dissolved in an alkylpolysiloxane or a liquid medium other than an alkylpolysiloxane, such as n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, or a mixture of these solvents.

[0054] Examples of solutions in which a silicone resin is dissolved in an alkylpolysiloxane include KF7312J (a 50:50 mixture of trimethylsilyl group-containing polysiloxane and decamethylcyclopentasiloxane), KF7312F (a 50:50 mixture of trimethylsilyl group-containing polysiloxane and octamethylcyclotetrasiloxane), KF9021L (a 50:50 mixture of trimethylsilyl group-containing polysiloxane and low-viscosity methylpolysiloxane), and KF7312L (a 50:50 mixture of trimethylsilyl group-containing polysiloxane and low-viscosity methylpolysiloxane), all of which are commercially available from Shin-Etsu Chemical Co., Ltd.

[0055] As the silicone resin alone, commercially available products may be used, such as MQ-1600 and MQ-1640 (each manufactured by Dow-Toray Industries, Inc.), KR-220L, KR-251, KR-311, and X-40-2406M (each manufactured by Shin-Etsu Chemical Co., Ltd.), R2701 (manufactured by Wacker Asahi Kasei Silicones Co., Ltd.), Silmer HQ20 (manufactured by Siltech), and SILDFORM FLEXIBLE RESIN (manufactured by MOMENTIVE).

[0056] The silicone resin may be used as a silicone resin emulsion. Examples of silicone resin emulsions include X-52-8005, X-52-8432, X-52-8407, X-52-8407, X-52-8499DA, X-52-8500DA, and KR-4000GE (each manufactured by Shin-Etsu Chemical Co., Ltd.), R2701 (manufactured by Wacker Asahi Kasei Silicones Co., Ltd.), and Siltech E-2199 (manufactured by Siltech). The commercially available products may contain MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0057] Amount of Silicone Resin The amount of silicone resin is 32% by weight or less relative to the silicone compound (i.e., the sum of the amount of silicone oil and the amount of silicone resin). The amount of silicone resin may be 30% by weight or less, 28% by weight or less, 26% by weight or less, 24% by weight or less, 22% by weight or less, 20% by weight or less, 18% by weight or less, 16% by weight or less, 14% by weight or less, 12% by weight or less, 10% by weight or less, or 1% by weight or more, 2% by weight or more, 4% by weight or more, 6% by weight or more, 8% by weight or more, 10% by weight or more, 12% by weight or more, 14% by weight or more, 16% by weight or more, 18% by weight or more, or 20% by weight or more relative to the silicone compound.

[0058] From the viewpoint of improving the chalk mark resistance, it is preferable that the amount of silicone resin is small relative to the silicone compound. Similarly, from the viewpoint of improving the texture, it is preferable that the amount of silicone resin is small relative to the silicone compound. From the viewpoint of improving the chalk mark resistance and / or the texture, the amount of silicone resin may be 30 wt% or less, 23 wt% or less, 16 wt% or less, or 12 wt% or less relative to the silicone compound.

[0059] From the viewpoint of improving the liquid repellency, the amount of the silicone resin is preferably large relative to the silicone compound, and from the viewpoint of improving the liquid repellency, the amount of the silicone resin may be 8 wt % or more, 16 wt % or more, 22 wt % or more, or 30 wt % or more relative to the silicone compound.

[0060] [Silicone Oil] The water repellent composition of the present disclosure contains a silicone oil. The silicone oil may be, for example, either a linear organopolysiloxane or a cyclic organopolysiloxane.

[0061] The silicone oil, which is a chain organopolysiloxane, may be a so-called straight silicone oil or a modified silicone oil. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, carbinol, mercapto, etc. Examples of silicone oils that are cyclic organopolysiloxanes include cyclic dimethylsiloxane oil, etc.

[0062] The chain organopolysiloxane may be a compound having saturated hydrocarbon groups at the side chains and terminals. The silicone oil may be, for example, a compound represented by the following formula (1):

[0063] [In the formula, R １１ , R １２ , R １３ , R １４ , R １５ , and R １６ are each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a is an integer of 1 or greater.

[0064] R １１ , R １２ , R １３ , R １４ , R １５ , and R １６ are each independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. The number of carbon atoms in such a monovalent saturated hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may be 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 2 or less.

[0065] R １１ , R １２ , R １３ , R １４ , R １５ , and R １６The monovalent saturated hydrocarbon groups in may be independently linear or branched, preferably linear, and more preferably linear alkyl groups.

[0066] In one aspect, R １１ , R １２ , R １３ , R １４ , R １５ , and R １６ The monovalent saturated hydrocarbon group in is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0067] In one aspect, R １１ , R １２ , R １３ , R １４ , R １５ , and R １６ At least one of the groups may be modified with a reactive group. Examples of the reactive group include the reactive groups exemplified above, such as —OR′, —N(R′) ２ , —COOR′, an epoxy group, a mercapto group, and a halogen atom (wherein R′ is independently in each occurrence a hydrogen atom, an amino group, or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms, or a combination thereof). The reactive group may or may not have an active hydrogen.

[0068] a is an integer equal to or greater than 1. The value of a may be selected so that the kinematic viscosity of the silicone oil represented by formula (1) falls within the range of kinematic viscosity of the silicone oil described below.

[0069] In one aspect, a may be 3 or more, 5 or more, 6 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, preferably 10 or more, and may be 10,000 or less, 7,500 or less, 5,000 or less, 3,000 or less, 1,500 or less, 1,000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, preferably 1,000 or less.

[0070] Examples of the silicone oil represented by formula (1) include dimethylpolysiloxane and diethylpolysiloxane.

[0071] The cyclic organopolysiloxane may be a compound having a saturated hydrocarbon group as a side chain. The silicone oil may be, for example, a compound represented by the following formula (2).

[0072] [In the formula, R １７ and R １８ are each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and w is an integer of 2 to 20.

[0073] R １７ and R １８ are each independently a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms. The number of carbon atoms in such a saturated hydrocarbon group may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may be 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 2 or less, with 1 to 10 being preferred.

[0074] R １７ and R １８ The saturated hydrocarbon groups in may be, independently of one another, linear or branched, preferably linear, and more preferably linear alkyl groups.

[0075] In one aspect, R １７ and R １８ The saturated hydrocarbon group in is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0076] In one aspect, R １７ and R １８ At least one of the groups may be modified with a reactive group. Examples of the reactive group include the reactive groups exemplified above, such as —OR′, —N(R′) ２, —COOR′, an epoxy group, a mercapto group, and a halogen atom (wherein R′ is independently in each occurrence a hydrogen atom, an amino group, or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms, or a combination thereof). The reactive group may or may not have an active hydrogen.

[0077] b is an integer of 2 to 20. b is preferably an integer of 3 to 10, and more preferably 4 or 5.

[0078] Examples of the compound represented by formula (2) include decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane.

[0079] The silicone oil may be used alone or in combination of two or more kinds.

[0080] The silicone oil is preferably liquid at 25° C. The kinematic viscosity of the silicone oil at 25° C. is 0.1 mm ２ / s or more, 1mm ２ / s or more, 10mm ２ / s or more, 50mm ２ / s or more, 100mm ２ / s or more, 200mm ２ / s or more, 500mm ２ / s or more, 1000mm ２ / s or more, 3000mm ２ / s or more, 5000mm ２ / s or more, 10000mm ２ / s or more, 30000mm ２ / s or more, 50000mm ２ / s or more, and may be 100,000 mm ２ / s or less, 50000mm ２ / s or less, 30000mm ２ / s or less, 10000mm ２ / s or less, 5000mm ２ / s or less, 3000mm ２ / s or less, 1000mm ２ / s or less, 500mm ２ / s or less, 300mm ２ / s or less, or 100 mm ２The kinematic viscosity at 25°C means a value obtained by a method in accordance with JIS K 2283:2000.

[0081] The number average molecular weight Mn of the silicone oil may be 200 or more, 300 or more, 500 or more, 700 or more, 1000 or more, 1500 or more, 2000 or more, 2500 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, 8000 or more, or 10000 or more, and may be 100000 or less, 80000 or less, 60000 or less, 50000 or less, 40000 or less, 30000 or less, 25000 or less, 20000 or less, 15000 or less, or 10000 or less.

[0082] The number-average molecular weight Mn of silicone oil can be obtained by GPC (gel permeation chromatography) (polystyrene equivalent). For gel permeation chromatography, an HLC-8420GPC EcoSEC Elite-WS (manufactured by Tosoh) was used. Two TSKgel SuperMultipore HZ-M columns were used. An RI detector was used. Standard polystyrene (SRM706a NIST) was used as the standard material. The analytical sample was prepared by dissolving silicone resin (or silicone oil) in tetrahydrofuran to prepare a 0.1 wt% solution, which was then passed through a 0.5 μm filter. When measuring the average molecular weight, the column was maintained at 40°C, tetrahydrofuran was used as the eluent, and 10 μL of analytical sample was injected at a flow rate of 0.35 mL / min.

[0083] As the silicone oil alone, commercially available products may be used, such as KF-96-6CS, KF-96-30CS, KF-96-50CS, KF-96-300CS, KF-96-1000CS, X-22-3701E, and X-22-173DX (each manufactured by Shin-Etsu Chemical Co., Ltd.).

[0084] Amount of Silicone Oil The amount of silicone oil may be 30% by weight or less, 28% by weight or less, 26% by weight or less, 24% by weight or less, 22% by weight or less, 20% by weight or less, 18% by weight or less, 16% by weight or less, 14% by weight or less, 12% by weight or less, 10% by weight or less, or 1% by weight or more, 2% by weight or more, 4% by weight or more, 6% by weight or more, 8% by weight or more, 10% by weight or more, 12% by weight or more, 14% by weight or more, 16% by weight or more, 18% by weight or more, or 20% by weight or more, based on the silicone compound (i.e., the sum of the amount of silicone oil and the amount of silicone resin).

[0085] From the viewpoint of improving the chalk mark resistance, the amount of silicone oil is preferably small relative to the silicone compound.Similarly, from the viewpoint of improving the texture, the amount of silicone oil is preferably small relative to the silicone compound.From the viewpoint of improving the chalk mark resistance and / or the texture, the amount of silicone resin may be 30 wt% or less, 23 wt% or less, 16 wt% or less, or 12 wt% or less relative to the silicone compound.

[0086] [Silicone Emulsion] The silicone compound may be a silicone emulsion emulsified with a dispersant, a surfactant, etc. That is, the silicone compound may be combined with a dispersant, a surfactant, etc., and contained in the water repellent composition in an emulsified state.

[0087] The dispersant and surfactant may be the dispersant of the present disclosure. The silicone compound may be emulsified by a known method. When the silicone compound is emulsified, the silicone compound is easily dispersed uniformly in the water repellent composition, and liquid repellency is easily imparted.

[0088] The silicone emulsion may be either an oil-in-water emulsion (O / W type) or a water-in-oil emulsion (W / O type). The liquid medium used in the silicone emulsion may be any of the liquid mediums described in the [Liquid Medium] section of this disclosure.

[0089] The silicone emulsions contained in the water repellent compositions of the present disclosure may be anionic, cationic, or nonionic, with nonionic surfactants being preferred.

[0090] The water repellent composition of the present disclosure may further contain the silicone resin and / or silicone oil exemplified above.

[0091] The water repellent composition of the present disclosure may not contain amino-modified silicone.

[0092] The water repellent composition of the present disclosure may be an aqueous dispersion.

[0093] The water repellent composition of the present disclosure may further contain the components described below in addition to the components described above.

[0094] [Hydrocarbon Group-Containing Polymer] The water repellent composition of the present disclosure may further contain a hydrocarbon group-containing polymer.

[0095] The hydrocarbon group-containing polymer is a polymer obtained by polymerizing a vinyl monomer. The monomer may be any compound having a polymerizable carbon-carbon double bond (ethylenically unsaturated double bond) (>C=C<), and may be a monomer containing a vinyl group, a vinylene group, a vinylidene group, an acryloyl group, a methacryloyl group, or a derivative group thereof.

[0096] [Characteristics, etc.] The characteristics, etc. that the hydrocarbon group-containing polymer of the present disclosure may have are shown below.

[0097] The hydrocarbon group-containing polymer is preferably a compound containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content of the hydrocarbon group-containing polymer may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased content means that the amount of fossil resource-based materials, such as petroleum, used is small, and from this perspective, the higher the biobased content of the hydrocarbon group-containing polymer, the better.

[0098] The melting point of the hydrocarbon group-containing polymer may be 30°C or higher, 40°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, and may be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower.

[0099] [Structure, etc.] The hydrocarbon group-containing polymer in the present disclosure may not have any one selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom.

[0100] The weight average molecular weight of the hydrocarbon group-containing polymer may be 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may be 5,000,000 or less, 3,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less. The weight average molecular weight may be a polystyrene-equivalent molecular weight measured by GPC.

[0101] (a) Hydrocarbon Group-Containing Monomer The hydrocarbon group-containing polymer of the present disclosure may have a repeating unit derived from a hydrocarbon group-containing monomer (a). The monomer (a) has one ethylenically unsaturated double bond and a hydrocarbon group having from 2 to 40 carbon atoms.

[0102] The monomer (a) preferably has a (meth)acrylic group as the group having an ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0103] Monomer (a) has a hydrocarbon group having from 2 to 40 carbon atoms. The hydrocarbon group having from 2 to 40 carbon atoms may have a substituent, but preferably does not have a substituent. Here, the hydrocarbon group is a monovalent group.

[0104] The hydrocarbon group contained in the monomer (a) may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched or linear, more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group).

[0105] The hydrocarbon group is typically monovalent and may be located at the end of the molecule, and the hydrocarbon group may have one or more methyl groups at the end. In this specification, a hydrocarbon compound (e.g., hydrocarbon wax) is understood to consist of only a monovalent hydrocarbon group and one hydrogen atom, and for example, an n-alkane having 20 carbon atoms (eicosane) is understood to consist of only an alkyl group having 20 carbon atoms and one hydrogen atom.

[0106] The number of carbon atoms in the hydrocarbon group may be 2 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0107] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR' and -N(R'). ２, —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) —OR′ (particularly —OH) as a substituent (e.g., other than at the terminal).

[0108] The hydrocarbon group-containing monomer (a) is a monomer represented by the following formula: ２ = C (-R ｂ )-C(=O)-R ｃ - (R ｄ ) ｋ [In the formula, R ｂ is a hydrogen atom, a monovalent organic group or a halogen atom, R ｃ represents a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, —CH ２ -, -CH(-) ２ ), -C ６ H ４ -, -O-, -S-, -C(=O)-, -S(=O) ２ - and -NR Ｃ１ - (R Ｃ１ is a group consisting of at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, k is 1 to 3, and R ｄ are each independently a hydrocarbon group having 2 to 40 carbon atoms.]

[0109] R ｂ R may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. ｂExamples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. ｂ is preferably a hydrogen atom, a methyl group, or a chlorine atom. ｂ is particularly preferably a hydrogen atom.

[0110] R ｃ is a divalent to tetravalent group. ａ is preferably a divalent group. ｃ represents a hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ It is preferable that Y is a group constituted by at least one selected from - and -NH-. ａ is preferably not a hydrocarbon group. Examples of hydrocarbon groups having one carbon atom include -CH ２ -, -CH(-) ２ or -C(-) ３ The hydrocarbon group having one carbon atom is repeated, and -(CH ２ ) m A hydrocarbon group having two or more carbon atoms may be formed, such as Y - (where m is an integer of 1 to 5). ａ may have an NH group.

[0111] R ｃ is -R ｃ '-, -R ｃ '-R ｃ '-, -R ｃ '-C(=O)-, -C(=O)-R ｃ '-, -R ｃ '-C(=O)-R ｃ '-, -R ｃ '-R'-, -R ｃ '-R'-R ｃ '-, -R ｃ '-R'-R ｃ '-C(=O)-,-R ｃ '-R'-C(=O)-R ｃ '-, -R ｃ '-R'-R ｃ '-C(=O)-R ｃ '-, or -R ｃ '-R'-R ｃ '-R'- [wherein, Rｃ ' is a direct bond, -O-, -NH- or -S(=O) ２ - and R' is -(CH ２ ) m - (m is an integer of 1 to 5) or -C ６ H ４ -(phenylene group).

[0112] R ｃ Specific examples of are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ ) m -O-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -C(=O)-O-, -NH-(CH ２ ) m -OC(=O)-, -NH-(CH ２ ) m -C(=O)-O-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -O-C ６ H ４ -, -O-(CH ２ ) m -NH-S(=O) ２ -, -O-(CH２ ) m -S(=O) ２ -NH-, -NH-(CH ２ ) m -O-C(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-O-, -NH-(CH ２ ) m -C(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-, -NH-(CH ２ ) m -NH-C(=O)-NH-, -NH-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m -NH-C ６ H ４ -, -NH-(CH ２ ) m -NH-S(=O)<000022​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH- [wherein m is an integer of 1 to 5, particularly 2 or 4] is preferred. ａ is -O- or -O-(CH ２ ) m —NH—C(═O)—, particularly —O—(CH ２ ) m It is more preferably —NH—C(═O)—.

[0114] R ｄ are each independently a hydrocarbon group having from 2 to 40 carbon atoms, and while the above description of (hydrocarbon group having from 2 to 40 carbon atoms) is incorporated herein by reference, it is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 12 to 18, 16 to 26, or 15 to 26, particularly 18 to 22, or 17 to 22.

[0115] Specific examples of the monomer (a) include: (a1) a monomer represented by the formula: CH2=C(-X ａ１ )-C(=O)-Y ａ１１ -Z (-Y ａ１２ -R ａ１ ) ｎ [In the formula, R ａ１ are each independently a hydrocarbon group having 2 to 40 carbon atoms, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ１１ is —O— or —NH—, and Y ａ１２ are each independently a direct bond, or —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ -, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.], and (a2) a monomer represented by the formula: CH2=C(-X ａ２ )-C(=O)-Yａ２ -R ａ２ [In the formula, R ａ２ is a hydrocarbon group having 2 to 40 carbon atoms, ａ２ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ２ is —O— or —NH—.

[0116] (a1) Monomer The monomer (a1) is a monomer different from the monomer (a2).

[0117] The monomer (a1) may be a monomer having a hydrocarbon group having 2 to 40 carbon atoms and an NH group-containing group. The monomer (a1) may contain an amide group, a urea group, a urethane group, or a sulfonamide group. The NH group-containing group may be an amide group, a urea group, a urethane group, or a sulfonamide group. The hydrocarbon-based monomer may be a combination of a hydrocarbon-based monomer having an amide group, a urea group, a urethane group, or a sulfonamide group and a hydrocarbon-based monomer not having an amide group, a urea group, a urethane group, or a sulfonamide group. When the monomer (a1) contains such a group, the effects of the present disclosure can be effectively achieved.

[0118] The monomer (a1) is —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ - is a (meth)acrylate or (meth)acrylamide having at least one group selected from the group consisting of:

[0119] The monomer (a1) has the formula: CH2=C(-X ａ１ )-C(=O)-Y ａ１１ -Z (-Y ａ１２ -R ａ１ ) ｎ [In the formula, R ａ１ are each independently a hydrocarbon group having 2 to 40 carbon atoms, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ１１ is —O— or —NH—, and Y ａ１２ are each independently a direct bond, or —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH２ -, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2. ａ１２ and / or Z may not be a direct bond. ａ１２ and Z may not be a direct bond at the same time.

[0120] R ａ１ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ａ１ In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22 carbon atoms.

[0121] X ａ１ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0122] Y ａ１２ represents -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'-, wherein each Y' independently represents a direct bond, -O-, -NH-, or -S(=O) ２ - and R' is -(CH ２ ) ｍ - (m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH ２ ) ｌ -C ６ H ４ -(CH ２ ) ｌ - (each l is independently an integer of 0 to 5; -C ６ H ４ - is a phenylene group.

[0123] Yａ１２ Specific examples thereof include direct bonding, -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S(=O) ２ -, -NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４ -, -NH-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ ) m -O-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -C(=O)-O-, -NH-(CH ２ ) m -O-C(=O)-, -NH-(CH ２ ) m -C(=O)-O-, -O-(CH ２ ) m -O-C(=O)-NH-, -O-(CH / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​２ ) m -NH-C(=O)-, -NH-(CH ２ ) m -NH-C(=O)-NH-, -NH-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m -NH-C ６ H ４ wherein m is an integer of 1 to 5.

[0124] Especially Y ａ１２ may have an NH group.

[0125] Y ａ１２ is -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S(=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ - is preferred. ａ１２ is more preferably —NH—C(═O)—, —C(═O)—NH—, —O—C(═O)—NH—, —NH—C(═O)—O— or —NH—C(═O)—NH—. ａ１２ may not be a direct bond.

[0126] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a linear or branched structure. Z preferably has 2 to 4 carbon atoms, and particularly preferably 2. Specific examples of Z include a direct bond, -CH ２ -, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ CH２ -, -CH ２ CH(-) ２ , -CH ２ (CH-)CH ２ -, -CH ２ CH ２ CH(-) ２ , -CH ２ CH ２ CH ２ CH ２ CH(-) ２ , -CH ２ CH ２ (CH-)CH ２ -, -CH ２ CH ２ CH ２ CH(-) ２ Z does not have to be a direct bond.

[0127] Monomer (a1) is CH2=C(-X ａ１ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ１ , C.H. ２ =C(-X ａ１ )-C(=O)-O-(CH ２ ) ｍ -OC(=O)-NH-R ａ１ , C.H. ２ =C(-X ａ１ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-OR ａ１ , C.H. ２ =C(-X ａ１ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-NH-R ａ１ Preferably, R ａ１ and X ａ１ has the same meaning as above.]. The monomer (a1) is CH2=C(-X ａ１ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ１ It is particularly preferred that:

[0128] Monomer (a1) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, monomer (a1) can be produced by reacting a (meth)acrylate having an isocyanate group in its side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0129] Preferred examples of the monomer (a) are as follows: stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate; stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0130]

[0131]

[0132]

[0133]

[0134]

[0135] [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.] The compound of the above chemical formula is an acrylic compound having a hydrogen atom at the α-position, but specific examples may be a methacrylic compound having a methyl group at the α-position and an α-chloroacrylic compound having a chlorine atom at the α-position.

[0136] The monomer (a1) has the formula: ａ１２ -C(=O)-NH-R ａ１３ -O-R ａ１１ [In the formula, R ａ１１ represents an organic residue having an ethylenically unsaturated polymerizable group, R ａ１２ is a hydrocarbon group having 2 to 40 carbon atoms, R ａ１３ is a hydrocarbon group having 1 to 5 carbon atoms.]

[0137] R ａ１１ is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a polymer carbon-carbon double bond. ａ１１１ =CH ２ , -CHR ａ１１１ =CH ２ , -CH ２ CHR ａ１１１ =CH ２ and the like. ａ１１１ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ａ１１ R may have various organic groups in addition to the ethylenically unsaturated polymerizable group, such as organic groups of chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. ａ１１ is -C(=O)CR ａ１１１ =CH ２ It is preferable that:

[0138] R ａ１２ is the same as the hydrocarbon group contained in the monomer (a) described above, and is a hydrocarbon group having from 2 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbon groups and cyclic hydrocarbon groups. Among these, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred. ａ１２ The number of carbon atoms is 6 or more and 40 or less, preferably 11 to 27, and particularly preferably 15 to 23.

[0139] R ａ１３is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched, and may have an unsaturated bond, but is preferably linear. ａ１３ The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. ａ１３ is preferably an alkylene group.

[0140] The amide group-containing monomer is R ａ１２ is one type (for example, R ａ１２ is only a compound having 17 carbon atoms), or R ａ１２ A combination of multiple ａ１２ a compound having 17 carbon atoms, and R ａ１２ and a compound having 15 carbon atoms.

[0141] An example of the amide group-containing monomer is carboxylic acid amide alkyl (meth)acrylate.Specific examples of the amide group-containing monomer include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristate amide ethyl (meth)acrylate, laurate amide ethyl (meth)acrylate, isostearate ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tertiary butylcyclohexyl caproate amide ethyl (meth)acrylate, adamantanecarboxylic acid ethyl amide (meth)acrylate, naphthalenecarboxylic acid amide ethyl (meth)acrylate, anthracenecarboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)acrylate, stearic acid amide propyl (meth)acrylate, palmitic acid amide ethyl vinyl ether, stearic acid amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, stearic acid amide ethyl allyl ether, and mixtures thereof.

[0142] The amide group-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamidoethyl (meth)acrylate, the amount of stearamidoethyl (meth)acrylate may be, for example, 40 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more, and 90 wt% or less, 80 wt% or less, or 70 wt% or less, based on the total weight of the amide group-containing monomers. The remaining monomer may be, for example, palmitamidoethyl (meth)acrylate.

[0143] (a2) Monomer Monomer (a2) has the formula: CH2=C(-X ａ２ )-C(=O)-Y ａ２ -R ａ２ [In the formula, R ａ２ is a hydrocarbon group having 2 to 40 carbon atoms, ａ２ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ２ is —O— or —NH—.]

[0144] The monomer (a2) is Y ａ２ a long chain acrylate ester monomer in which Y is —O—; ａ２ is a long chain acrylamide monomer in which R is —NH—. ａ２ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ａ２ In the formula (I), the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example, 16 to 26, and particularly preferably 18 to 22. ａ２ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0145] Preferred examples of the long-chain acrylate ester monomer include lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, and behenyl α-chloroacrylate. Preferred examples of the long-chain acrylamide monomer include stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0146] The hydrocarbon group-containing polymer of the present disclosure may contain repeat units derived from the following monomers:

[0147] (b) Hydrophilic Group-Containing Monomer The hydrocarbon group-containing polymer of the present disclosure may contain a repeating unit derived from a hydrophilic group-containing monomer (b). The monomer (b) is a monomer other than the monomer (a) that has a hydrophilic group.

[0148] The monomer (b) preferably has a (meth)acrylic group as the group having an ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond. The monomer (a) may have one or two groups having an ethylenically unsaturated double bond, but preferably has only one.

[0149] The hydrophilic group is preferably an oxyalkylene-containing group (the alkylene group has 2 to 6 carbon atoms), and particularly preferably an oxyethylene group. In particular, the monomer (b) is preferably an oxyalkylene (meth)acrylate, for example, polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or polyalkylene (or monoalkylene) glycol di(meth)acrylate, or polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0150] Monomer (b) has the formula: CH ２ =CX ｂ C(=O)-Y ｂ - (R ｂ O) ｎ -A ｂ [In the formula, Xｂ is a hydrogen atom or a methyl group, and Y ｂ is —O— or —NH—, R ｂ are each independently an alkylene group having 2 to 6 carbon atoms; ｂ represents a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH ２ =CX ｂ C(═O)—, and n is an integer of 1 to 90.

[0151] Examples of monomer (b) are those of the formula: CH ２ =CX ｂ C(=O)-O-(R ｂ O) ｎ -A ｂｉ (b1) and CH ２ =CX ｂ C(=O)-O-(R ｂ O) ｎ -C(=O)CX ｂ =CH ２ (b2), CH ２ =CX ｂ C(=O)-NH-(R ｂ O) ｎ -A ｂｉ (b3) wherein X ｂ are each independently a hydrogen atom or a methyl group; ｂｉ are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms; ｂ are each independently an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 90.

[0152] n may be, for example, 1 to 50, particularly 1 to 30, and especially 1 to 15 or 2 to 15. Alternatively, n may be, for example, 1. R ｂ may be a linear or branched alkylene group, for example, a group of the formula -(CH ２ ) ｘ - or - (CH ２ ) ｘ１ -(CH(CH ３ )) ｘ２- [wherein x1 and x2 are 0 to 6, for example, 2 to 5, and the sum of x1 and x2 is 1 to 6. -(CH ２ ) ｘ１ - and - (CH (CH ３ )) ｘ２ The order of - is not limited to the illustrated formula and may be random. ｂ O) n In -, R may be two or more types (for example, two to four types, particularly two types), and -(R ｂ O) n - is, for example, -(R １ O) ｎ１ - and - (R ２ O) ｎ２ - [wherein, R １ and R ２ are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90.

[0153] R in formulas (b1), (b2) and (b3) ｂ is particularly preferably an ethylene group, a propylene group or a butylene group, and particularly preferably a butylene group. ｂ R may be a combination of two or more alkylene groups. In this case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. ｂ Examples of the combination include a combination of an ethylene group / propylene group, a combination of an ethylene group / butylene group, and a combination of a propylene group / butylene group. The monomer (b) may be a mixture of two or more types. In this case, at least one of the monomers (b) is a mixture of R in formula (b1), (b2), or (b3). ｂ is preferably an ethylene group, a propylene group, or a butylene group. When a polyalkylene glycol di(meth)acrylate represented by formula (b2) is used, it is not preferable to use it alone as the monomer (b), but it is preferable to use it in combination with the monomer (b1). In that case, it is also preferable to keep the content of the compound represented by formula (b2) to less than 30% by weight of the monomer (b) used.

[0154] Specific examples of the monomer (b) can be exemplified by, for example, the following, but are not limited thereto. CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)O-H CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)O-H CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)O-H CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)O-H CH2=CHCOO-C(CH3)(CH2CH3)O-H CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)5-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O)5-CH3 CH2=CHCOO-(CH2CH2O)9-CH3 CH2=CHCOO-(CH2CH2O) 23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3

[0155] CH2=CHCOO-(CH2CH(CH3)O)9-H CH2=CHCOO-(CH2CH(CH3)O)9-CH3 CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3 CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=CHCOO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0156] CH2=CHCOO-(CH2CH2O)9-H CH2=C(CH3)COO-CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH3)O-H CH2=C(CH3)COO-CH(CH3)CH2O-H CH2=C(CH3)COO-CH2CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH(CH3)O-H CH2=C(CH3)COO-CH2CH(CH3)CH2O-H CH2=C(CH3)COO-CH(CH3)CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH2CH3)O-H CH2=C(CH3)COO-CH2C(CH3)2O-H CH2=C(CH3)COO-CH(CH2CH3)CH2O-H CH2=C(CH3)COO-C(CH3)2CH2O-H CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H CH2=C(CH3)COO-(CH2CH2O)2-H CH2=C(CH3)COO-(CH2CH2O)4-H CH2=C(CH3)COO-(CH2CH2O)5-H CH2=C(CH3)COO-(CH2CH2O)6-H CH2=C(CH3)COO-(CH2CH2O)9-H CH2=C(CH3)COO-(CH2CH2O)5-CH3 CH2=C(CH3)COO-(CH2CH2O)9-CH3 CH2=C(CH3)COO-(CH2CH2O) 23 -CH3 CH2=C(CH3)COO-(CH2CH2O) 90 -CH3 CH2=C(CH3)COO-(CH2CH(CH3)O)9-H

[0157] CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)COO-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0158] CH2=CH-C(=O)-NH-CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2C(CH3)2O-H CH2=CH-C(=O)-NH-(CH2CH2O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)5-H CH2=CH-C(=O)-NH-(CH2CH2O)6-H CH2=CH-C(=O)-NH-(CH2CH2O)9-H CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 23-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0159] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0160] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0161] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0162] The monomer (b) may be X ２ is a hydrogen atom. The monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0163] (c) Ionic Group-Containing Monomer The hydrocarbon group-containing polymer of the present disclosure may contain a repeating unit derived from an ionic group-containing monomer (c). The monomer (c) is preferably a monomer containing one ethylenically unsaturated double bond and an ionic group (particularly, an acrylic monomer). The ionic group is an anionic group and / or a cationic group, or a salt thereof.

[0164] The monomer (c) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0165] Examples of the monomer having an anionic group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having an anionic group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphate, vinylbenzenesulfonic acid, acrylamido-tertiarybutylsulfonic acid, and salts thereof.

[0166] Examples of salts of anionic groups include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0167] In the monomer having a cationic group, examples of the cationic group are amino groups, preferably tertiary amino groups and quaternary amino groups. In the tertiary amino group, two groups bonded to the nitrogen atom may be the same or different and may be an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an aromatic aliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an aromatic aliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have an ethylenically unsaturated double bond. The cationic group may be in the form of a salt.

[0168] The cationic group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and salts thereof are preferred.

[0169] Specific examples of the monomer having a cationic group are as follows: CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0170] The ionic group-containing monomer (c) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0171] (d) Halogenated Olefin Monomer The hydrocarbon group-containing polymer of the present disclosure may have a repeating unit derived from a halogenated olefin monomer (d). The halogenated olefin monomer (d) may not contain a fluorine atom. The halogenated olefin monomer (d) is preferably an olefin having 2 to 20 carbon atoms and substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. The halogenated olefin monomer (d) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred examples of the halogenated olefin monomer (d) include vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because it enhances water repellency (particularly the durability of water repellency). The presence of repeating units derived from the halogenated olefin monomer (d) can improve the washing durability of the hydrocarbon group-containing polymer.

[0172] (e) Crosslinkable Monomer The hydrocarbon group-containing polymer of the present disclosure may contain a repeating unit derived from a crosslinkable monomer (e). The crosslinkable monomer (e) has a reactive group and / or an ethylenically unsaturated double bond (preferably, a (meth)acrylate group). The crosslinkable monomer (e) may be a monomer that does not contain a fluorine atom. The crosslinkable monomer (e) may be a compound having at least two ethylenically unsaturated double bonds (preferably, a (meth)acrylate group), or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, and a carboxyl group.

[0173] Examples of the crosslinkable monomer may be a vinyl monomer having a reactive group, a mono(meth)acrylate, a di(meth)acrylate or a di(meth)acrylamide having a reactive group.

[0174] Examples of crosslinkable monomers include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0175] (f) Cyclic hydrocarbon group-containing monomer The hydrocarbon group-containing polymer of the present disclosure may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (f). The cyclic hydrocarbon group-containing monomer (f) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group. The hydrocarbon group-containing polymer of the present disclosure may be a styrene polymer having a repeating unit derived from styrene or a styrene derivative.

[0176] The cyclic hydrocarbon group-containing monomer (f) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0177] The cyclic hydrocarbon group may be alicyclic or aromatic. The cyclic hydrocarbon group may be saturated or unsaturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, with a bridged ring group being preferred. The cyclic hydrocarbon group may have a chain group (e.g., a halogen atom, a linear or branched chain hydrocarbon group (particularly a linear or branched chain hydrocarbon group having 1 to 20 carbon atoms)).

[0178] The cyclic hydrocarbon group may have 4 or more, 6 or more, or 8 or more carbon atoms, and may have 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less carbon atoms.

[0179] Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a bornyl group, an isobornyl group, a norbornyl group, a dicyclopentanyl group, a dicyclopentenyl group, a benzyl group, a phenyl group, a naphthyl group, a 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (for example, a cyclohexylene group, an adamantylene group, a phenylene group, a naphthylene group, etc.), and groups which are substitution products thereof.

[0180] Specific examples of the cyclic hydrocarbon group-containing monomer (f) include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0181] An example of the cyclic hydrocarbon group-containing monomer (f) is a styrene compound. The styrene compound may be modified with a chain group (for example, a halogen atom, or a linear or branched hydrocarbon group (particularly a linear or branched hydrocarbon group having 1 to 20 carbon atoms). Specific examples thereof include styrene, 4-t-butylstyrene, 3,5-di-t-butylstyrene, 2,4,6-tri-t-butylstyrene, 4-methylstyrene, 3,5-dimethylstyrene, and 2,4,6-trimethylstyrene. The styrene compound may be an α-methylstyrene compound or an α-chlorostyrene compound in which the α-position is a chlorine atom, or may be a styrene compound in which the α-position is a hydrogen atom.

[0182] (g) Polysiloxane Group-Containing Monomer The hydrocarbon group-containing polymer of the present disclosure may have a repeating unit derived from a polysiloxane group-containing monomer (g). The monomer (g) has one ethylenically unsaturated double bond and a polysiloxane group.

[0183] The monomer (g) preferably has a (meth)acrylic group, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0184] The polysiloxane group contained in the monomer (g) is the same as that described above for the polysiloxane group. The monomer (g) may have a polydimethylsiloxane group on its side chain.

[0185] The ethylenically unsaturated double bond and the polysiloxane group may be linked by an optional linker group.

[0186] Monomer (g) has the formula: CH ２ =C(-X ｇ )-C(=O)-Y ｇ (R) ｇ ｋ [In the formula, R ｇ is a group having a polydimethylsiloxane group, and X ｇ is a hydrogen atom, a monovalent organic group or a halogen atom, ｇ represents a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, —CH ２ -, -CH(-)２ ), -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NH-, and k is an integer of 1 to 3.

[0187] X ｇ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. ｇ Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. ｇ is preferably a hydrogen atom, a methyl group, or a chlorine atom. ｇ is particularly preferably a hydrogen atom.

[0188] Y ｇ is a divalent to tetravalent group. ｇ is preferably a divalent group. ｇ represents a hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ It is preferable that Y is a group constituted by at least one selected from - and -NH-. ｇ is preferably not a hydrocarbon group. Examples of hydrocarbon groups having one carbon atom include -CH ２ -, -CH(-) ２ or -C(-) ３ The hydrocarbon group having one carbon atom is repeated, and -(CH ２ ) m A hydrocarbon group having two or more carbon atoms may be formed, such as Y - (where m is an integer of 1 to 5). ｇ may have an NH group.

[0189] Y ｇ-Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [Wherein, Y' is a direct bond, -O-, -NH- or -S(=O) ２ - and R' is -(CH ２ ) m - (m is an integer of 1 to 5) or -C ６ H ４ -(phenylene group).

[0190] Y ｇ Specific examples of are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ ) m -O-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -C(=O)-O-, -NH-(CH ２ ) m -OC(=O)-, -NH-(CH ２ ) m -C(=O)-O-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m-NH-C(=O)-NH-、-O-(CH ２ ) m -O-C ６ H ４ -、-O-(CH ２ ) m -NH-S(=O) ２ -、-O-(CH ２ ) m -S(=O) ２ -NH-、-NH-(CH ２ ) m -O-C(=O)-NH-、-NH-(CH ２ ) m -NH-C(=O)-O-、-NH-(CH ２ ) m -C(=O)-NH-、-NH-(CH ２ ) m -NH-C(=O)-、-NH-(CH ２ ) m -NH-C(=O)-NH-、-NH-(CH ２ ) m -O-C ６ H ４ -、-NH-(CH ２ ) m -NH-C ６ H ４ -、-NH-(CH ２ ) m -NH-S(=O) ２ -、or -NH-(CH ２ ) m -S(=O) ２ -NH- is [where m is 1 to 5, particularly 2 or 4].

[0191] Y ｇ is, -O-, -NH-, -O-(CH ２ ) m -O-C(=O)-、-O-(CH ２ ) m -NH-C(=O)-、-O-(CH ２ ) m -O-C(=O)-NH-、-O-(CH ２ ) m -NH-C(=O)-O-、-O-(CH ２ ) m -NH-C(=O)-NH-、-O-(CH ２) m -NH-S(=O) ２ -, -O-(CH ２ ) m -S(=O) ２ -NH-, -NH-(CH ２ ) m -NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH- [wherein m is an integer of 1 to 5, particularly 2 or 4] is preferred. ｇ is -O- or -O-(CH ２ ) m —NH—C(═O)—, particularly —O—(CH ２ ) m It is more preferably —NH—C(═O)—.

[0192] R ｇ is a group having a polydimethylsiloxane group, and the above description of (polysiloxane group) is used for the polydimethylsiloxane group.

[0193] An example of the monomer (g) is: CH2=C(-X g )-C(=O)-Y g -[-Si(R s )2-O-] a -Si(R s )3 CH2=C(-X g )-C(=O)-Y g -L s1 -[-Si(R s )2-O-] a -Si(R s )3 CH2=C(-X g )-C(=O)-Y g -L s1 -OL s1 -[-Si(R s )2-O-] a -R s CH2=C(-X g )-C(=O)-Y g -L s1 -[-Si(R s )2-O-] a -Si(R s)3 CH2=C(-X g )-C(=O)-Y g -L s1 -OL s1 -[-Si(R s )2-O-] a -R s CH2=C(-X g )-C(=O)-Y g -L s1 -[-Si(R s )2-O-] a -Si(R s ) 3、 CH2=C(-X g )-C(=O)-Y g -L s1 -[-Si(R s )2-O-] a -R s [In the formula, the above explanations are used for each symbol.]

[0194] (h) Other Monomers The other monomers are not limited to these examples and include acrylonitrile, short-chain alkyl (meth)acrylate, vinyl acetate, vinyl alkyl ether, etc. The other monomers (h) may be used alone or in combination of two or more.

[0195] [Polymer Composition] The hydrocarbon group-containing polymer of the present disclosure may be one type of polymer selected from the group consisting of monomers (a) to (g), or may be a copolymer of two or more types. The combination of monomers (a) to (g) constituting the repeating units of the hydrocarbon group-containing polymer of the present disclosure is not particularly limited, and examples are as follows (parentheses omitted): a a+b a+b+c a+c a+d a+b+c+d a+b+c+d+e a+b+c+d+e+f In the above combinations, monomer (g) may be used in place of or in addition to monomer (a). Another monomer (h) may be used in the above combination. It is preferable to use monomer (a), monomer (b), and monomer (c) in combination.

[0196] The amount of repeating units derived from monomer (a) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the hydrocarbon group-containing polymer.

[0197] The amount of monomer (a) (particularly monomer (a1)) may be more than 90% by weight, 92% by weight or more, 94% by weight or more, 96% by weight or more, 98% by weight or more, 99% by weight or more, 99.5% by weight or more, or 100% by weight, based on the hydrocarbon group-containing polymer, for example, 93% by weight or more, preferably more than 97% by weight, and 100% by weight or less, 99% by weight or less, 97% by weight or less, 95% by weight or less, or 93% by weight or less, and in one embodiment, more than 90% by weight but 100% by weight or less. The amount of monomer (a1) may be 100% by weight based on the hydrocarbon group-containing polymer.

[0198] In the monomer (a), the amount of the monomer (a1) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, preferably 30% by weight or more, and may be 100% by weight or less, 90% by weight or less, 80% by weight or less, 50% by weight or less, or 30% by weight or less.

[0199] The amount of monomer (a2) in monomer (a) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, and may be 100% by weight or less, 90% by weight or less, 80% by weight or less, 50% by weight or less, or 30% by weight or less.

[0200] The amount of repeating units derived from monomer (b) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the hydrocarbon group-containing polymer. The amount of the repeating units derived from monomer (b) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0201] The amount of repeating units derived from monomer (c) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the hydrocarbon group-containing polymer. The amount of the repeating units derived from monomer (c) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0202] The amount of repeating units derived from monomer (d) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the hydrocarbon group-containing polymer; and the amount of repeating units derived from monomer (d) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the hydrocarbon group-containing polymer. The amount of the repeating units derived from monomer (d) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0203] The amount of repeating units derived from monomer (e) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the hydrocarbon group-containing polymer. The amount of the repeating units derived from monomer (e) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0204] The amount of repeating units derived from monomer (f) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the hydrocarbon group-containing polymer. The amount of the repeating units derived from monomer (f) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0205] The amount of repeating units derived from monomer (g) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the hydrocarbon group-containing polymer. The amount of the repeating units derived from monomer (g) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a).

[0206] The amount of repeating units derived from monomer (h) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, and may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the hydrocarbon group-containing polymer. The amount of the repeating units derived from monomer (h) may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 1000 parts by weight or more, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0207] When the monomer (g) is used instead of the monomer (a), "100 parts by weight of the amount of repeating units derived from the monomer (a)" in the above description of the amount of each monomer may be read as "100 parts by weight of the amount of repeating units derived from the monomer (g)."

[0208] [Polymerization Method] The hydrocarbon group-containing polymer can be produced by a known polymerization method, and the polymerization reaction conditions can be selected arbitrarily. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0209] In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of the monomers.

[0210] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate or butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, or methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, or isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCFC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3,000 parts by weight, for example, 50 to 2,000 parts by weight, per 100 parts by weight of the total of the monomers.

[0211] Emulsion polymerization involves emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, purging with nitrogen, and then polymerizing the mixture at a temperature ranging from 50 to 80°C for 1 to 20 hours with stirring. Examples of polymerization initiators that can be used include water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount ranging from 0.01 to 10 parts by weight per 100 parts by weight of the monomer.

[0212] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to polymerize the monomer by microparticulating it in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in a range of 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsification and copolymerization properties.

[0213] The water-soluble organic solvent may be any of the organic solvents described above. Examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0214] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomers.

[0215] [Amount of Polymer] The amount of the hydrocarbon group-containing polymer in the water repellent composition may be 0.01 wt% or more, 0.03 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, or 30 wt% or more, or may be 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, or 3 wt% or less. The hydrocarbon group-containing polymer itself may be used as the water repellent composition. The amount of the hydrocarbon group-containing polymer may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, relative to 100 parts by weight of the silicone compound, and may be 1000 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0216] [Wax] The water repellent composition of the present disclosure may contain a wax, particularly a hydrocarbon wax. The wax may be an organic substance that is solid at room temperature and becomes liquid when heated, and may be, for example, a hydrocarbon compound or a compound having a hydrocarbon group (e.g., an alkyl group) having 6 to 40 carbon atoms.

[0217] The waxes in the present disclosure can be adhered to a substrate (particularly a fibrous substrate) to impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate.

[0218] [Characteristics of Wax, etc.] The characteristics of wax, etc. are shown below.

[0219] The wax may be in a particulate (powder) form. The average particle size of the wax may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. The above particle size is the primary particle size. A particle size within the above range can provide excellent particle stability and good liquid repellency. The average particle size can be measured using a microscope (scanning electron microscope). Specifically, a wax particle sample is observed under a microscope at an arbitrary magnification. Next, if the particle shape is spherical, the diameter is considered to be the particle size, and if the particle shape is non-spherical, the average value of the longest and shortest diameters is considered to be the particle size. By measuring the particle size of all particles present within the field of view, and then moving the field of view and measuring the particle size again, particle sizes are measured at 100 or more points, and the average value is considered to be the average particle size.

[0220] The HD (n-hexadecane) contact angle of the wax may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may be 100° or less, 90° or less, or 75° or less. When the wax has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly oil repellency) to the substrate. The HD contact angle is the static contact angle of the wax with respect to a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle one second after the drop lands.

[0221] The water contact angle of the wax may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the wax has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the wax with respect to a spin-coated film, and is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0222] The wax may be a low molecular weight (e.g., a molecular weight of 1000 or less, or 500 or less) or a polymer. When the wax is a polymer, its weight average molecular weight may be 1000 or more, 3000 or more, 5000 or more, 7500 or more, 10000 or more, 30000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, or 10,000,000 or less, 7,500,000 or less, 5,000,000 or less, 3,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 3 ...,000 or less, 75000 or less, 50000 or less, or 3,000 or less.

[0223] The melting point of the wax may be 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, particularly preferably 55°C or higher, and may be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower, preferably 120°C or lower. The melting point of the wax may be measured in accordance with JIS K 2235-1991. The melting point usually corresponds to the peak top temperature of the endothermic peak with the maximum temperature before melting observed in DSC (differential scanning calorimetry).

[0224] [Types of Wax, etc.] Examples of waxes include mineral waxes (petroleum waxes) such as paraffin wax, microcrystalline wax, montan wax, ozokerite wax, ceresin wax, and petrolatum wax; and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax, and are preferably paraffin wax or microcrystalline wax. The wax in the present disclosure may be a hydrocarbon wax, preferably a chain aliphatic hydrocarbon, for example, a linear or branched hydrocarbon, and particularly a linear hydrocarbon.

[0225] [Amount of Wax] The amount of wax may be 0.1 part by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the silicone compound, or may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the hydrocarbon group-containing polymer.

[0226] [Isocyanate Derivative] The water repellent composition of the present disclosure may contain an isocyanate derivative. The isocyanate derivative has a hydrocarbon group having from 2 to 40 carbon atoms, particularly a monovalent hydrocarbon group having from 2 to 40 carbon atoms.

[0227] The isocyanate derivative is a compound obtained by reacting an active hydrogen compound with a raw material isocyanate, and has a portion derived from the active hydrogen-containing compound and a portion derived from the raw material isocyanate. Unlike isocyanate-based curing agents, the isocyanate derivative does not usually have an isocyanate group.

[0228] The isocyanate derivative has an -NHCO- group formed by the reaction of an active hydrogen compound with a raw material isocyanate (wherein -NHCO- may be part of a urethane group or a urea group). -NHCO- is a group formed by the reaction of an active hydrogen-containing group (typically a hydroxy group) of the active hydrogen compound with an active hydrogen-reactive group (typically an isocyanate group) of the raw material isocyanate. The isocyanate derivative is typically a urethane (particularly a polyurethane).

[0229] The hydrocarbon group having 2 to 40 carbon atoms contained in the isocyanate derivative is preferably a monovalent hydrocarbon group. With regard to the hydrocarbon group having 2 to 40 carbon atoms, the details already explained above in (Hydrocarbon group having 2 to 40 carbon atoms) are applicable.

[0230] The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic, or linear, and is more preferably linear, particularly linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0231] The weight average molecular weight of the isocyanate derivative may be 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less.

[0232] [Active Hydrogen Compound] The active hydrogen compound contains an active hydrogen group that reacts with an isocyanate group.

[0233] Examples of the active hydrogen group include a hydroxy group, an amino group, and a carboxyl group, and a typical example is a hydroxy group.

[0234] (α1) Hydrocarbon Alcohol The active hydrogen compound may be an active hydrogen compound (α1) composed of a hydrocarbon group and a hydroxyl group.

[0235] The hydrocarbon group in the active hydrogen compound (α1) is the aforementioned hydrocarbon group having 2 to 40 carbon atoms, and the above description is incorporated herein.

[0236] The active hydrogen compound (α1) preferably has one hydroxy group per molecule.

[0237] Examples of the active hydrogen compound (α1) include linear saturated hydrocarbon group-containing alcohols such as n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, and eicosanol; branched saturated hydrocarbon group-containing alcohols such as isomyristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol; linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icosenyl alcohol, docosenyl alcohol, tetracosenyl alcohol, hexacosenyl alcohol, and octacosenyl alcohol; and branched unsaturated hydrocarbon group-containing active hydrogen compounds such as phytol.

[0238] Here, a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol may be used in combination, and when a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 40 parts by mass or more, preferably 55 parts by mass or more, more preferably 70 parts by mass or more, and for example, 90 parts by mass or less, preferably 80 parts by mass or less, per 100 parts by mass of the total of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. The blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and for example, 60 parts by mass or less, preferably 45 parts by mass or less, more preferably 30 parts by mass or less, per 100 parts by mass of the total of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. When the blending ratio of the linear saturated hydrocarbon group-containing alcohol is equal to or greater than the above lower limit, the crystallinity of the hydrocarbon group is improved, and as a result, the liquid repellency of the treated object treated with this water repellent composition can be improved.

[0239] (α2) Sugar alcohol / hydroxy acid modified compound The active hydrogen compound may be a sugar alcohol / hydroxy acid modified compound (α2), which is a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) in which the hydrocarbon group having from 2 to 40 carbon atoms has been modified. The type of sugar alcohol / hydroxy acid is not limited and may be cyclic or acyclic. Examples of sugar alcohols include monosaccharides, reducing sugars, amino sugars, aldonic acids, and aldonic acid lactones, and examples of hydroxy acids include hydroxy polycarboxylic acids. The sugar alcohol / hydroxy acid may be a substance present in a living body. Examples of sugar alcohols / hydroxy acids include, but are not limited to, compounds derived from aldoses and ketoses, such as tetroses, pentoses, hexoses, and heptoses, and specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, gulose, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, mannopyranose, and the like. Examples of suitable sugar alcohols / hydroxy acids include talopyranose, allopyranose, altropyranose, idopyranose, gulopyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol, pentaerythritol, dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconic acid lactone, glyceric acid lactone, xylonic acid lactone, glucosamine, galactosamine, and mixtures thereof. The number of carbon atoms in the sugar alcohol / hydroxy acid may be 2 or more, 4 or more, or 6 or more, and 30 or less, 20 or less, or 10 or less. The average OH value of compound (α2) may range from greater than 0 to about 230, preferably from about 10 to about 175, and most preferably from about 25 to about 140.

[0240] The number of hydrocarbon groups having 2 to 40 carbon atoms in the sugar alcohol / hydroxy acid modified product (α2) may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may be 12 or less, 9 or less, 6 or less, or 3 or less.

[0241] In the sugar alcohol / hydroxy acid modified compound (α2), at least one active hydrogen atom (for example, a hydrogen atom in an OH group or a carboxyl group) of the sugar alcohol and / or the hydroxy acid is -R α２ , -C(O)R α２ , -(CH2CH2O) n (CH(CH3)CH2O) m R α２ , -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α２ or mixtures thereof, wherein R α２ is a hydrogen atom or a hydrocarbon group having from 2 to 40 carbon atoms, each n is independently 0 to 20, each m is independently 0 to 20, and m+n may be greater than 0. Compound (α2) has at least one active hydrogen, and for example, in a sugar alcohol / hydroxy acid modified product, at least one (one or more) of the active hydrogens of the sugar alcohol / hydroxy acid may be unmodified, and the active hydrogen (e.g., an —OH group) may react with an active hydrogen reactive group (particularly an isocyanate group) of compound (b) to form —NHCO—.

[0242] (α21) Sorbitan Modification The sugar alcohol / hydroxy acid modification (α2) may be a sorbitan modification (α21) in which sorbitan is modified with a hydrocarbon group having from 2 to 40 carbon atoms, and may in particular be an alkylsorbitan. α２ , -C(O)R α２ , -(CH2CH2O) n (CH(CH3)CH2O) m R α２ , -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α２ or a mixture thereof (wherein Rα２ is a hydrocarbon group having 2 to 40 carbon atoms). For example, sorbitan can be converted to -C(O)R α２ The alkyl sorbitan may be a mono-, di-, or tri-substituted compound. Here, the sorbitan may contain an amount of sorbitol, isosorbide, or other intermediates or by-products. Commercially available sorbitans such as SPAN can be used as the alkyl sorbitan.

[0243] In one embodiment, at least one active hydrogen substituent is —C(O)R α２ and R α２ may be a straight or branched chain alkyl group having 6 to 40 carbon atoms, more preferably 7 to 21 carbon atoms, and most preferably 11 to 21 carbon atoms. Preferred compounds include mono-, di-, and tri-substituted sorbitans derived from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and mixtures thereof. Particularly preferred compounds include mono-, di-, and tri-substituted sorbitan stearates or sorbitan behenin.

[0244] In one embodiment, R α２ may contain at least one unsaturated bond. Examples of such compounds (wherein at least one active hydrogen substituent is —C(O)R α２ and R α２ contains at least one unsaturated bond), sorbitan trioleate (i.e., in which R α２ Ha-C7H 14 CH=CHCH 17 Other examples include, but are not limited to, mono-, di-, and tri-substituted sorbitans derived from palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid.

[0245] In one embodiment, the sorbitan modification (α21) has at least one active hydrogen substituent, and the active hydrogen substituent is independently —(CHCHO). n (CH(CH3)CH2O) m R α２ or -(CHCHO)n (CH(CH3)CH2O) m C(O)R α２ (wherein each m is independently 0 to 20, each n is independently 0 to 20, and m+n is greater than 0.) Such compounds are known as polysorbates and are commercially available under the trade name TWEEN. These sorbitans are also known as R α２ Commercially available polysorbates can be mono-, di-, or trisubstituted with each R 2 From various polysorbates where R is H (unsubstituted), α２ It is known that sorbitan derivatives contain a wide variety of mixtures ranging from polysorbates in which m is a linear or branched alkyl group having 6 to 40 carbons (fully substituted), and mixtures of these various substitutions. Examples of such sorbitan modifications (α21) include polysorbates such as polysorbate tristearate and polysorbate monostearate. m+n is greater than 0 and R α２ Examples of sorbitan modifications (α21) containing at least one unsaturated bond include, but are not limited to, polysorbate trioleate (where R α２ is C7H 14 CH=CHCH 17 and is commercially available under the name Polysorbate 80. Sorbitan modifications (α21) may include mixtures of compounds with various active hydrogen substituents, and R α２ a compound in which R α２ may include mixtures with fully saturated compounds.

[0246] (α22) Citric Acid Modifications The sugar alcohol / hydroxy acid modification (α2) may be a citric acid modification (α22) in which citric acid is modified with a hydrocarbon group having from 6 to 40 carbon atoms, and may in particular be an alkyl citrate. For example, the citric acid modification (α22) may exist as a mono-, di-, or tri-substituted alkyl group. Mixtures of citrates with various values ​​of active hydrogen substituents may also be used, and R α２a compound having a hydrocarbon group having at least one unsaturated bond, and R α２ The citric acid modification (α22) may contain a mixture of -(CH2CH2O) and a compound in which -(CH2CH2O) is a fully saturated hydrocarbon. n (CH(CH3)CH2O) m R α２ or -(CHCHO) n (CH(CH3)CH2O) m C(O)R α２ wherein R α２ is a hydrocarbon group having 6 to 40 carbon atoms.) Examples of citric acid modifications (α22) include, but are not limited to, trialkyl citrates.

[0247] (α23) Pentaerythritol Modification The sugar alcohol / hydroxy acid modification (α21) may be a pentaerythritol modification (α23) in which pentaerythritol is modified with a hydrocarbon group having from 6 to 40 carbon atoms, and may be a mono-, di-, or tri-substituted product having a hydrocarbon group (particularly an alkyl group) having from 6 to 40 carbon atoms, such as a dipentaerythriol ester. The active hydrogen substituent is —CHC[CHOR α２ ]3, where R α２ is a hydrocarbon group having 6 to 40 carbon atoms.) The pentaerythritol modification (α23) is a compound having a mixture of hydrocarbon groups with different chain lengths, or R α２ a compound in which R α２ The carboxylic acid may contain a mixture of fully saturated compounds with the carboxylic acid.

[0248] (α3) Cationic Active Hydrogen Compound The active hydrogen compound may be a cationic active hydrogen compound (α3) having an active hydrogen group and a cationic group.

[0249] The cationic active hydrogen compound (α3) preferably has two or more hydroxy groups per molecule.

[0250] An example of the cationic group is a tertiary amino group.

[0251] That is, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a cationic group.

[0252] Such cationic active hydrogen compounds can impart good dispersibility in a liquid medium (e.g., water) and can also introduce cationic groups having affinity for textile products (described later) into the resin, thereby improving washing durability.

[0253] More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as the active hydrogen groups and a tertiary amino group as the cationic group.

[0254] Examples of such cationic active hydrogen compounds include alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, and propanolamine, and trialkanolamines such as N-triethanolamine and N-triisopropanolamine, and preferably N-methyldiethanolamine.

[0255] The cationic active hydrogen compound (or the portion of the water-repellent compound derived from the cationic active hydrogen compound) may form a salt with an acid compound.

[0256] Examples of the acid compound include organic acids and inorganic acids. Examples of the organic acid include acetic acid, lactic acid, tartaric acid, malic acid, etc., preferably acetic acid and lactic acid, and more preferably acetic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, etc., preferably hydrochloric acid. Examples of the acid compound include organic acids. When the acid compound contains an organic acid, the acid volatilizes upon heat treatment, thereby improving the liquid repellency of an article treated with this water repellent composition. Furthermore, the acid volatilizes upon heat treatment, which makes it easier for cationic groups to be adsorbed onto textile products, thereby improving the washing durability of the textile products.

[0257] (α4) Other Active Hydrogen-Containing Compounds The active hydrogen compound (α) may contain other active hydrogen compounds (α4).

[0258] (α41) Compound The active hydrogen compound (α4) is represented by the formula R α４１ -X α４１ [In the formula, In the formula, R α４１ is a C1-C2 alkyl group which may contain at least one unsaturated group; 30 Straight or branched chain alkyl, hydroxy-functional C1-C 30 Straight or branched chain alkyl, hydroxy-functional straight or branched chain C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Straight or branched alkyl, amine functional C1-C 30 linear or branched alkyl, Y － R α４１１ R α４１２ R α４１３ N ＋ -R α４１４ - (where Y is a halide ion, e.g., Cl － ), HOS(=O) ２ -R α４１４ - or R α４１１ R α４１２ C=N- (where R α４１１ , R α４１２ , R α４１３ are each independently —H or C1-C6 alkyl, and R α４１４ is a divalent alkyl group having 1 to 20 carbon atoms; α４１ is -OH, -C(O)OH, -SH, -NH(R'), -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CHCHO) s (CH(CH3)CH2O) t isocyanate-reactive functional groups such as —H, where R ’ represents —H or a monovalent organic group, s represents an integer of 0 to 50, t represents an integer of 0 to 50, and s+t is greater than 0.

[0259] Compound (α41) may be a hydrophilic, water-soluble material comprising at least one hydroxy-terminated polyether, wherein X α４１ is -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O)s(CH(CH3)CH2O) t The -(CHCHO)- represents an oxyethylene group (EO), and the -(CH(CH)CHO)- represents an oxypropylene group (PO). These polyethers can contain only EO groups, only PO groups, or a mixture thereof. These polyethers may also exist as designated PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymers.

[0260] In one embodiment, X α４１ is -OH, -C(O)OH, -SH, -NH(R ’ ) and R α４１ is a C-C group optionally containing at least one unsaturated group 30 Straight or branched chain alkyl, hydroxy-functional C1-C 30 Straight or branched chain alkyl, hydroxy-functional straight or branched chain C1-C 30 Polyethers, hydroxy-functional linear or branched polyesters, hydroxy- or amine-functional linear or branched organosiloxanes, thiol-functional C1-C 30 Straight or branched alkyl, amine functional C1-C 30 It is selected from straight or branched chain alkyl.

[0261] X α４１ may be —OH, and examples of such compounds (α41) include alkyl alcohols such as propanol, butanol, or fatty alcohols including stearyl alcohol (R α４１ optionally containing at least one unsaturated group, C1-C 30 alkyl diols or polyols (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 59 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69 , R 70 , R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 , R 89 , R 90 , Rα４１ is a hydroxy-functional C-C 30 alkylene glycol ethers such as triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or glycol ethers (R ) having a mixture of PEG, PPG or THF units; α４１ is a hydroxy-functional straight or branched chain C-C 30 Polyether), polyester polyol (R α４１ is a hydroxy-functional linear or branched polyester), silicone prepolymer polyol (R α４１ is a hydroxy-functional linear or branched organosiloxane), N,N-dimethylaminoethanol (R α４１ is an amine functional C-C 30 straight or branched chain alkyl), choline chloride or betaine HCl (R α４１ Is Y － R α４１１ R α４１２ R α４１３ N ＋ -R α４１４ -), butanone oxime (R α４１ is R α４１１ R α４１２ Polyether polyols include, but are not limited to, polyether glycols (wherein the hydroxyl group is C═N—). The polyether polyols can contain only EO groups, only PO groups, only THF groups, or mixtures thereof. These polyethers can also exist as block copolymers, such as those designated by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). The polyether glycols preferably have an average molecular weight of about 200 or greater, most preferably 350 to 2000.

[0262] X α４１may be —C(O)OH, and examples of such compounds (α41) include fatty acids (R α41) such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, or erucic acid. α４１ is a C-C group optionally containing at least one unsaturated group 30 hydroxy-containing acids (R alkyl esters), such as hydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybehenic acid, hydroxylignoceric acid, hydroxypalmitoleic acid, hydroxylinoleic acid, hydroxyarachidonic acid, hydroxyoleic acid, or hydroxyerucic acid; α４１ is a hydroxy-functional C-C 30 linear or branched alkyl), and mercaptoalkanoic acids such as mercaptopropionic acid (R α４１ is a thiol functional C-C 30 and the like. The alkyl groups include, but are not limited to, straight or branched chain alkyl groups.

[0263] X α４１ may be —SH, and examples of such compounds (α41) include alkyl thiols (R α４１ is a C-C group optionally containing at least one unsaturated group 30 and the like. The alkyl groups include, but are not limited to, straight or branched chain alkyl groups.

[0264] X α４１ may be —NH(R′), and examples of such compounds (α41) include alkylamines (R α４１ is a C-C group optionally containing at least one unsaturated group 30 an alkanolamine (R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 2 α４１ is a hydroxy-functional C-C 30linear or branched alkyl), silicone prepolymer polyamine (R α４１ is an amine-functional linear or branched organosiloxane), alkyldiamine (R α４１ is an amine functional C-C 30 straight-chain or branched-chain alkyl), and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid (R α４１ is HO-S(O)2R α４１４ -), but are not limited to.

[0265] Compound (α42) Compound (α42) is a compound represented by the formula R α４２１ -(OCH2CH(OR α４２２ ) CH2) z -OR α４２３ [In the formula, R α４２１ , R α４２２ and R α４２３ is at least one R α４２１ , R α４２２ or R α４２３ are —H, and each independently represents —H, —R α４２４ , -C(O)R α４２４ and R α４２４ are independently a straight-chain or branched-chain alkyl group having 5 to 29 carbon atoms which may contain at least one unsaturated bond, and z is 1 to 15.

[0266] Compound (α42) may be a compound generally known as polyglycerol. Other specific examples include, but are not limited to, triglycerol monostearate, triglycerol distearate, hexaglycerol monostearate, hexaglycerol distearate, decaglyceryl mono(caprylate / caprate), decaglyceryl di(caprylate / caprate), decaglycerol, polyglycerol-3, and C18 diglyceride.

[0267] (α43) Chain Extender The compound (α4) may be a chain extender (α43). The chain extender (α43) is a compound having two or more (for example, two) functional groups containing active hydrogen in the molecule. As the chain extender, known chain extenders can be used, and examples thereof include aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; phenolic hydroxyl group-containing compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, and o,o'-diallyl-bisphenol A; and alcohol amines such as aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, and aminohexylpropanolamine.

[0268] Starting Isocyanate The isocyanate derivative has a moiety derived from the starting isocyanate.

[0269] Examples of raw material isocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4', or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or aromatic polyisocyanates selected from 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI), ω,ω'-diisocyanato-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4-, or 1,8-naphthalene diisocyanate or mixtures thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate;acyclic aliphatic polyisocyanates selected from trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaprate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate; 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate or a mixture thereof) (hydrogenated MDI), methylcyclohexyl Cycloalicyclic polyisocyanates selected from among methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); bridged cycloaliphatic polyisocyanates selected from among norbornene diisocyanate, norbornane diisocyanatomethyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, and di(diisocyanatomethyl)tricyclodecane; and biuret-modified products of the above-mentioned isocyanates, polymers of polyisocyanates (for example, dimers, trimers (for example, isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (for example, allophanate derivatives produced by the reaction of the above-mentioned polyisocyanates with monohydric alcohols or dihydric alcohols), polyol derivatives (for example, polyol derivatives (alcohol adducts, preferably trimethylolpropane) produced by the reaction of the above-mentioned polyisocyanates with trihydric alcohols (for example, trimethylolpropane, etc.) Examples of the derivatives include biuret derivatives (e.g., biuret derivatives formed by the reaction of the above-mentioned polyisocyanates with water or amines), urea derivatives (e.g., urea derivatives formed by the reaction of the above-mentioned polyisocyanates with diamines), oxadiazinetrione derivatives (e.g., oxadiazinetrione formed by the reaction of the above-mentioned polyisocyanates with carbon dioxide), carbodiimide derivatives (e.g., carbodiimide derivatives formed by the decarboxylation condensation reaction of the above-mentioned polyisocyanates), uretdione derivatives, and uretonimine derivatives.

[0270] The average number of isocyanate groups in the raw material isocyanate is 2 or more, preferably 2.5, more preferably 2.9, and for example, 3.8 or less. The raw material isocyanate may be a polyisocyanate having a plurality of isocyanate groups.

[0271] [Method for Synthesizing Isocyanate Derivatives] To obtain an isocyanate derivative, an active hydrogen compound is reacted with a raw material isocyanate. The reaction may be carried out in one step or in multiple successive steps. For example, if unreacted active hydrogen groups or active hydrogen-reactive groups exist in the product, the synthesis may be carried out successively. Successive reactions are particularly useful when using a substituted sugar alcohol with a high OH number. Reaction conditions such as reaction concentration and reaction temperature are not particularly limited and can be determined by those skilled in the art. Specifically, the active hydrogen compound and the raw material isocyanate may be blended so that the equivalent ratio of active hydrogen-reactive groups (isocyanate groups) to active hydrogen groups (active hydrogen-reactive groups / active hydrogen groups) is, for example, 1.2 or more, preferably 1.5 or more, and, for example, 2.0 or less.

[0272] [Composition of Isocyanate Derivative] The amount of the portion derived from the active hydrogen compound may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the amount of the isocyanate derivative.

[0273] The amount of the portion derived from the hydrocarbon alcohol (α1) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the portion derived from the active hydrogen compound.

[0274] The amount of the portion derived from the sugar alcohol / hydroxy acid modified product (α2) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, relative to the portion derived from the active hydrogen compound, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less.

[0275] The amount of the portion derived from the cationic active hydrogen compound (α3) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the portion derived from the active hydrogen compound.

[0276] The amount of the portion derived from the other active hydrogen-containing compound (α4) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the portion derived from the active hydrogen compound.

[0277] The amount of the portion derived from the raw isocyanate may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, or 15% by weight or less, based on the isocyanate derivative.

[0278] [Amount of Isocyanate Derivative] The amount of the isocyanate derivative may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the silicone compound, and may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the hydrocarbon group-containing polymer.

[0279] [Dispersant] The water repellent composition of the present disclosure may contain a dispersant. The dispersant may be at least one selected from organic dispersants and inorganic dispersants. The dispersant may be at least one selected from anionic dispersants, nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants. In particular, the water repellent composition of the present disclosure may contain a nonionic dispersant, or a combination of a nonionic surfactant and a cationic surfactant. By containing a dispersant, water repellency, slip resistance, and storage stability can be favorably achieved.

[0280] As the dispersant, an organic dispersant and an inorganic dispersant may be used individually, or a combination of an organic dispersant and an inorganic dispersant may be used.

[0281] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may refer to a surfactant.

[0282] The dispersant may not have a fluorine atom.

[0283] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant, which may be a nonionic surfactant.

[0284] The nonionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the nonionic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0285] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0286] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0287] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0288] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0289] Examples of alkanolamides are those formed from fatty acids and alkanolamines. The alkanolamides may be monoalkanolamides or dialkanolamines. Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0290] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0291] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0292] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0293] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, those in which the alkylene oxide adduct moiety and the polyalkylene glycol moiety have a structure of polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not have to contain an aromatic group.

[0294] The nonionic dispersant has the formula: １ O-(CH ２ CH ２ O) ｐ - (R ２ O) ｑ -R ３ [In the formula, R １ is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms, and R ２ are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), ３ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.

[0295] R １ R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. １ Preferred specific examples of R include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. ２ Examples of the nonionic dispersant are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R ２ O) ｑ - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, with the oxypropylene chain being preferred.

[0296] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C １２ -C １６ ) thiol, sorbitan mono fatty acid (C ７ -C １９ ) or alkyl(C １２ -C １８ ) condensation products with amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0297] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may contain a compound with an HLB (hydrophilic-hydrophobic balance) of 10 or less, or may be a mixture of a compound with an HLB of less than 15 (particularly 5 or less) and a compound with an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylene having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0298] [Cationic Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0299] The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0300] The cationic dispersant may be aliphatic or aromatic, and examples thereof include ammonium salts (e.g., quaternary ammonium salts). The cationic dispersant may be an oxyethylene adduct ammonium salt. Specific examples include amine salt-type dispersants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymer-type cationic dispersants such as Polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0301] The low molecular weight cationic dispersant is R ２１ -N ＋ (-R ２２ ) (-R ２３ ) (-R ２４ ) X － [In the formula, R ２１ , R ２２ , R ２３ and R ２４ is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group. ２１ , R ２２ , R ２３ and -R ２４ Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups) and aromatic groups (e.g., benzyl and phenyl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms) and benzalkonium chloride.

[0302] Specifically, the low molecular weight cationic dispersant is represented by the formula: １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g. C１２ ~C ５０ ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group of the formula R ２ is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH ３ , C ２ H ５ is particularly preferred), and X is a halogen atom (e.g., chlorine), or C １ ~C ４ or a fatty acid salt of C １ ~C ４ where p is 1 or 2, q is 2 or 3, and p+q=4. １ may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0303] Examples of low molecular weight cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0304] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to -47) having a cationic group (e.g., ammonium group, quaternary ammonium group). Examples of the polymeric cationic dispersant include cationic natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0305] [Anionic Dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0306] The anionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the anionic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0307] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid type dispersants, phosphate mono- or diester type dispersants, and sulfosuccinate esters. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0308] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant, which may be an amphoteric surfactant.

[0309] The amphoteric dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the amphoteric dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0310] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0311] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0312] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0313] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0314] [Amount of Dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the silicone compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less. The amount of the dispersant may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrocarbon group-containing polymer, and may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0315] [Liquid Medium] The water repellent composition of the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The water repellent composition may be a dispersion or a solution. The water repellent composition of the present disclosure is preferably an aqueous dispersion.

[0316] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., alcohol, polyols such as glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination.

[0317] The water repellent composition of the present disclosure may be an organic solvent solution or an organic solvent dispersion. An organic solvent solution refers to a liquid in which a solute is dissolved in a solvent to form a uniform phase. An organic solvent dispersion refers to a liquid in which a solute is suspended or floated in the solvent in the form of particles, and which can be separated into a solute (dispersoid) and a solvent by centrifugation or the like.

[0318] [Amount of Liquid Medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the silicone compound.

[0319] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the silicone compound.

[0320] The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the silicone compound.

[0321] [Organic Acid] The water repellent composition of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one organic acid may be used, or two or more organic acids may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0322] [Amount of Organic Acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the silicone compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the water repellent composition is 3 to 10, for example, 5 to 9, particularly 6 to 8. The water repellent composition may be acidic (pH 7 or less, for example, 6 or less). The amount of the organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrocarbon group-containing polymer, and may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0323] [Inorganic Acid] The water repellent composition of the present disclosure may contain an inorganic acid. Known inorganic acids can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present disclosure, one type of inorganic acid may be used, or two or more types may be used in combination. Addition of an inorganic acid can improve the stability of the aqueous dispersion.

[0324] [Amount of Inorganic Acid] The amount of inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the silicone compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of inorganic acid may be adjusted so that the pH of the water repellent composition is 3 to 10, for example, 5 to 9, particularly 6 to 8. The water repellent composition may be acidic (pH 7 or less, for example, 6 or less). The amount of the inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrocarbon group-containing polymer, and may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0325] [Hardening Agent] The water repellent composition of the present disclosure may contain a hardening agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). When the water repellent composition is for paper (e.g., an oil-proofing agent for paper), it does not need to contain a hardening agent.

[0326] The curing agent (crosslinking agent) in the water repellent composition can satisfactorily cure the water repellent composition. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with active hydrogen or an active hydrogen-reactive group. Examples of the active hydrogen-reactive compound include isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, melamine compounds, and urea-based compounds.

[0327] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

[0328] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate, Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0329] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3,5-triisocyanatocyclohexane, 4,4'methylenebis(cyclohexyl isocyanate), and 1,3-bis(isocyanatomethyl)cyclohexane. These may be used alone or in combination of two or more.

[0330] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0331] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0332] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0333] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as the water repellent composition.

[0334] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, and pyrazole compounds. The polyisocyanate compounds can be used alone or in combination of two or more.

[0335] An epoxy compound is a compound having an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound having a chloromethyl group. An example of a chloromethyl group-containing compound is chloromethyl polystyrene. A carboxyl group-containing compound is a compound having a carboxyl group. Examples of a carboxyl group-containing compound are (poly)acrylic acid, (poly)methacrylic acid, etc.

[0336] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resin and methyl etherified melamine resin. Specific examples of urea compounds include dimethylol dihydroxyethylene urea (DMDHEU) and dimethyl dihydroxyethylene urea.

[0337] [Amount of Curing Agent] The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the silicone compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of the curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrocarbon group-containing polymer, and may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0338] [Other Components] The water repellent composition may contain other components in addition to the above-mentioned components. Examples of other components include water and / or oil repellents, antislip agents, antistatic agents, preservatives, antibacterial agents, deodorizers, penetrants, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components include texture adjusters, softeners, antibacterial agents, flame retardants, wrinkle inhibitors, crosslinking agents, film-forming aids, compatibilizers, UV absorbers, antioxidants, pH adjusters, insect repellents, antifoaming agents, shrinkage inhibitors, anti-wrinkle agents, shape retention agents, drape retention agents, ironing improvers, polymer dispersants, scum dispersants, fluorescent brighteners, dye fixatives, and foam inhibitors. These may be used alone or in combination of two or more.

[0339] (Antistatic Agent) Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, and nonionic antistatic agents such as aminoalcohols and its derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. Ionic conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ionic conductive groups may also be used. These may be used alone or in combination of two or more.

[0340] (Preservatives) Preservatives can be used primarily to enhance preservative and bactericidal properties and maintain preservative properties during long-term storage. Examples of preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The content of the preservative is preferably 0.0001 to 1 wt % relative to the total weight of the water repellent composition. When the content of the preservative is equal to or greater than the lower limit of the above range, the effect of adding the preservative can be sufficiently obtained, and when it is equal to or less than the upper limit, the storage stability of the water repellent composition is good.

[0341] (Antibacterial Agent) An antibacterial agent is a component that has the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors resulting from microbial decomposition products. Examples of the antibacterial agent include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylenebiguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0342] (Deodorant) Examples of deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (e.g., zinc complex of trisodium methylglycine diacetate described in WO 2012 / 090580).

[0343] (Anti-slip Agent) A component that has the effect of suppressing slippage of fibers and sewn parts during sewing or wearing. Examples of anti-slip agents include polysiloxane compounds, colloidal silicas (silica particle dispersions), silicone resin derivatives, colloidal organic silicones, and amino-modified silicones.

[0344] (Softener) Softener is a component that has the effect of imparting a soft and smooth texture to fabrics. Examples of softener components include cationic surfactants such as quaternary ammonium salts and amine salts, anionic surfactants such as soap, sulfated oil, higher alcohol sulfate ester salts and sulfonate salts, nonionic surfactants such as polyhydric alcohols and polyethylene glycols, amphoteric surfactants such as betaines and amino acids, and siloxane resins.

[0345] [Amount of Other Components] The amount of each or the total amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the silicone compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, relative to 100 parts by weight of the hydrocarbon group-containing polymer, and may be 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0346] <Applications of Water Repellent Composition> Examples of applications of the water repellent composition according to the present disclosure include an external treatment agent (surface treatment agent) or an internal treatment agent, a repellent (a water repellent, an oil repellent, or a water and oil repellent, etc., particularly a water repellent), an antifouling agent, a soil release agent, a stripping agent, a release agent (an external release agent or an internal release agent), and the like.

[0347] <Method for Producing Treated Product> The method for producing a treated product in the present disclosure includes treating a substrate with a water repellent composition.

[0348] [Treated Products] Substrates that can be treated with the water repellent composition of the present disclosure include textiles, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Various examples of textile products can be mentioned. Examples include natural fibers of animal and plant origin such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber; and mixtures thereof. As an example of a substrate that can be treated with the water repellent composition, a woven or knitted fabric will be described in detail.

[0349] (Woven and knitted fabrics) - Manufacturing method of woven and knitted fabrics Woven and knitted fabrics can be obtained by weaving and knitting long and short fiber yarns made of the above-mentioned fibers to obtain a greige fabric, which is then post-processed and subjected to a water-repellent treatment. The weaving and knitting can be performed using known looms and knitting machines, and the preparation process prior to the weaving and knitting can also be performed using known equipment.

[0350] The woven or knitted fabric can be post-processed using known scouring and dyeing methods and equipment suited to the fiber material of the woven or knitted fabric.

[0351] After the post-processing, the woven or knitted fabric may be subjected to a water-repellent treatment. In the water-repellent treatment, first, an aqueous solution containing a water repellent (which may be the water-repellent composition of the present disclosure) is prepared. Next, the aqueous solution is applied to the woven or knitted fabric after the post-processing using a padding method, a spray method, a kiss roll coater method, a slit coater method, or the like, and then dried and subjected to a dry heat treatment. The aqueous solution may also contain a crosslinking agent, a softener, an antistatic agent, or the like, as necessary. After the water-repellent treatment, the woven or knitted fabric may be calendered.

[0352] The woven and knitted fabrics are suitable for use in clothing applications where water repellency is required, particularly in sportswear applications for outdoor activities, skiing, snowboarding, golf, etc., and uniform applications.

[0353] The woven / knitted fabric of the present disclosure may be provided as a laminated fabric having a moisture-permeable waterproof layer on one side thereof. The moisture-permeable waterproof layer may be laminated directly onto the woven / knitted fabric, or may be laminated onto the woven / knitted fabric via an adhesive layer. When the laminated fabric of the present disclosure is used for clothing or the like, the woven / knitted fabric side is arranged to repel rainwater and the like.

[0354] - Moisture-permeable waterproof layer The moisture-permeable waterproof layer is a layer that covers one side of a woven or knitted fabric, and is formed from a waterproof and moisture-permeable resin or structural film.

[0355] The moisture-permeable waterproof layer may be formed by applying a resin (the resin that constitutes the moisture-permeable waterproof layer) directly to the woven or knitted fabric, or may be laminated to one side of the woven or knitted fabric via an adhesive layer described below.

[0356] The resin that constitutes the moisture-permeable waterproof layer is not particularly limited, but non-porous and porous resins are used. For non-porous ones, polyurethane resins and polyester elastomer resins that contain hydrophilic components are used to provide moisture permeability. For porous ones, polyurethane resins that form wet-process porous membranes and polyurethane resins that are made porous by electrospinning are used, as well as porous PTFE membranes and porous membranes made of PE or PP.

[0357] As the polyurethane resin, a conventionally known resin obtained by reacting a polyisocyanate component with a polyol component can be used.

[0358] A moisture-permeable waterproof membrane having a microporous structure can be obtained by wet coagulation of a DMF solution of a polyurethane resin containing an inorganic fine powder. Examples of inorganic fine powder include fine powders made of silicon dioxide, aluminum dioxide, or titanium dioxide. The average primary particle size of the inorganic fine powder is preferably about 7 to 40 nm. The content of the inorganic fine powder is preferably 3 to 50 wt %, and more preferably 5 to 50 wt %, of the total weight of the moisture-permeable waterproof layer.

[0359] The thickness of the moisture-permeable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. A thickness within this range provides an excellent balance between waterproofness and moisture permeability, and is also advantageous in terms of texture.

[0360] Adhesive layer: The laminated fabric preferably includes an adhesive layer. That is, the woven or knitted fabric and the moisture-permeable waterproof layer are preferably laminated via an adhesive layer. In terms of moisture permeability, it is also preferable that the adhesive layer be a discontinuous layer such as a dot or grid pattern.

[0361] The type of adhesive that constitutes the adhesive layer is not particularly limited, but it is preferable that it has excellent adhesion to the moisture-permeable waterproof layer. For example, if a resin containing polyurethane resin as the main component is selected as the resin that constitutes the moisture-permeable waterproof layer, it is preferable to use an adhesive layer made of a polyurethane-based adhesive. The polyurethane-based adhesive may be of any structure, such as an ether-based, ester-based, or polycarbonate-based adhesive.

[0362] The adhesive layer may be formed over the entire surface of one side of the woven or knitted fabric, or may be formed in a pattern from the viewpoint of moisture permeability, texture, etc. The pattern shape is not particularly limited, but examples include dots, lines, a grid, a checkerboard pattern, a tortoiseshell pattern, etc., and it is preferable that any of these patterns be uniformly arranged over the entire surface.

[0363] The thickness of the adhesive layer is preferably about 10 to 100 μm, and more preferably 20 to 80 μm.

[0364] In the laminated fabric of the present disclosure, a lining fiber fabric may be laminated on the moisture-permeable waterproof layer (on the side of the moisture-permeable waterproof layer opposite to the side on which the woven or knitted fabric of the present disclosure is laminated). The lining fiber fabric can protect the moisture-permeable waterproof layer and can provide even better waterproofness (water pressure resistance) and strength.

[0365] Examples of the fiber fabric for the lining include various woven fabrics, knitted fabrics, etc. Among them, knitted fabrics are preferred because, compared with woven fabrics, the constituent yarns are more likely to protrude from the surface, resulting in an uneven surface, and the knitted fabric exhibits a stronger anchoring effect, making it less likely to peel off from the moisture-permeable waterproof layer.

[0366] Furthermore, tricot knitted fabrics are also preferred in that they can be produced as long grey fabrics during knitting, have few seams, and can be evenly layered on the moisture-permeable waterproof layer.

[0367] The material of the fibers constituting the lining fiber fabric is not particularly limited and can be selected as appropriate, but nylon fiber is preferred. This is because acid dyes are generally used in nylon fibers, which makes it less likely for the disperse dye to migrate and sublimate into the moisture-permeable waterproof layer, a problem that occurs with polyester fibers, etc., which use disperse dyes. The form (long fiber, short fiber, or spun yarn) or fineness of the fibers constituting the lining fiber fabric is not particularly limited and can be selected as appropriate as long as the effects of the present disclosure are not impaired.

[0368] Characteristics of the Laminated Fabric The laminated fabric has excellent waterproofness. A suitable example of the waterproofness of the laminated fabric of the present disclosure is a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) of, for example, 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more.

[0369] The laminated fabric has excellent moisture permeability. A preferred example of the moisture permeability of the laminated fabric of the present disclosure is a moisture permeability of, for example, 10,000 g / m2, as measured in accordance with JIS L 1099:2021 B-1 method (potassium acetate method). 2 24 hours or more, preferably 15,000 g / m 2 24 hours or more, more preferably 20,000 g / m2 The upper limit of the moisture permeability is not particularly limited, but is, for example, 40,000 g / m 2 24h or 35,000g / m 2 24h mm. In addition, the moisture permeability measured in accordance with JIS L 1099:2021 A-1 method (calcium chloride method) is, for example, 4000 g / m 2 24 hours or more, preferably 8000 g / m 2 24 hours or more, more preferably 10,000 g / m 2 24 hours or more. The upper limit of the moisture permeability is 13,000 to 15,000 g / m2, which is the limit of the measurement method. 2 ・It will take about 24 hours.

[0370] In the laminated fabric of the present disclosure, the peel strength between the woven or knitted fabric and the breathable waterproof layer, as measured in accordance with the method of JIS K 6404-2, is preferably 2.55 N / 2.54 cm or more for clothing applications, and may be preferably 5 N / 2.54 cm or more for use in applications.

[0371] - Manufacturing method of laminated fabric There are no particular limitations on the manufacturing method of the laminated fabric, and examples include the first manufacturing method and the second manufacturing method shown below. First manufacturing method: Includes a step of forming the moisture-permeable waterproof layer by applying a resin that constitutes the moisture-permeable waterproof layer to the surface of a woven or knitted fabric. Second manufacturing method: Includes a step of forming an adhesive layer on the woven or knitted fabric or the moisture-permeable waterproof layer, and a step of bonding the woven or knitted fabric and the moisture-permeable waterproof layer together via the adhesive layer.

[0372] In the first manufacturing method, the resin that constitutes the moisture-permeable waterproof layer can be applied to the surface of the woven or knitted fabric by, for example, a coating method. A knife coater or a comma coater can be used in the coating method. From the viewpoint of providing excellent moisture permeability, it is preferable to obtain the moisture-permeable waterproof layer by a wet method.

[0373] In the second manufacturing method, examples of techniques for forming an adhesive layer on a woven or knitted fabric or a moisture-permeable waterproof layer include lamination. In the lamination method, a resin solution or a hot-melt method can be used to form the adhesive layer. First, a moisture-permeable waterproof layer-forming resin composition (e.g., a resin composition containing a resin and an organic solvent) is applied to the surface of a release material (such as release paper, release cloth, or release film) with a clearance, and a moisture-permeable waterproof layer is formed while adjusting the thickness. The film is then dried and heat-treated to obtain a film. The release material can be removed as appropriate after lamination or aging. Furthermore, when laminating using a hot-melt method, the release material can be peeled off and the film can be laminated alone. Furthermore, the moisture-permeable waterproof membrane can be formed by laminating a membrane produced by a solventless extrusion method such as the T-die method or inflation method, a porous membrane produced by electrospinning, or a porous membrane made of PTFE, PE, PP, or the like.

[0374] An adhesive layer is then formed on the woven or knitted fabric or the moisture-permeable waterproof layer. For example, in the case of a method using a resin solution, a two-component curing polyurethane resin solution adjusted to a viscosity in the range of 500 to 5,000 mPa·s may be applied to the entire surface or in a pattern. The resulting solution is then dried to form an adhesive layer, and the woven or knitted fabric and the moisture-permeable waterproof layer are bonded together via the adhesive layer, and the two are then pressure-bonded or thermocompression-bonded, thereby completing the second manufacturing method.

[0375] On the other hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practical use, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, the hot melt resin is first melted while taking into consideration the melting point of the resin and its viscosity when melted. The second manufacturing method can then be carried out by applying the molten resin to the woven or knitted fabric or the moisture-permeable waterproof layer to form an adhesive layer, and bonding the woven or knitted fabric and the moisture-permeable waterproof layer together under pressure. Alternatively, if texture is important, the resin can be applied in a pattern to the moisture-permeable waterproof membrane and then bonded to the woven or knitted fabric.

[0376] Thereafter, a lining fiber fabric can be laminated on the moisture-permeable waterproof layer using any known appropriate method.

[0377] - Uses of laminated fabrics The laminated fabrics have excellent water repellency and breathable waterproof properties, and the breathable waterproof layer does not peel off even in harsh environments, making them suitable for use in fields such as uniforms, sportswear, and outdoor products used outdoors.

[0378] [Treatment Method] The water repellent composition of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The water repellent composition of the present disclosure may be dispersed and diluted in an organic solvent or water, if necessary, and applied to the surface of the substrate by a known method such as dip coating, spray coating, foam coating, or the like, followed by drying. After drying, a textile product is obtained to which the solid components of the water repellent composition are attached. If necessary, the composition may be applied together with an appropriate crosslinking agent and cured. Furthermore, the water repellent composition of the present disclosure may be used in combination with various additives such as water and / or oil repellents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and antifoaming agents. Examples of the various additives may be the same as those described above under "Other Components" for the water repellent composition. The concentration of the silicone compound or hydrocarbon group-containing polymer in the treatment agent to be brought into contact with the substrate may be varied depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0379] [Textile Products] Various examples of textile products that serve as substrates include cloth products and paper products.

[0380] Examples of textile products include natural fibers of animal or plant origin such as cotton, linen, wool, silk, etc., synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., semi-synthetic fibers such as rayon, acetate, etc., inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, etc., or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, nonwoven fabrics, clothing fabrics, and carpets, but the treatment may also be applied to fibers, yarns, and intermediate textile products (for example, slivers or rovings) in a state prior to being made into textiles.

[0381] Examples of paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating mediums, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc.

[0382] The water repellent composition can be applied to a textile by any of the known methods for treating textiles (e.g., fabrics) with a liquid. The textile may be immersed in the water repellent composition, or the solution may be applied or sprayed onto the textile. The treated textile is preferably dried and cured by heating to develop water and oil repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0383] Alternatively, the polymer may be applied to the textile by a cleaning process, such as in a laundry application or a dry cleaning process.

[0384] The treated textile may be fabric, including woven fabric, knitted fabric, and nonwoven fabric, clothing fabric, carpet, etc., but may also be fiber or yarn or intermediate textile (e.g., sliver or roving, etc.). The water repellent composition of the present disclosure is particularly effective in making textiles (e.g., synthetic fibers) water repellent.

[0385] The fibers constituting the textile product may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers or inorganic fibers. The fibers may be used alone or in combination of two or more types.

[0386] Examples of natural fibers include cellulosic fibers such as cotton, flax, and pulp, chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as ground wood pulp (GP), pressure-raised ground wood pulp (PGW), and thermomechanical pulp (TMP), chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N wood), bleached softwood kraft pulp (NBKP; N wood, NB wood), unbleached hardwood kraft pulp (LUKP; L wood), and bleached hardwood kraft pulp (LBKP, L wood), recycled paper pulps such as deinking pulp (DIP) and waste pulp (WP), and semi-chemical pulp (CP).

[0387] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymer polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupra, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0388] Alternatively, the textile may be leather. The manufacturing polymer may be applied to the leather from an aqueous solution or emulsion at various stages of leather processing, for example, during the wet processing of the leather or during the finishing of the leather, to render the leather hydrophobic and oleophobic. Alternatively, the textile may be paper. The manufacturing polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example, during the drying of the paper.

[0389] The term "treatment" means that the water repellent composition is applied to a substrate by immersion, spraying, coating, etc. The treatment allows the silicone compound and / or polymer, which are the active ingredients of the water repellent composition, to penetrate into the substrate and / or adhere to the surface of the substrate.

[0390] [Pretreatment of Textile Products] The textile product may be pretreated before being treated with the water repellent composition of the present disclosure. Pretreatment of the textile product can impart excellent fastness to the textile product after treatment with the water repellent composition.

[0391] Examples of pretreatments for textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphate, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0392] The method for pretreating a textile product is not limited, and the textile product can be pretreated by a conventionally known method. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the surface of the textile product by a known method such as dip coating, spray coating, foam coating, etc., followed by drying. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of a method for pretreating a textile product, a method for pretreating a textile product with a hydrocarbon-based water repellent will be described in detail.

[0393] The pretreatment method for textile products is to add -SO ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and —O—P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as a "specific functional group").

[0394] M １ Examples of M include H, K, Na, and ammonium ions which may have a substituent. ２ Examples of X include H, K, Na, and ammonium ions which may have a substituent. １ or X ２ When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0395] Fibers containing the specific functional groups (hereinafter sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following methods: (i) A compound having the specific functional groups is attached to a fiber material. The attachment of the compound may be in a state where a portion of the compound is chemically bonded to a portion of the fiber, to the extent that a sufficient amount of the specific functional groups remains. (ii) Fibers are prepared in which the specific functional groups are directly introduced into the material that constitutes the fiber.

[0396] In the case of (i), for example, functional group-containing fibers can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the above-mentioned specific functional groups.

[0397] The raw material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, paper, etc.

[0398] In this embodiment, from the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use a textile material containing polyamide and polyester as raw materials, and it is particularly preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate and polylactic acid, and mixed fibers containing these.

[0399] Above -SO ３ M１ A phenolic polymer can be used as the compound having the formula:

[0033] Such a phenolic polymer can be, for example, one containing at least one compound represented by the following general formula:

[0400] [In formula (2), X ２ Ha-SO ３ M ３ (In the formula, M ３ represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0401] [In the formula, M ４ represents a monovalent cation.

[0402] The above M ３ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0403] The above M ４ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0404] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0405] Above - COOM ２ Examples of compounds having the formula include polycarboxylic acid polymers.

[0406] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0407] Examples of methods for producing polycarboxylic acid polymers include adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt and heating the mixture at 30 to 150°C for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, or isopropyl alcohol, or an aqueous solvent such as acetone, may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite; hydrogen peroxide; and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0408] In addition to the above-mentioned monomers, copolymerizable monomers can be used for radical polymerization. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Preferred acrylates and methacrylates have a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination of two or more.

[0409] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0410] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0411] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (trade name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0412] The above -O-P(O)(OX １ ) (OX ２ ) may be exemplified by phosphate ester compounds represented by the following general formula: [In the formula, X １ or X ２ is as defined above, and X ３ represents an alkyl group having 1 to 22 carbon atoms.

[0413] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0414] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0415] As the phosphate ester compound, for example, commercially available products such as "Phosphanol ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0416] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the compounds described above. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0417] Methods for treating textile materials with the pretreatment liquid include, for example, padding, immersion, spraying, and coating. Examples of padding include methods using padding devices described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include methods using coating machines described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion include methods using batch dyeing machines described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). These machines include jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatment include air spraying, in which the treatment liquid is atomized using compressed air, and methods using a hydraulic atomization air spray. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be adjusted appropriately, taking into account various conditions, such as the purpose and performance. Furthermore, when the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after application to remove the water. The drying method is not particularly limited, and may be either a dry heat method or a wet heat method. The drying temperature is also not particularly limited, and may be, for example, drying at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment at a temperature of 100 to 180°C for 10 seconds to 5 minutes may be performed after drying.

[0418] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the specific functional group (e.g., a phenolic polymer compound) adsorbed during the treatment may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0419] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0420] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can both be achieved at high levels.

[0421] The pH of the pretreatment liquid is preferably adjusted to 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0422] The pretreatment solution may contain a salt to effectively adsorb the compound having the specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0423] In the functional group introduction step using a pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By performing sufficient removal, it is possible to prevent the development of water repellency in the subsequent water repellent treatment from being hindered, and in addition, the feel of the resulting textile product is improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with a hydrocarbon-based water repellent.

[0424] (ii) An example of a fiber in which the specific functional group is directly introduced into the material that constitutes the fiber is cationic dyeable polyester (CD-PET).

[0425] From the viewpoint of improving the water repellency of the resulting textile product, the functional group-containing fiber preferably has a surface zeta potential of −100 to −0.1 mV, more preferably −50 to −1 mV. The zeta potential of the fiber surface can be measured, for example, using a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0426] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0427] <Test Method> The test procedure is as follows.

[0428] [Water Repellency Test] The water repellency of the test cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). The water repellency was evaluated according to the following criteria. The higher the score, the better the water repellency, and intermediate scores (95, 85, 75) were assigned depending on the condition.

[0429] 100 No wetting or water droplets were observed on the surface. 90 No wetting on the surface, but small water droplets were observed. 80 Small individual water droplets were observed on the surface. 70 Wetting was observed on half of the surface, with small individual wettings penetrating the fabric. 50 Wetting was observed on the entire surface. 0 Wetting was observed on both the front and back surfaces.

[0430] [Feeling] The test cloth was evaluated by handling using the following five-point scale. Depending on the condition, an intermediate value (3-4, 4-5) was assigned. 1: hard to 5: soft

[0431] [Chalk mark resistance] The test cloth was placed on a flat surface, and the surface of the test cloth was lightly scratched with a fingernail. The chalk-like scratch marks left by the fingernail were visually evaluated. ○: Almost no mark ○△: Light mark △: Mark visible △×: Slightly dark mark ×: Dark mark

[0432] [Slip resistance] The test fabric was subjected to a warp slippage test at a load of 160 N in accordance with ISO 13936-2, and seam slippage (mm) was measured. The smaller the seam slippage value, the better the slip resistance.

[0433] [Peel Strength] A hot melt adhesive tape ("MELCO Tape" manufactured by Sun Chemical Industry Co., Ltd.) was thermally bonded to the test fabric using a thermocompression bonding device at 160°C for 15 seconds, and the peel strength between the test fabric and the seam tape was measured using an autograph (AGS-J manufactured by Shimadzu Corporation). The gripper was pulled at a moving speed of 200 mm / min, and the average stress was taken as the peel strength [N / inch].

[0434] [Preparation of Raw Materials] Preparation Example 1 9.0 g of MQ-1600 (Dow-Toray Industries, Inc.) as a silicone resin, 9.0 g of KF-96-6CS (polydimethylsiloxane, Shin-Etsu Chemical Co., Ltd.) as a silicone oil, and 22 g of KF-96-50CS (polydimethylsiloxane, Shin-Etsu Chemical Co., Ltd.) as a silicone oil with a number average molecular weight of 1500 or more were mixed and mixed until the MQ-1600 was dissolved. 4.0 g of polyoxyethylene alkyl ether was added and mixed. Next, 89 g of pure water was added in small amounts as an aqueous medium to the mixture to obtain a dispersion containing 30.0 mass% of silicone resin and silicone oil in total.

[0435] Preparation Examples 2 to 5: Except for changing the compounding formulation according to Table 1, the same procedure as in Preparation Example 1 was carried out to obtain dispersions containing a total of 30.0% by mass of silicone resin and silicone oil.

[0436] Comparative Preparation Example 1 20 g of MQ-1600 (Dow Toray Industries, Inc.) as a silicone resin and 20 g of KF-96-6CS (polydimethylsiloxane, Shin-Etsu Chemical Co., Ltd.) as a silicone oil with a number average molecular weight of 1,500 or less were mixed and mixed until the MQ-1600 was dissolved. 4.0 g of polyoxyethylene alkyl ether was added and mixed. Next, 89 g of pure water was added in small amounts as an aqueous medium to the mixture to obtain a dispersion containing 30.0 mass% of silicone resin and silicone oil in total.

[0437] Comparative Preparation Example 2 20 g of KF-96-50CS (polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone oil having a number average molecular weight of 1500 or more and 4.0 g of polyoxyethylene alkyl ether were added and mixed. Next, 89 g of pure water as an aqueous medium was added little by little to the mixture to obtain a dispersion containing 30.0 mass % of silicone oil in total.

[0438] Comparative Preparation Example 3 20 g of KF-96-30CS (polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone oil having a number average molecular weight of 1500 or more and 4.0 g of polyoxyethylene alkyl ether were added and mixed. Next, 89 g of pure water as an aqueous medium was added little by little to the mixture to obtain a dispersion containing 30.0 mass % silicone oil in total.

[0439] Comparative Preparation Example 4 9.0 g of MQ-1600 (Dow Toray Industries, Inc.) as a silicone resin, 9.0 g of KF-96-6CS (polydimethylsiloxane, Shin-Etsu Chemical Co., Ltd.) as a silicone oil having a number average molecular weight of 1500 or less, and 22 g of FZ-3710 (Dow Toray Industries, Inc.) as an amino-modified silicone oil were mixed and mixed until the MQ-1600 was dissolved. 4.0 g of polyoxyethylene alkyl ether was added and mixed. Next, 89 g of pure water was added in small amounts to the mixture as an aqueous medium, and a dispersion containing a total of 30.0 mass% of silicone resin and silicone oil was obtained.

[0440] (Production Example of Acrylic Polymer-Containing Aqueous Dispersion) Production Example 1: A 500 ml plastic container was charged with 30 g of water-soluble glycol solvent as an organic solvent, 120 g of pure water and 60 g of stearyl acrylate as liquid medium, and 2.0 g of cationic emulsifier, 2.0 g of sorbitan fatty acid ester, 6.0 g of polyoxyethylene alkyl ether, and 0.1 g of acetic acid as surfactants, heated to 80° C., stirred at 2000 rpm with a homomixer for 1 minute, and then emulsified and dispersed with ultrasound for 15 minutes. The emulsified dispersion was transferred to a 500 cc four-neck flask equipped with a nitrogen inlet tube, thermometer, stirring rod, and reflux condenser. After nitrogen substitution, 0.2 g of lauryl mercaptan was charged and stirred, and then 1.0 g of azo-group-containing water-soluble initiator was added, and the mixture was heated to 60° C. and reacted for 4 hours to obtain an aqueous dispersion of a polymer. Thereafter, pure water was added to prepare an aqueous dispersion having a nonvolatile content of 30%.

[0441] Preparation Example 2: A 500 ml plastic container was charged with 30 g of water-soluble glycol solvent as an organic solvent, 180 g of pure water as a liquid medium, 48 g of stearyl acrylate, and surfactants including 2.0 g of cationic emulsifier, 2.0 g of sorbitan fatty acid ester, 6.0 g of polyoxyethylene alkyl ether, and 0.1 g of acetic acid. The mixture was heated to 60°C and stirred at 2000 rpm with a homomixer for 1 minute, followed by ultrasonic emulsification for 15 minutes. The resulting emulsion was then transferred to a 500 ml autoclave, purged with nitrogen, and charged with 0.2 g of lauryl mercaptan and 12 g of vinyl chloride as chain transfer agents. 1.0 g of an azo-group-containing water-soluble initiator was then added, heated to 60°C, and reacted for 4 hours to obtain an aqueous dispersion of the polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a nonvolatile content of 30%.

[0442] Production Examples 3 and 4 Aqueous dispersions containing an acrylic polymer, a surfactant, and a liquid medium and having a non-volatile content of 30% were prepared in the same manner as in Production Example 2, except that the formulation was changed according to Table 2.

[0443] Production Example 5 1. Synthesis of Aliphatic Polyisocyanate Derivative In a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, Inc., product name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, hindered phenol-based antioxidant), and 0.25 parts by mass of tetraphenyl dipropylene glycol diphosphite (organic phosphite ester, cocatalyst) were mixed under a nitrogen atmosphere. 10.7 parts by mass of 1,3-butanediol was then added to the mixture, and nitrogen was introduced into the liquid phase for 1 hour. The mixture was then heated to 80°C and reacted for 3 hours, after which the temperature was lowered to 60°C. Subsequently, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added as an isocyanuration catalyst, and the mixture was allowed to react for 1.5 hours. Subsequently, 0.04 parts by mass of o-toluenesulfonamide was added per 100 parts by mass of HDI. The reaction mixture was then passed through a thin-film distillation apparatus (temperature 150°C, vacuum degree 93.3 Pa) and distilled until the amount of residual HDI monomer was 0.5% or less, yielding an aliphatic polyisocyanate derivative (isocyanurate derivative of hexamethylene diisocyanate). The resulting aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average number of isocyanate functional groups of 3.0.

[0444] 2. Production of Hydrocarbon-Based Polyurethane: 100.20 g of the aliphatic polyisocyanate derivative, 67.60 g of Kalcol 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound, and 22.30 g of oleic alcohol were mixed in a reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, and the mixture was reacted in a nitrogen atmosphere at 110°C for 4 hours until the isocyanate group concentration reached 3.67%. The reaction solution was then cooled to 80°C, and 9.90 g of N-methyldiethanolamine as a cationic active hydrogen compound was added, followed by a reaction at 80°C for 1 hour. Next, 50.00 g of methyl ethyl ketone was added as a solvent, and the mixture was reacted at 80°C until disappearance of the isocyanate groups was confirmed by infrared absorption spectroscopy. Next, 57.69 g of methyl ethyl ketone was added to the reaction solution, the temperature was raised to 80°C, and the reaction solution was mixed until completely dissolved, after which it was cooled to 75°C. Thereafter, 18.96 g of acetic acid was added as an acid compound to neutralize the mixture. Next, while maintaining the reaction solution at 75°C, 800.0 g of ion-exchanged water heated to 70°C was gradually added to emulsify (internal emulsification). The mixture was then evaporated in an evaporator at a water bath temperature of 60°C under reduced pressure until the solids concentration reached 20 wt% or more. The solids concentration excluding the acid compound (acetic acid) was then adjusted with ion-exchanged water to 20 wt%, thereby obtaining an aqueous dispersion containing polyurethane.

[0445] Production Example 6: 116 g of sorbitan tristearate and 150 g of 4-methyl-2-pentanone (MIBK) were charged into a 500 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser. Next, to remove excess water vapor from this mixture, the mixture was stirred while maintaining the temperature of the mixture at 70°C, refluxed for 1 hour, and then allowed to cool to 50°C. Then, while maintaining stirring, 30 g of Desmodur N-100 (a biuret derivative of hexamethylene diisocyanate, Covestro) was added dropwise to the mixture using a dropping funnel. After completion of the dropwise addition, one drop of dibutyltin dilaurate was added as a catalyst, and the mixture was allowed to react at 80°C for 1 hour. Next, 25 g of sorbitan monostearate was added, and the mixture was allowed to react for an additional 4 hours at 80°C. The reaction mixture was then cooled to 60°C, and the recovered mixture was slowly mixed with water at 60°C containing an arbitrary amount of cationic emulsifier and polyoxyethylene alkyl ether. The mixture was stirred at 6000 rpm for 1 minute using a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. The solvent (MIBK) was then removed under reduced pressure, and pure water was added to adjust the concentration, yielding an aqueous dispersion containing polyurethane with a solids concentration of 20%.

[0446] Preparation Example 7: 150 g of methyl ethyl ketone (MEK) and 51 g of stearyl alcohol were charged into a 500 mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser. Next, to remove excess water vapor from this mixture, the mixture was stirred while maintaining the temperature of the mixture at 70 ° C., refluxed for 1 hour, and then allowed to cool to 50 ° C. 30 g of Desmodur N3200A (a biuret derivative of hexamethylene diisocyanate, manufactured by Covestro) was added to the mixture, and the mixture was further reacted at 80 ° C. for 4 hours. After cooling to 60 ° C., the reaction solution was recovered, and the reaction solution was slowly mixed with water at 60 ° C. containing an arbitrary amount of polyoxyethylene alkyl ether. This mixture was stirred at 6000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 15 minutes. Next, the solvent (MEK) was removed under reduced pressure, and then pure water was added to adjust the concentration, to obtain an aqueous dispersion containing polyurethane with a solids concentration of 20%.

[0447] (Production Example of Wax-Containing Aqueous Dispersion) Production Example 8: 150 g of paraffin wax (melting point 75°C), 350 g of pure water, 4.5 g of polyoxyethylene alkyl ether, and 3 g of sorbitan fatty acid ester were placed in a pressure reactor and sealed. The mixture was heated to 110 to 120°C with stirring, and then emulsified under high pressure for 30 minutes to prepare an aqueous wax dispersion. Pure water was then added to prepare an aqueous wax dispersion with a solids content of 30% by weight.

[0448] Production Example 9: A reaction vessel was charged with 150 g of oxidized polypropylene wax having a melting point of 150° C., an acid value of 44 mgKOH / g, and a density of 0.93, 325 g of ion-exchanged water, 25 g of a surfactant with an HLB of 15, and 5 g of a 48% aqueous potassium hydroxide solution, and the mixture was sealed. The temperature was raised to 160° C. with stirring, and then high-pressure emulsification was carried out under high pressure for 1 hour, followed by cooling to 90° C. to obtain an aqueous dispersion of polypropylene wax. Pure water was then added to prepare an aqueous dispersion of polypropylene wax with a solids content of 30% by weight.

[0449] Preparation Example 10: Methyl hydrogen silicone oil ( 1 Charge 12 g of 1H NMR-based SiH:SiCH3 (molar ratio 60:40) and 0.02 g of hydrosilylation Pt catalyst. A stirrer, thermometer, and reflux condenser were set up, and 36 g of CH2=CH-(CH2CH2)n-CH2CH3 (n=11) was charged into the dropping funnel. While maintaining the temperature at 70°C, CH2=CH-(CH2CH2)n-CH2CH3 (n=11) was added dropwise from the dropping funnel. After the addition was complete, the reaction was continued for another 3 hours at 70°C. Infrared spectroscopy (IR) confirmed that the SiH peak had disappeared, yielding Silicone Polymer 1.

[0450] Preparation Example 6: 28 g of silicone polymer 1, 5.6 g of water-soluble glycol solvent, 60 g of pure water, 1.7 g of sorbitan fatty acid ester, 0.7 g of polyoxyethylene alkyl ether, and 0.6 g of cationic emulsifier were charged into a 250 ml plastic container, heated to 75°C, stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasound for 10 minutes to obtain an aqueous dispersion. Pure water was then added to prepare an aqueous dispersion with a solids concentration of 30%.

[0451] Example 1: A silicone resin, MQ-1600 (manufactured by Dow Toray Industries, Inc.), and a silicone oil, KF-96-50CS (polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) having a number average molecular weight of 1500 or more, were mixed in a weight ratio of 30:70, and the mixture was further diluted with toluene to prepare a treatment solution with a silicone compound concentration of 4.0%. Polyester and nylon fabrics were immersed in this treatment solution and then subjected to a centrifugal spin-drying machine for approximately 60 seconds. The treated fabrics were dried overnight at room temperature and then passed through a pin tenter at 170°C for 1 minute for curing. The test fabrics thus treated were used to test for water repellency, texture, chalk mark resistance, and slip resistance. The results are shown in Table 3-1.

[0452] Examples 2 to 10: Except for changing the compounding formulation according to Table 3-1, fabrics were treated in the same manner as in Example 1, and tests for water repellency, texture, chalk mark resistance, and slip resistance were carried out. The results are shown in Table 3-1.

[0453] Comparative Examples 1 to 8: Except for changing the compounding formulation according to Table 3-2, fabrics were treated in the same manner as in Example 1, and tests for water repellency, texture, chalk mark resistance, and slip resistance were carried out. The results are shown in Table 3-2.

[0454] Examples 11 to 15, Comparative Examples 9 to 12 A silicone compound dispersion and tap water were mixed to obtain the composition shown in Table 4 (in the table, the numerical values ​​indicate (wt%)), to obtain a treatment liquid for each water repellent composition. A polyester cloth and a nylon cloth were immersed in this treatment liquid and then wrung out with a mangle. The treated cloth was passed through a pin tenter at 170°C for 1 minute, dried, and cured. Using the test cloth treated in this manner, tests were conducted on water repellency, texture, chalk mark resistance, slip resistance, and peel strength. The results are shown in Table 4.

[0455] Examples 16 to 31 A silicone compound dispersion, other components, and tap water were mixed to obtain the compositions shown in Table 5 (in the table, the values ​​indicate (wt%)), to obtain treatment solutions for water repellent compositions. Polyester cloth and nylon cloth were immersed in these treatment solutions and then squeezed with a mangle. The treated cloths were passed through a pin tenter at 170°C for 1 minute, dried, and cured. Tests for water repellency, texture, chalk mark resistance, and slip resistance were carried out using the test cloths treated in this manner. The results are shown in Table 5.

[0456]

[0457]

[0458]

[0459]

[0460]

[0461]

Claims

A water repellent composition for textile products containing synthetic fibers, comprising: the water repellent composition contains a silicone compound consisting of a silicone oil and a silicone resin; In a GPC chart of the silicone compound, a peak top is present in a region of molecular weight of 1,500 or more, The component of the silicone compound having a molecular weight of 1,500 or more includes a silicone oil other than amino-modified silicone, A water repellent composition, wherein the amount of the silicone resin is 32% by weight or less based on the silicone compound. The water repellent composition of claim 1 , further comprising a surfactant. The water repellent composition according to claim 2 , wherein the surfactant comprises a nonionic surfactant.

4. The water repellent composition according to claim 1, wherein the silicone oil has a number average molecular weight Mn of 50,000 or less.

5. The water repellent composition according to claim 1, wherein the silicone oil has a number average molecular weight Mn of 30,000 or less.

6. The water repellent composition according to claim 1, wherein the silicone resin has a number average molecular weight Mn of 1,000 or more. The water repellent composition according to any one of claims 1 to 6, wherein the number average molecular weight Mn of the silicone compound is 20,000 or less. The water repellent composition according to any one of claims 1 to 7, which is in the form of an organic solvent solution, an organic solvent dispersion, or an aqueous dispersion. A method for producing a textile product, comprising applying the water repellent composition according to any one of claims 1 to 8 to a textile substrate. Before applying the water repellent composition to the fiber substrate, -SO ３ M １ (In the formula, M １ represents a monovalent cation), -COOM ２ (In the formula, M ２ represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. A textile product to which the silicone oil and the silicone resin in the water repellent composition according to any one of claims 1 to 8 are attached. -SO ３ M １ (In the formula, M １ represents a monovalent cation), -COOM ２ (In the formula, M ２ represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

Images