Method for producing liquid-repellent fibers

Abstract

The present invention addresses the problem of providing a method for imparting liquid repellency to fibers even when the amount of water and / or a surfactant is reduced, preferably without using water and / or a surfactant. Provided is a method for producing liquid-repellent fibers, the method comprising a fiber treatment step in which supercritical carbon dioxide is used as a treatment medium and a fiber base material is treated with a repellent containing a liquid-repellent compound, whereby liquid repellency can be imparted to the fibers even when the amount of water and / or a surfactant is reduced, preferably without using water and / or a surfactant.

Description

Method for manufacturing liquid-repellent fibers

[0001] The present disclosure relates to a method for producing liquid-repellent fibers, and more particularly to a method for producing liquid-repellent fibers using supercritical carbon dioxide as a treatment medium.

[0002] In recent years, research and development into technology for applying supercritical carbon dioxide to fabric treatment has been progressing.

[0003] Patent Document 1 discloses a fiber treatment method characterized by using a fiber treatment agent that contains supercritical carbon dioxide or liquefied carbon dioxide, water, and a surfactant and forms reverse micelles when treating fibers or textile products.

[0004] Japanese Patent Application Laid-Open No. 2004-76190

[0005] However, Patent Document 1 does not specifically describe how to impart liquid repellency to fibers. Furthermore, the combined use of water and a surfactant is essential, which may be industrially disadvantageous from the viewpoint of productivity. Furthermore, with the recent worsening of environmental issues, water is a precious resource, and reducing its industrial consumption and wastewater volume has become a major challenge.

[0006] An object of the present disclosure is to provide a novel method that can impart liquid repellency to fibers using a reduced amount of water and / or surfactant, preferably without using water and / or surfactant.

[0007] The present disclosure includes the following aspects: [Item 1] A method for producing a liquid-repellent fiber, comprising a fiber treatment step of treating a fiber substrate with a repellent agent containing a liquid-repellent compound using supercritical carbon dioxide as a treatment medium. [Item 2] The method for producing a liquid-repellent fiber according to Item 1, wherein the liquid-repellent compound has a water contact angle of 35° or more. [Item 3] The liquid-repellent compound is a compound represented by the following formula: -X-R ｎ[wherein X is a direct bond or a group having a valence of 1+n, R is, independently in each occurrence, an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent or a polysiloxane group, and n is from 1 to 3.] [Item 4] A method for producing a liquid-repellent fiber according to Item 3, wherein R is an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, and R has 12 or more carbon atoms. [Item 5] X is a direct bond, -O-, -C(=O)-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), １ and X is a hydrocarbon group having 1 to 40 carbon atoms. ２ Item 6. The method for producing a liquid-repellent fiber according to Item 3 or 4, wherein X is a 1+n valent group consisting of one or more selected from the group consisting of -X １ - or -X １ -X ２ -X １ - [wherein, X １ is independently in each occurrence a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, —SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and X ２ [Item 7] The method for producing a liquid-repellent fiber according to any one of Items 3 to 5, wherein the liquid-repellent compound is a group represented by the following formula: CH ２ =C(-Q)-C(=O)-X-R ｎ[wherein Q is a hydrogen atom, a monovalent organic group or a halogen atom, and X is a direct bond, —O—, —C(═O)—, —S(═O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), １ and X is a hydrocarbon group having 1 to 40 carbon atoms. ２ and a 1+n-valent group consisting of one or more selected from the group consisting of: R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and n is an integer from 1 to 3. [Item 8] A method for producing a liquid-repellent fiber according to any one of items 1 to 6, wherein X is a compound represented by the following formula: -X １ - or -X １ -X ２ -X １ - [wherein, X １ is independently in each occurrence -O-, -NR'-, -C(=O)-NR'-, -NR'-C(=O)-, or -NR'-C(=O)-NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and X ２ [Item 9] The method for producing a liquid-repellent fiber according to Item 7, wherein the liquid-repellent compound is a group represented by the following formula: -X-R ｎ[wherein X is a direct bond or a group having a valence of 1+n, R is, independently in each occurrence, an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, and n is 1 to 3.] [Item 10] The method for producing a liquid-repellent fiber according to any one of Items 1 to 6, wherein the base compound is a compound modified with a group represented by the formula: [wherein X is a direct bond or a group having a valence of 1+n, R is, independently in each occurrence, an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, and n is 1 to 3.] [Item 11] The method for producing a liquid-repellent fiber according to any one of Items 1 to 6, wherein the base compound is a compound selected from the group consisting of starch, cellulose, curdlan, pullulan, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, xanthan gum, gella gum, tamarind seed gum, cycloamylose, glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, stepioxide, dextrin, cyclodextrin, glycerin, polyglycerin, menthol, xylitol, sucrose, cellulose, cellulose acetate ... Item 11. A method for producing a liquid-repellent fiber according to Item 9, wherein the base compound is one or more selected from the group consisting of clalose, fructose, maltose, trehalose, lactosucrose, erythritol, vanillin, cholesterol, glucosamine, catechin, anthocyanin, quercetin, citric acid, malic acid, gluconic acid, alginic acid, butyric acid, lactic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, chlorogenic acid, aldonic acid, uronic acid, aldaric acid, phytic acid, ascorbic acid, and derivatives thereof. [Item 12] A method for producing a liquid-repellent fiber according to Item 9 or 10, wherein the base compound is a glycerin polymer or a citric acid polymer. [Item 12] The method for producing a liquid-repellent fiber according to any one of Items 9 to 11, wherein the matrix compound has a hydroxy group, and the hydroxy group forms a group represented by the following formula in the liquid-repellent compound: -O-, -O-C(=O)-, -O-C(=O)-NR'-, or -O-C=S-NR'- [wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms]. [Item 13] The method for producing a liquid-repellent fiber according to any one of Items 9 to 12, wherein the matrix compound has a carboxy group, and the carboxy group forms a group represented by the following formula in the liquid-repellent compound: -C(=O)- -C(=O)-O- -C(=O)-NR'-, or -C(=O)-S- [wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms]. [Item 14] The liquid repellent compound is represented by the following formula: A(-X-Rｎ ) ｍ [Item 15] A method for producing a liquid-repellent fiber according to any one of Items 1 to 6, wherein the liquid-repellent compound is a compound represented by the following formula: [wherein A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocycle which may have a substituent, X is, independently in each occurrence, a direct bond or a 1+n-valent group, R is, independently in each occurrence, an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, n is, independently in each occurrence, 1 to 3, and m is, independently in each occurrence, 1 to 6. ｎ ) ｍ [Item 16] A method for producing a liquid-repellent fiber according to any one of items 1 to 6, wherein the liquid-repellent fiber is a compound obtained by polymerizing, via a substituent possessed by A, a compound represented by the following formula: [wherein A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocycle which may have a substituent, X is, independently in each occurrence, a direct bond or a 1+n-valent group, R is, independently in each occurrence, an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, n is, independently in each occurrence, 1 to 3, and m is, independently in each occurrence, 1 to 6. １ - or -X １ -X ２ -X １ - [wherein, X １ is independently in each occurrence a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —C(OR′)R′—, or —C(OR′)(—) ２ (R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and X ２is a hydrocarbon group having 1 to 40 carbon atoms.] [Item 17] A method for producing a liquid-repellent fiber according to any one of Items 1 to 6, wherein the liquid-repellent compound is a reaction product of an isocyanate group-containing compound and an isocyanate-reactive compound. [Item 18] A method for producing a liquid-repellent fiber according to any one of Items 1 to 6, wherein the liquid-repellent compound has a polysiloxane group. [Item 19] A method for producing a liquid-repellent fiber according to Item 18, wherein the liquid-repellent compound has the polysiloxane group in a side chain. [Item 20] A method for producing a liquid-repellent fiber according to any one of Items 1 to 6, wherein the liquid-repellent compound has an amine skeleton, and Ｎ -R ｎ [In the formula, X Ｎ [Item 21] The method for producing a liquid-repellent fiber according to any one of Items 1 to 6, wherein the fiber is an amine-modified product, and the fiber has one or more aliphatic hydrocarbon-containing groups represented by the formula: [wherein R is a direct bond or a 1+n-valent group, R is, in each occurrence, independently an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, and n is an integer of from 1 to 3.] At least one of the aliphatic hydrocarbon-containing groups is bonded to a nitrogen atom of the amine skeleton. [Item 21] The amine skeleton is composed of a monovalent to trivalent amino group and a linear saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom. [Item 22] The method for producing a liquid-repellent fiber according to any one of Items 1 to 21, wherein the fiber is a polyester or polyester-blended fiber. [Item 23] The method for producing a liquid-repellent fiber according to any one of Items 1 to 22, wherein the water concentration in the treating agent for treating the fiber substrate is 0.001 mol / L or less. [Item 24] A composition comprising the liquid-repellent compound defined in any one of items 1 to 21 and supercritical carbon dioxide. [Item 25] A repellent agent comprising the liquid-repellent compound defined in any one of items 1 to 21 and supercritical carbon dioxide. [Item 26] A fiber treated to be water-repellent with a composition or agent comprising the liquid-repellent compound defined in any one of items 1 to 21.

[0008] According to the method for producing a liquid-repellent fiber of the present disclosure, various liquid-repellent compounds can be used to impart liquid repellency to fibers, even with reduced amounts of water and / or surfactant, or preferably without using water and / or surfactant.

[0009] <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 N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain.

[0010] 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 １－２０ Examples 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.

[0011] In this specification, when a term (symbol) that may appear multiple times in a chemical structure is defined, that definition applies independently to each occurrence, regardless of whether "independently at each occurrence," "independently from each other," "independently from each other," or similar expressions are explicitly stated, unless otherwise stated.

[0012] <Repellent> The repellent in the present disclosure can impart liquid repellency to a fiber substrate and can function as at least one selected from the group consisting of a water repellent, an oil repellent, an oil-resistant agent, and a water-resistant agent. According to the present disclosure, the repellent can satisfactorily impart liquid repellency to a fiber substrate even when the amount of water and / or surfactant in the repellent is reduced, which is advantageous from the viewpoints of industry and / or environmental protection.

[0013] The repellent agent of the present disclosure includes a liquid repellent compound. The repellent agent of the present disclosure may consist solely of the liquid repellent compound. The repellent agent of the present disclosure may include, in addition to the liquid repellent compound, supercritical carbon dioxide as a treatment medium and / or other components.

[0014] The repellent agent in 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 repellent agent in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0015] [Liquid-repellent Compound] The liquid-repellent compound in the present disclosure is capable of adhering to a fibrous substrate and imparting liquid-repellency to the fibrous substrate.

[0016] The water contact angle of the liquid-repellent compound 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. The water contact angle of the liquid-repellent compound 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 liquid-repellent compound 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 fiber substrate. The water contact angle is the static contact angle of the liquid-repellent compound with respect to the spin-coated film as shown in the examples, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0017] The solubility parameter (SP value) of the liquid repellent compound may be 6 or more, 7 or more, 7.5 or more, 8 or more, 8.5 or more, 9 or more, 9.5 or more, 10 or more, 10.5 or more, 11 or more, 11.5 or more, or 12 or more, preferably 8 or more, more preferably 9 or more. The solubility parameter (SP value) of the liquid repellent compound may be 18 or less, 16 or less, 15.5 or less, 15 or less, 14.5 or less, 14 or less, 13.5 or less, 13 or less, 12.5 or less, 12 or less, 11.5 or less, or 11 or less, preferably 14 or less, more preferably 12 or less. The solubility parameter is defined as the square root of the cohesive energy density, which is the cohesive energy divided by the molar molecular volume.

[0018] The solubility of the liquid-repellent compound in supercritical carbon dioxide (25 MPa, 120°C) may be 0.001 mg / mL or more, 0.005 mg / mL or more, 0.01 mg / mL or more, 0.05 mg / mL or more, 0.1 mg / mL or more, 0.5 mg / mL or more, or 1 mg / mL or more, preferably 0.005 mg / mL or more, more preferably 0.01 mg / mL or more. The solubility of the liquid-repellent compound in supercritical carbon dioxide (25 MPa, 120°C) may be 50 mg / mL or less, 10 mg / mL or less, 5 mg / mL or less, 1 mg / mL or less, 0.5 mg / mL or less, or 0.1 mg / mL or less, preferably 5 mg / mL or less, more preferably 1 mg / mL or less.

[0019] The dust absorption rate of the liquid-repellent compound may be 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, and is preferably 50% or more, more preferably 80% or more, and particularly preferably 90% or more. Here, the dust absorption rate is the percentage obtained by dividing the weight of the liquid-repellent compound attached to the fiber by the weight of the liquid-repellent compound dissolved in supercritical carbon dioxide during treatment and multiplying the result by 100.

[0020] The melting point of the liquid-repellent compound may be 60°C or higher, 80°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, or 150°C or higher, and it is preferable that the melting point of the liquid-repellent compound is higher than the treatment temperature.

[0021] Examples of the liquid repellent compound include, but are not limited to, acrylic polymer-type liquid repellent compounds, matrix-modified liquid repellent compounds, ring-modified liquid repellent compounds, isocyanate-based liquid repellent compounds, polysiloxane group-containing liquid repellent compounds, etc. The liquid repellent compound may be a combination of multiple types (e.g., two or three types) of liquid repellent compounds, as described in detail below.

[0022] In the present disclosure, the liquid-repellent compound preferably has a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and is particularly preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, and is 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. The number of carbon atoms in the hydrocarbon group 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. Note that the monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, may correspond to R described below.

[0023] The hydrocarbon group having 6 to 40 carbon atoms and optionally having a substituent in the present disclosure may be a hydrocarbon group having a substituent, or may be an unsubstituted hydrocarbon group. Examples of the substituent include -OR', -N(R') ２, —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 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 total 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. In the substituted hydrocarbon group, the amount of carbon atoms relative to the total amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, a group having 6 to 40 carbon atoms may have 1 to 3 (for example, 1) -OR' (particularly -OH) as a substituent (for example, other than at a terminal).

[0024] The liquid repellent compound may have 2 or more, 5 or more, 10 or more, 25 or more, 50 or more, 75 or more, 100 or more, 300 or more, or 500 or more hydrocarbon groups per molecule, and preferably has 10 or more hydrocarbon groups. The liquid repellent compound may have 1000 or less, 500 or less, 300 or less, 100 or less, 75 or less, or 50 or less hydrocarbon groups per molecule.

[0025] The amount of hydrocarbon groups (particularly aliphatic hydrocarbon groups) having 6 to 40 carbon atoms and which may have a substituent in the liquid repellent compound may be 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 preferably 5% by weight or more. The amount of hydrocarbon groups (particularly aliphatic hydrocarbon groups) having 6 to 40 carbon atoms and which may have a substituent in the liquid repellent compound may be 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, or 25% by weight or less, and preferably 70% by weight or less.

[0026] The liquid-repellent compound in the present disclosure does not necessarily have any group 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. Even if the liquid-repellent compound does not contain these fluorine-containing groups, it can still impart liquid repellency to a substrate.

[0027] The liquid repellent compound in the present disclosure is represented by the following formula: -X-R ｎ [wherein X is a direct bond or a group having a valence of 1+n, R is, independently in each occurrence, an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, and n is from 1 to 3.] When the liquid-repellent compound has this group, it can impart good liquid repellency to the fibrous substrate.

[0028] [X] X is a direct bond or a 1+n-valent group, where n can be 1 to 3, 2 to 3, 1 to 2, 1, 2, or 3.

[0029] The molecular weight of X may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. The molecular weight of X may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more.

[0030] X is a direct bond, —O—, —C(═O)—, or —S(═O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), １ and X is a hydrocarbon group having 1 to 40 carbon atoms. ２ and may be a (1+n) valent group consisting of one or more selected from the group consisting of: In this specification, the right side of the group described as X is bonded to R.

[0031] [X １ ] X １ is a non-hydrocarbon linker.

[0032] X １ is a direct bond or a divalent or higher valent group. １ The valence of X may be 2 to 4, 2 to 3, or 2. １ is preferably not only a direct bond.

[0033] X １ The molecular weight of X may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. １ may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0034] X １ is -O-, -C(=O)-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). １ Examples of include a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, —SO ２ -, -SO ２ NR'-, -C(OR')R'-, -C(OR')(-) ２ and the like (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms).

[0035] [X ２ ] X ２ is a hydrocarbon linker, which is a hydrocarbon group having 1 to 40 carbon atoms.

[0036] X ２ is a divalent or higher valent group. ２ The valency of may be, for example, 2-4, 2-3, or 2.

[0037] X ２The number of carbon atoms in X may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more. ２ may have 40 or fewer, 35 or fewer, 30 or fewer, 25 or fewer, 20 or fewer, 15 or fewer, 10 or fewer, or 5 or fewer carbon atoms.

[0038] X ２ X may be a cyclic, branched, or straight chain hydrocarbon group. ２ may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, for example, an aliphatic hydrocarbon group (e.g., a saturated aliphatic hydrocarbon group).

[0039] X ２ Examples of -(CH ２ ) ｐ -(p is 1 to 40, for example, 1 to 10), a linear hydrocarbon group having an unsaturated bond of 1 to 40 carbon atoms, for example, 1 to 10 carbon atoms, a hydrocarbon group having a branched structure of 1 to 40 carbon atoms, for example, 1 to 10 carbon atoms, -(CH ２ ) ｑ -C ６ H ４ -(CH ２ ) ｒ -(q and r are each independently 0 to 40, for example, 1 to 10; -C ６ H ４ - is a phenylene group).

[0040] [Examples of X] Examples of X are explained below. In the following, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each occurrence.

[0041] Preferred examples of X include -X １ -or-X １ -X ２ -X １ -. X is -X １ - or -X １ -X ２ -X １ - [wherein, X １is independently in each occurrence a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, —SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and X ２ is a hydrocarbon group having 1 to 40 carbon atoms.]

[0042] X may have an amide group, a urea group, or a urethane group. Specific examples of such X include: —O—C(═O)—NR′—, —NR′—C(═O)—, —NR′—C(═O)—O—, —NR′—C(═O)—NR′—, —C(═O)—NR′—, and the like.

[0043] Examples of X include, when X is divalent, -X １ -, -X １ -C(=O)-, -C(=O)-X １ -, -X １ -C(=O)-X １ -, -X １ -X ２ -, -X １ -X ２ -X １ -, -X １ -X ２ -X １ -C(=O)-, -X １ -X ２ -C(=O)-X １ -, -X １ -X ２ -X １ -C(=O)-X １ -, -X １ -X ２ -X １ -X ２ - etc.

[0044] Examples of X include, when X is trivalent, -X１ (-) ２ , -X １ -X １ (-) ２ , -X １ -X ２ (-X １ -) ２ , -X ２ (-X １ -) ２ , -X ２ (-X １ -C(=O)-) ２ , -X ２ (-C(=O)-X １ -) ２ , -X ２ (-X １ -C(=O)-X １ -) ２ , -X ２ (-X １ -X ２ -) ２ , -X ２ (-X １ -X ２ -X １ -) ２ , -X ２ (-X １ -X ２ -X １ -C(=O)-) ２ , -X ２ (-X １ -X ２ -C(=O)-X １ -) ２ , -X ２ (-X １ -X ２ -X １ -C(=O)-X １ -) ２ , -X ２ (-X １ -X ２ -X １ -X ２ -) ２ etc. etc.

[0045] Examples of X include, when X is tetravalent, -X １ -X ２ (-X １ -) ３ , -X ２ (-X１ -) ３ , -X ２ (-X １ -C(=O)-) ３ , -X ２ (-C(=O)-X １ -) ３ , -X ２ (-X １ -C(=O)-X １ -) ３ , -X ２ (-X １ -X ２ -) ３ , -X ２ (-X １ -X ２ -X １ -) ３ , -X ２ (-X １ -X ２ -X １ -C(=O)-) ３ , -X ２ (-X １ -X ２ -C(=O)-X １ -) ３ , -X ２ (-X １ -X ２ -X １ -C(=O)-X １ -) ３ , -X ２ (-X １ -X ２ -X １ -X ２ -) ３ etc.

[0046] Specific examples of X when X is divalent include -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR'-, and -O-X ２ -S(=O) ２ —NR′—, —O—X ２ —NR′—, —O—X ２ -NR'-S(=O) ２ -, -O-X ２ -NR'-C(=O)-, -O-X ２ -NR'-C(=O)-O-, -O-X ２ -NR'-C(=O)-NR'-, -O-X２ -NR'-X ２ -, -O-X ２ -O-, -O-X ２ -O-C(=O)-, -O-X ２ -OC(=O)-NR'-, -O-X ２ -C(=O)-O-, -O-X ２ -C(=O)-NR'-, -O-X ２ -O-X ２ -, -O-X ２ -, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -NR'-X ２ -S(=O) ２ -NR'-, -NR'-X ２ -NR'-, -NR'-X ２ -NR'-S(=O) ２ -, -NR'-X ２ -NR'-C(=O)-, -NR'-X ２ -NR'-C(=O)-O-, -NR'-X ２ -NR'-C(=O)-NR'-, -NR'-X ２ -NR'-X ２ -, -NR'-X ２ —O—, —NR′-X ２ -OC(=O)-, -NR'-X ２ -OC(=O)-NR'-, -NR'-X ２ -O-X ２ -, -NR'-X ２ -C(=O)-O-, -NR'-X ２ -C(=O)-NR'-, -NR'-X ２ -, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -C(=O)-S-, -SO ２ -, -SO ２ NR'-, -C(OR')(R')(-) 、 etc.

[0047] Specific examples of X include, when X is trivalent, -X ２ (-O-) ２ -, -X ２ (-O-C(=O)-) ２ -, -X ２ (-OC(=O)-O-) ２-、-X ２ (-O-C(=O)-NR’-) ２ -、-X ２ (-O-X ２ -S(=O) ２ -NR’-) ２ -、-X ２ (-O-X ２ -NR’-) ２ -、-X ２ (-O-X ２ -NR’-S(=O) ２ -) ２ -、-X ２ (-O-X ２ -NR’-C(=O)-) ２ -、-X ２ (-O-X ２ -NR’-C(=O)-O-) ２ -、-X ２ (-O-X ２ -NR’-C(=O)-NR’-) ２ -、-X ２ (-O-X ２ -NR’-X ２ -) ２ -、-X ２ (-O-X ２ -O-) ２ -、-X ２ (-O-X ２ -O-C(=O)-) ２ -、-X ２ (-O-X ２ -O-C(=O)-NR’-) ２ -、-X ２ (-O-X ２ -C(=O)-O-) ２ -、-X ２ (-O-X ２ -C(=O)-NR’-) ２ -、-X ２ (-O-X ２ -O-X ２ -) ２ -、-X ２ (-O-X ２ -) ２ -、-X ２ (-NR’-) ２ -、-X ２ (-NR’-C(=O)-) ２ -、-X２ (-NR’-C(=O)-O-) ２ -、-X ２ (-NR’-C(=O)-NR’-) ２ -、-X ２ (-NR’-X ２ -S(=O) ２ -NR’-) ２ -、-X ２ (-NR’-X ２ -NR’-) ２ -、-X ２ (-NR’-X ２ -NR’-S(=O) ２ -) ２ -、-X ２ (-NR’-X ２ -NR’-C(=O)-) ２ -、-X ２ (-NR’-X ２ -NR’-C(=O)-O-) ２ -、-X ２ (-NR’-X ２ -NR’-C(=O)-NR’-) ２ -、-X ２ (-NR’-X ２ -NR’-X ２ -) ２ -、-X ２ (-NR’-X ２ -O-) ２ -、-X ２ (-NR’-X ２ -O-C(=O)-) ２ -、-X ２ (-NR’-X ２ -O-C(=O)-NR’-) ２ -、-X ２ (-NR’-X ２ -O-X ２ -) ２ -、-X ２ (-NR’-X ２ -C(=O)-O-) ２ -、-X ２ (-NR’-X ２ -C(=O)-NR’-) ２ -、-X ２ (-NR’-X ２ -) ２ -、-X ２(-C(=O)-) ２ -, -X ２ (-C(=O)-O-) ２ -, -X ２ (-C(=O)-NR'-) ２ -, -X ２ (-C(=O)-S-) ２ -, -X ２ (-SO ２ -) ２ -, -X ２ (-SO ２ NR'-) ２ -, -X ２ (-C(OR')(R')(-)) ２ -, -C(OR')(-) ２、 etc.

[0048] Specific examples of X include, when X is tetravalent, -X ２ (-O-) ３ -, -X ２ (-O-C(=O)-) ３ -, -X ２ (-OC(=O)-O-) ３ -, -X ２ (-OC(=O)-NR'-) ３ -, -X ２ (-O-X ２ -S(=O) ２ -NR'-) ３ -, -X ２ (-O-X ２ -NR'-) ３ -, -X ２ (-O-X ２ -NR'-S(=O) ２ -) ３ -, -X ２ (-O-X ２ -NR'-C(=O)-) ３ -, -X ２ (-O-X ２ -NR'-C(=O)-O-) ３ -, -X ２ (-O-X ２ -NR'-C(=O)-NR'-) ３ -, -X ２ (-O-X ２ -NR'-X ２ -) ３ -, -X２ (-O-X ２ -O-) ３ -、-X ２ (-O-X ２ -O-C(=O)-) ３ -、-X ２ (-O-X ２ -O-C(=O)-NR’-) ３ -、-X ２ (-O-X ２ -C(=O)-O-) ３ -、-X ２ (-O-X ２ -C(=O)-NR’-) ３ -、-X ２ (-O-X ２ -O-X ２ -) ３ -、-X ２ (-O-X ２ -) ３ -、-X ２ (-NR’-) ３ -、-X ２ (-NR’-C(=O)-) ３ -、-X ２ (-NR’-C(=O)-O-) ３ -、-X ２ (-NR’-C(=O)-NR’-) ３ -、-X ２ (-NR’-X ２ -S(=O) ２ -NR’-) ３ -、-X ２ (-NR’-X ２ -NR’-) ３ -、-X ２ (-NR’-X ２ -NR’-S(=O) ２ -) ３ -、-X ２ (-NR’-X ２ -NR’-C(=O)-) ３ -、-X ２ (-NR’-X ２ -NR’-C(=O)-O-) ３ -、-X ２ (-NR’-X ２ -NR’-C(=O)-NR’-) ３ -、-X ２ (-NR’-X２ -NR'-X ２ -) ３ -, -X ２ (-NR'-X ２ -O-) ３ -, -X ２ (-NR'-X ２ -OC(=O)-) ３ -, -X ２ (-NR'-X ２ -OC(=O)-NR'-) ３ -, -X ２ (-NR'-X ２ -O-X ２ -) ３ -, -X ２ (-NR'-X ２ -C(=O)-O-) ３ -, -X ２ (-NR'-X ２ -C(=O)-NR'-) ３ -, -X ２ (-NR'-X ２ -) ３ -, -X ２ (-C(=O)-) ３ -, -X ２ (-C(=O)-O-) ３ -, -X ２ (-C(=O)-NR'-) ３ -, -X ２ (-C(=O)-S-) ３ -, -X ２ (-SO ２ -) ３ -, -X ２ (-SO ２ NR'-) ３ -, -X ２ (-C(OR')(R')(-)) ３ -, etc.

[0049] [R] R is a monovalent aliphatic hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent. R may be cyclic, branched, or linear, preferably branched or linear, and more preferably linear. R is preferably a saturated aliphatic hydrocarbon group (alkyl group), which may have a substituent.

[0050] The number of carbon atoms in R 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. The number of carbon atoms in R 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.

[0051] [Acrylic Polymer-Type Liquid-Repellent Compound] The liquid-repellent compound may be an acrylic polymer (acrylic polymer-type liquid-repellent compound). The acrylic polymer-type liquid-repellent compound contains repeating units derived from the hydrocarbon monomers shown below. It may further contain repeating units derived from a crosslinkable monomer, a halogenated olefin monomer, and / or other monomers.

[0052] (Hydrocarbon Monomer) The acrylic polymer type liquid repellent compound is represented by the following formula: CH ２ =C(-Q)-C(=O)-X-R ｎ [wherein Q is a hydrogen atom, a monovalent organic group or a halogen atom, and X is a direct bond, —O—, —C(═O)—, —S(═O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), １ and X is a hydrocarbon group having 1 to 40 carbon atoms. ２ and a 1+n-valent group consisting of one or more selected from the group consisting of: R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and n is an integer from 1 to 3. The hydrocarbon monomer itself may be used as the liquid repellent compound.

[0053] The explanations for X, R, and n are as given in the above section on liquid-repellent compounds.

[0054] In particular, in the acrylic polymer type liquid repellent compound, X is represented by the following formula: １ - or -X １ -X ２ -X１ - [wherein, X １ is independently in each occurrence -O-, -NR'-, -C(=O)-NR'-, -NR'-C(=O)-, or -NR'-C(=O)-NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and X ２ is a hydrocarbon group having 1 to 40 carbon atoms.]

[0055] Q is a hydrogen atom, a monovalent organic group, or a halogen atom. Examples of monovalent organic groups include a cyano group, an aliphatic hydrocarbon group having 1 to 6 carbon atoms (e.g., an alkyl group, an alkenyl group, etc.), and an aromatic group having 5 to 12 carbon atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Q may be a hydrogen atom, a halogen atom, a methyl group, a cyano group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is, for example, a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom, and particularly preferably a hydrogen atom or a methyl group.

[0056] From the viewpoint of liquid repellency, the hydrocarbon monomer may include a hydrocarbon monomer containing an amide group, a urea group, or a urethane group in X. The hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group, or a urethane group and a hydrocarbon monomer not having an amide group, a urea group, or a urethane group.

[0057] The hydrocarbon monomer may be only a non-cyclic hydrocarbon group-containing monomer, or may also include a cyclic hydrocarbon group-containing monomer. The cyclic hydrocarbon group-containing monomer is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0058] The cyclic hydrocarbon group-containing monomer preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may, for example, have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0059] The cyclic hydrocarbon group may be alicyclic or aromatic, preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a linear or branched chain hydrocarbon group).

[0060] 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.

[0061] 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.

[0062] Specific examples of the cyclic hydrocarbon group-containing monomer 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.

[0063] Specific examples of hydrocarbon monomers are as follows: The compound of the following chemical formula is an acrylic compound in which the α-position is a hydrogen atom, but the α-position may be other Q, such as a methacrylic compound in which the α-position is a methyl group, or an α-chloroacrylic compound in which the α-position is a chlorine atom. CH ２ =CHC(=O)OC ｐ H ２ｐ NHC(=O)C ｑ H ２ｑ＋１ CH ２ =CHC(=O)OC ２ H ４ NHC(=O)C １７ H ３５ CH ２ =CHC(=O)OC ２ H ４ NHC(=O)C １５ H ３１ CH ２ =CHC(=O)OC ２ H ４ NHC(=O)C １７ H ３５ and CH ２ =CHC(=O)OC ２ H ４ NHC(=O)C １５ H ３１ Mixture with CH ２ =CHC(=O)OC ｑ H ２ｑ＋１ CH ２ =CHC(=O)OC １８ H ３７ CH ２ =CHC(=O)OC １６ H ３３ CH ２ =CHC(=O)OC ２ H ４ OC(=O)NHC ｑ H ２ｑ＋１ CH ２ =CHC(=O)OC ２ H ４ NHC(=O)OC ｑ H ２ｑ＋１ CH ２ =CHC(=O)OC ２ H ４ NHC(=O)NHC ｑ H ２ｑ＋１ CH２ =CHC(=O)OC ４ H ８ OC(=O)NHC ｑ H ２ｑ＋１ CH ２ =CHC(=O)OC ２ H ４ OC(=O)NHC １８ H ３７ CH ２ =CHC(=O)OC ２ H ４ NHC(=O)OC １８ H ３７ CH ２ =CHC(=O)NHC ｐ H ２ｐ OC(=O)NHC ｑ H ２ｑ＋１ CH ２ =CHC(=O)OC ｐ H ２ｐ－１ (NH(C=O)C ｑ H ｑ＋１ )(NH(C=O)C ｑ H ｑ＋１ )CH ２ =CHC(=O)OC ｐ H ２ｐ－１ (NH(C=O)C １７ H ３５ (NH(C=O)C １７ H ３５ )CH ２ =CHC(=O)OC ｐ H ２ｐ－１ (O(C=O)NHC ｑ H ｑ＋１ (CH ２ O(C=O)NHC ｑ H ｑ＋１ )CH ２ =CHC(=O)OCH ２ CH(O(C=O)NHC １８ H ３７ (CH ２ O(C=O)NHC １８ H ３７ [In the above formula, p is 1 to 40 (for example, 1 to 6), and q is 6 to 40 (for example, 12 to 30).]

[0064] (Halogenated Olefin Monomer) The acrylic polymer-type liquid-repellent compound may have a repeating unit derived from a halogenated olefin monomer. The halogenated olefin monomer preferably does not contain fluorine atoms. The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms and substituted with 1 to 10 chlorine, bromine, or iodine atoms. The halogenated olefin monomer is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and 1 to 5 chlorine atoms. Preferred examples of the halogenated olefin monomer 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 is preferred because it enhances water repellency (particularly water repellency durability). The presence of repeating units derived from a halogenated olefin monomer enhances the washing durability of the acrylic polymer-type liquid-repellent compound.

[0065] (Crosslinkable Monomer) The acrylic polymer type liquid repellent compound may have a repeating unit derived from a crosslinkable monomer. The crosslinkable monomer is a monomer capable of imparting crosslinkability to the polymer and may have at least two groups selected from the group consisting of reactive groups and olefinic carbon-carbon double bonds. The crosslinkable monomer may be a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group.

[0066] The crosslinkable monomer 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.

[0067] Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a carbonyl group, and an isocyanate group.

[0068] Specific examples of crosslinkable monomers include diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxyethyl (meth)acrylamide, glycidyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 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. These may be used alone or in combination of two or more. These may be used alone or in combination of two or more.

[0069] (Other Monomers) The acrylic polymer type liquid repellent compound may contain repeating units derived from other monomers other than the above-mentioned monomers.

[0070] Specific examples of other monomers include acrylonitrile, alkoxypolyalkylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, organosiloxane-containing (meth)acrylate, vinyl acetate, vinyl alkyl ether, etc. The other monomers are not limited to these examples. These may be used alone or in combination of two or more.

[0071] (Composition, etc.) The amount of repeating units derived from hydrocarbon-based monomers may be 5 wt% or more, 15 wt% or more, 20 wt% or more, 25 wt% or more, 35 wt% or more, 45 wt% or more, 55 wt% or more, or 65 wt% or more relative to the acrylic polymer-type liquid-repellent compound. The amount of repeating units derived from hydrocarbon-based monomers may be 98 wt% or less, 95 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or less, or 60 wt% or less relative to the acrylic polymer-type liquid-repellent compound. Of the hydrocarbon-based monomers, hydrocarbon-based monomers having an amide group, urea group, or urethane group may be 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, or 75 wt% or more. Among the hydrocarbon monomers, the hydrocarbon monomer having an amide group, urea group, or urethane group may be 80% by weight or less, 60% by weight or less, 40% by weight or less, or 20% by weight or less. Among the hydrocarbon monomers, the cyclic hydrocarbon group-containing monomer may be 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, 30% by weight or more, 50% by weight or more, or 75% by weight or more. Among the hydrocarbon monomers, the cyclic hydrocarbon group-containing monomer may be 80% by weight or less, 60% by weight or less, 40% by weight or less, or 20% by weight or less.

[0072] The amount of repeating units derived from halogenated olefin monomers may be 3% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, or 35% by weight or more, relative to the acrylic polymer type liquid repellent compound. The amount of repeating units derived from halogenated olefin monomers may be 80% by weight or less, 70% by weight or less, 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, or 10% by weight or less, preferably 60% by weight or less, relative to the acrylic polymer type liquid repellent compound.

[0073] The amount of repeating units derived from cyclic hydrocarbon group-containing monomers may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, based on the acrylic polymer type liquid repellent compound. The amount of repeating units derived from halogenated olefin monomers may be 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or 5% by weight or less, based on the acrylic polymer type liquid repellent compound.

[0074] The amount of the repeating units derived from the crosslinkable monomer may be 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, or 20% by weight or more, based on the acrylic polymer type liquid repellent compound. The amount of the repeating units derived from the crosslinkable monomer may be 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, or 20% by weight or less, based on the acrylic polymer type liquid repellent compound.

[0075] The amount of repeating units derived from other monomers may be 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, or 20% by weight or more, relative to the acrylic polymer type liquid repellent compound. The amount of repeating units derived from other monomers may be 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, or 20% by weight or less, relative to the acrylic polymer type liquid repellent compound.

[0076] The weight average molecular weight of the acrylic polymer type liquid repellent compound may be 500 or more, 1000 or more, 2500 or more, 5000 or more, 10000 or more, 25000 or more, or 50000 or more, and is preferably 5000 or more. The weight average molecular weight of the acrylic polymer type liquid repellent compound may be 1,000,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, or 10,000 or less, and is preferably 100,000 or less.

[0077] (Polymerization Method) The acrylic polymer type liquid repellent compound 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.

[0078] 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.

[0079] 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, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] [Base Material Modified Liquid-Repellent Compound] The liquid-repellent compound may be a base material modified with a hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent (base material modified liquid-repellent compound).

[0085] The base material-modified liquid repellent compound is a compound represented by the following formula: -X-R ｎ [wherein X is a direct bond or a group having a valence of 1+n, R is independently in each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and n is 1 to 3.]

[0086] Examples of matrix compounds include starch, cellulose, curdlan, pullulan, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, xanthan gum, gelatin gum, tamarind seed gum, cycloamylose, glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, stephoxide, dextrin, cyclodextrin, glycerin, polyglycerin, and menthol. , xylitol, sucralose, fructose, maltose, trehalose, lactosucrose, erythritol, vanillin, cholesterol, glucosamine, catechin, anthocyanin, quercetin, citric acid, malic acid, gluconic acid, alginic acid, butyric acid, lactic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, chlorogenic acid, aldonic acid, uronic acid, aldaric acid, phytic acid, and ascorbic acid, and derivatives thereof.

[0087] The matrix compound may be a polymer (e.g., a condensation product or a crosslinked product) of the compounds exemplified above. Suitable examples of the polymer include glycerin polymer and citric acid polymer.

[0088] The condensation reaction or crosslinking reaction for obtaining a polymer is not limited, and a known method of causing polymerization to proceed at the functional groups of a base compound can be used, and known catalysts, dehydration condensing agents, crosslinking agents, etc. Examples of the catalyst, dehydration condensing agent, and crosslinking agent that can be used include acids such as p-toluenesulfonic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, sulfuric acid, and fluoroboric acid; acid halides such as acetyl chloride, propionic acid chloride, and benzoic acid chloride; bases such as sodium methoxide, potassium tert-butoxide, sodium hydride, potassium carbonate, cesium carbonate, triethylamine, and diisopropylamine; tetrabutylammonium bromide, sodium acetate, Burgess reagent, N,N'-dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (WSC) or its hydrochloride, N,N'-carbonyldiimidazole, 1H-benzotriazole-1- condensing agents such as yloxytris(dimethylamino)phosphonium hexafluorophosphate (BOP), O-(7-azabenzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HATU), 2-chloro-1,3-dimethylimidazolium chloride, bromotripyrrolidinophosphonium hexafluorophosphate (PyBrop), diethylphosphocyanidate (diethyl cyanophosphate; DEPC), diphenylphosphoryl azide (diphenylphosphoryl azide; DPPA), 4-(4,6-dimethoxy[1,3,5]triazin-2-yl)-4-methylmorpholinium chloride (DMTMM); Lawesson's reagent, and the like.

[0089] The explanations for X, R, and n are as given in the above section on liquid-repellent compounds.

[0090] The base compound may have a hydroxy group. In this case, the hydroxy group may form a group represented by the following formula in the base-modified liquid repellent compound: -O-, -O-C(=O)-, -O-C(=O)-NR'-, or -O-C=S-NR'- (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms).

[0091] The base compound may have a carboxy group. In this case, the carboxy group may form a group represented by the following formula in the liquid repellent compound: -C(=O)- -C(=O)-O- -C(=O)-NR'-, or -C(=O)-S- (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms).

[0092] The weight average molecular weight of the base compound may be 500 or more, 1000 or more, 2500 or more, 5000 or more, 10000 or more, 25000 or more, 50000 or more, 100000 or more, or 250000 or more. The weight average molecular weight of the acrylic polymer type liquid repellent compound may be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 250000 or less, or 10000 or less.

[0093] (Method for producing a base material-modified liquid repellent compound) The method for modifying the base material compound with a hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, is not particularly limited. For example, methods such as a urethane bond formation reaction, a urea bond formation reaction, an ester bond formation reaction, an amide bond formation reaction, and an ether bond formation reaction can be used. In the bond formation reaction, an acylating agent, a condensing agent, a catalyst, etc. are appropriately used.

[0094] The hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, of the base compound may be modified by reacting the base compound with a hydrocarbon group-containing reactant. The hydrocarbon group-containing reactant is a compound having an aliphatic hydrocarbon group and a group capable of reacting with the functional group of the base compound.

[0095] Examples of hydrocarbon group-containing reactants are: ２ N-R HO-R HO(O=)C-R G(O=)C-R RC(=O)OC(=O)R O=C=N-R S=C=N-R (CH ２ OCH)CH ２ OR G-R (wherein R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms and optionally having a substituent, as defined above, and G is a halogen atom (particularly F, Cl, Br, or I).)

[0096] Urethane bond formation The base compound and the hydrocarbon group may be bonded via a urethane bond. The urethane bond may be formed, for example, by reacting a hydroxyl group-containing base compound with an aliphatic hydrocarbon-containing isocyanate. A tin catalyst or an amine may be used as a catalyst during the reaction. For example, by reacting a hydroxyl group-containing base compound with an aliphatic hydrocarbon group-containing isocyanate in an organic solvent for a certain period of time, the hydroxyl group reacts with the isocyanate group, thereby producing a base-modified liquid-repellent compound in which the base compound and the hydrocarbon group are bonded via a urethane bond.

[0097] Urea bond formation The base compound and the hydrocarbon group may be bonded via a urea bond. The urea bond may be formed, for example, by reacting an amino group-containing base compound with an aliphatic hydrocarbon group-containing isocyanate group (or by reacting an isocyanate group-containing base compound with an aliphatic hydrocarbon group-containing amine). A catalyst may be used as appropriate during the reaction. For example, by reacting an amino group-containing base compound with an aliphatic hydrocarbon-containing isocyanate in an organic solvent for a certain period of time, the amino group reacts with the isocyanate group, thereby obtaining a base-modified liquid-repellent compound in which the base compound and the hydrocarbon group are bonded via a urea bond.

[0098] Ester bond formation The base compound and the hydrocarbon group may be bonded via an ester bond. The ester bond may be formed, for example, by reacting a hydroxyl group-containing base compound with an aliphatic hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing base compound with an aliphatic hydrocarbon group-containing alcohol). An acylation catalyst, a condensing agent, or the like may be used during the reaction. For example, by reacting a hydroxyl group-containing base compound with an aliphatic hydrocarbon group-containing carboxylic acid in an organic solvent for a certain period of time, the hydroxyl group reacts with the carboxylic acid, thereby obtaining a base-modified liquid-repellent compound in which the base compound and the hydrocarbon group are bonded via an ester bond.

[0099] Amide bond formation The base compound and the hydrocarbon group may be bonded via an amide bond. The amide bond may be formed, for example, by reacting an amino group-containing base compound with an aliphatic hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing base compound with an aliphatic hydrocarbon group-containing amine). An acylation catalyst, a condensing agent, or the like may be used during the reaction. For example, by reacting an amino group-containing base compound with an aliphatic hydrocarbon group-containing carboxylic acid in an organic solvent for a certain period of time, the amino group reacts with the carboxylic acid, thereby obtaining a base-modified liquid-repellent compound in which the base compound and the hydrocarbon group are bonded via an amide bond.

[0100] Ether bond formation The base compound and the hydrocarbon group may be bonded via an ether bond. The ether bond may be formed, for example, by reacting a halogen-containing base compound with an aliphatic hydrocarbon group-containing alcohol (or by reacting a hydroxyl group-containing base compound with an aliphatic hydrocarbon group-containing halide). An acid catalyst, a base catalyst, or the like may be used during the reaction. For example, by heating and reacting a halogen-containing base compound with an aliphatic hydrocarbon group-containing alcohol in an organic solvent in the presence of a catalyst, the aliphatic hydrocarbon group-containing alcohol acts as a nucleophile, and a base-modified liquid-repellent compound in which the base compound and the hydrocarbon group are bonded via an ether bond is obtained.

[0101] [Ring-modified liquid-repellent compound] The liquid-repellent compound may be a liquid-repellent compound (ring-modified liquid-repellent compound) in which an aromatic ring or a nitrogen-containing heterocycle is modified with an aliphatic hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent.

[0102] The ring-modified liquid repellent compound is represented by the following formula: A(-X-R ｎ ) ｍ [wherein A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocycle which may have a substituent, X is, independently in each occurrence, a direct bond or a 1+n-valent group, R is, independently in each occurrence, an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, n is, independently in each occurrence, 1 to 3, and m is, independently in each occurrence, 1 to 6.]

[0103] The explanations for X, R, and n are as given in the above section on liquid-repellent compounds.

[0104] A is an m-valent group. m may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and preferably 2 or more. m may be 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less, and preferably 4 or less.

[0105] A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocycle which may have a substituent. Examples of the aromatic ring include hydrocarbon aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring; heteroaromatic rings such as a pyridine ring, a pyrimidine ring, a quinoline ring, a furan ring, a pyrrole ring, and a pyrazole ring; and the like. Examples of the nitrogen-containing heterocycle include non-aromatic nitrogen-containing heterocycles such as pyrrolidine, pyrazolidine, triazolidine, oxazolidine, isoxazolidine, thiazolidine, isothiazolidine, piperidine, piperazine, and morpholine; aromatic nitrogen-containing heterocycles such as a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, an oxazine ring, and a thiazine ring; and the like.

[0106] The aromatic ring or nitrogen-containing hetero ring may have a substituent. Examples of the aromatic ring or nitrogen-containing hetero ring that may have a substituent include, but are not limited to, —OR′, —N(R′) ２ , —COOR′ (wherein R′ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a halogen atom, optionally substituted with one or more halogen atoms, C １－６ Alkyl group, C ２－６ Alkenyl group, C ２－６ Alkynyl group, C ３－１０ Cycloalkyl group, C ３－１０ Unsaturated cycloalkyl groups, 5- to 10-membered heterocyclyl groups, 5- to 10-membered unsaturated heterocyclyl groups, C ６－１０ Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0107] The aromatic ring or nitrogen-containing heterocycle may be a 4-, 5-, 6-, 7-, or 8-membered ring. The aromatic ring or nitrogen-containing heterocycle may be a condensed polycycle containing 2 to 5 (preferably 2 to 3) 4- to 8-membered rings.

[0108] The ring-modified liquid-repellent compound may be a polymer (for example, a condensate or crosslinked product) of the ring-modified liquid-repellent compound. In the polymer, polymerization may proceed via the substituent of A.

[0109] The condensation reaction or crosslinking reaction for obtaining a polymer is not limited, and a known method of proceeding with polymerization at the functional group possessed by A can be used, and known catalysts, dehydration condensing agents, crosslinking agents, etc. may also be used. Examples of the catalyst, dehydration condensing agent, and crosslinking agent that can be used include acids such as p-toluenesulfonic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, sulfuric acid, and fluoroboric acid; acid halides such as acetyl chloride, propionic acid chloride, and benzoic acid chloride; bases such as sodium methoxide, potassium tert-butoxide, sodium hydride, potassium carbonate, cesium carbonate, triethylamine, and diisopropylamine; tetrabutylammonium bromide, sodium acetate, Burgess reagent, N,N'-dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (WSC) or its hydrochloride, N,N'-carbonyldiimidazole, 1H-benzotriazole-1- condensing agents such as yloxytris(dimethylamino)phosphonium hexafluorophosphate (BOP), O-(7-azabenzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HATU), 2-chloro-1,3-dimethylimidazolium chloride, bromotripyrrolidinophosphonium hexafluorophosphate (PyBrop), diethylphosphocyanidate (diethyl cyanophosphate; DEPC), diphenylphosphoryl azide (diphenylphosphoryl azide; DPPA), 4-(4,6-dimethoxy[1,3,5]triazin-2-yl)-4-methylmorpholinium chloride (DMTMM); Lawesson's reagent, and the like.

[0110] In the ring-modified liquid repellent compound, X is represented by the following formula: １- or -X １ -X ２ -X １ - [wherein, X １ is independently in each occurrence a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —C(OR′)R′—, or —C(OR′)(—) ２ [R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms], and X ２ is a hydrocarbon group having 1 to 40 carbon atoms.] This can impart good liquid repellency to the substrate.

[0111] (Method for producing ring-modified liquid-repellent compound) The method for modifying the hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, on the aromatic ring or nitrogen-containing heterocycle is not particularly limited. For example, methods such as urethane bond formation reaction, urea bond formation reaction, ester bond formation reaction, amide bond formation reaction, and ether bond formation reaction can be used. In the bond formation reaction, an acylating agent, a condensing agent, a catalyst, etc. are appropriately used.

[0112] The hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, on the aromatic ring or nitrogen-containing heterocycle may be modified by reacting it with a hydrocarbon group-containing reactant. The hydrocarbon group-containing reactant is a compound having an aliphatic hydrocarbon group and a group capable of reacting with a functional group possessed by the aromatic ring or nitrogen-containing heterocycle.

[0113] Examples of hydrocarbon group-containing reactants are: ２ N-R HO-R HO(O=)C-R G(O=)C-R RC(=O)OC(=O)R O=C=N-R S=C=N-R (CH ２ OCH)CH ２ OR G-R (wherein R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, as defined above, and G is a halogen atom (particularly F, Cl, Br, or I).)

[0114] Urethane bond formation An aromatic ring or nitrogen-containing heterocycle and a hydrocarbon group may be bonded via a urethane bond. The urethane bond may be formed, for example, by reacting a hydroxyl group-containing aromatic ring or nitrogen-containing heterocycle with an aliphatic hydrocarbon-containing isocyanate. A tin catalyst or an amine can be used as a catalyst during the reaction. For example, by reacting a hydroxyl group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing isocyanate in an organic solvent for a certain period of time, the hydroxyl group reacts with the isocyanate group, thereby obtaining a ring-modified liquid-repellent compound in which the aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group are bonded via a urethane bond.

[0115] Urea bond formation An aromatic ring or nitrogen-containing heterocycle and a hydrocarbon group may be bonded via a urea bond. The urea bond may be formed, for example, by reacting an amino group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing isocyanate group (or by reacting an isocyanate group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing amine). A catalyst may be used as appropriate during the reaction. For example, by reacting an amino group-containing aromatic ring or nitrogen-containing heterocycle with an aliphatic hydrocarbon-containing isocyanate in an organic solvent for a certain period of time, the amino group reacts with the isocyanate group, thereby obtaining a ring-modified liquid-repellent compound in which the aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group are bonded via a urea bond.

[0116] Ester bond formation An aromatic ring or nitrogen-containing heterocycle and a hydrocarbon group may be bonded via an ester bond. The ester bond may be formed, for example, by reacting a hydroxyl group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing alcohol). An acylation catalyst, a condensation agent, or the like may be used during the reaction. For example, by reacting a hydroxyl group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing carboxylic acid in an organic solvent for a certain period of time, the hydroxyl group reacts with the carboxylic acid, thereby obtaining a ring-modified liquid-repellent compound in which the aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group are bonded via an ester bond.

[0117] Amide bond formation An aromatic ring or nitrogen-containing heterocycle and a hydrocarbon group may be bonded via an amide bond. The amide bond may be formed, for example, by reacting an amino group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing amine). An acylation catalyst, a condensation agent, or the like may be used during the reaction. For example, by reacting an amino group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing carboxylic acid in an organic solvent for a certain period of time, the amino group reacts with the carboxylic acid, thereby obtaining a ring-modified liquid-repellent compound in which the aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group are bonded via an amide bond.

[0118] Ether bond formation An aromatic ring or nitrogen-containing heterocycle and a hydrocarbon group may be bonded via an ether bond. The ether bond may be formed, for example, by reacting a halogen-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing alcohol (or by reacting a hydroxyl group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing halide). An acid catalyst, a base catalyst, or the like may be used during the reaction. For example, by heating and reacting a halogen-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing alcohol in an organic solvent in the presence of a catalyst, the hydrocarbon group-containing alcohol acts as a nucleophile, and a ring-modified liquid-repellent compound in which the aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group are bonded via an ether bond is obtained.

[0119] [Isocyanate-Based Liquid-Repellent Compound] The liquid-repellent compound may be a liquid-repellent compound (isocyanate-based liquid-repellent compound) that is a reaction product of an isocyanate group-containing compound and an isocyanate-reactive compound, and preferably may be an isocyanate-based liquid-repellent compound having a hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent.

[0120] Examples of isocyanate group-containing compounds that can be used to prepare isocyanate-based liquid repellent compounds include higher functional isocyanates, including isocyanates, diisocyanates, triisocyanates, and polymeric isocyanates, which may be aliphatic (including alicyclic) or cyclic (including aromatic). Examples of diisocyanates include 4,4'-methylenediphenylene diisocyanate (MDI), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, o-, m-, and p-xylylene diisocyanate, 4,4'-diisocyanatodiphenyl ether, 3,3'-dichloro-4,4'-diisocyanatodiphenylmethane, 4,4'-diphenyl diisocyanate, 4,4'-diisocyanatodibenzyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl, 2,2'-dichloro-5,5'-dimethoxy-4,4'-diisocyanatodiphenyl, 1,3-diisocyanatobenzene, and 1,2-naphthylenediisocyanate. isocyanate, 4-chloro-1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, and 1,8-dinitro-2,7-naphthylene diisocyanate; alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate; aliphatic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, and 1,2-ethylene diisocyanate; and cyclic diisocyanates such as isophorone diisocyanate (IPDI) and dicyclohexylmethane-4,4′-diisocyanate. Examples of triisocyanates include aliphatic triisocyanates such as 1,3,6-hexamethylene triisocyanate, and aromatic triisocyanates such as tri-(4-isocyanatophenyl)-methane. Examples of polymeric isocyanates include polymethylene polyphenylisocyanate (PAPI).

[0121] The isocyanate-reactive compound is a compound containing an isocyanate-reactive group, and examples thereof include monofunctional, difunctional, and polyfunctional alcohols, thiols, and amines. Examples of the isocyanate-reactive compound include straight-chain or branched long-chain alkanols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, 2-ethylhexanol, glycidol, (iso)stearyl alcohol, behenyl alcohol, and the like, and alkyl alcohols having C6 to C40 alkyl chains; and alcohols containing poly(oxyalkylene) groups such as methyl or ethyl ethers of polyethylene glycol, and hydroxy-terminated methyl or ethyl ethers of random or block copolymers of ethylene oxide and / or propylene oxide with polysiloxane (e.g., polydimethylsiloxane) groups-containing alcohols. Further examples include diols, triols, and polyols such as 1,4-butanediol, 1,6-hexanediol, 1-10-decanediol, 4,4'-isopropylidenediphenol (bisphenol A), glycerol, pentaerythritol, dipentaerythritol, polycaprolactone diols, fatty acid dimer diols, and alkyl esters such as -OCH ２ CH ２ -, -O(CH ２ ) ４ -, -OCH ２ CH ２ CH ２ -, -OCH(CH ３ ) CH ２ -, and -OCH(CH ３ ) CH(CH ３)-, and other poly(oxy)alkylene diols having oxyalkylene groups having 2 to 4 carbon atoms (the oxyalkylene units in the poly(oxyalkylene) may be the same as in polypropylene glycol or may be present as a mixture), as well as ester diols such as glycerol monostearate and polysiloxane-containing diols (e.g., polydimethylsiloxane-containing diols). Isocyanate-reactive compounds include amino-containing compounds such as octadecylamine, di(octadecyl)amine, 1,6-hexamethylenediamine, and other amino-terminated polyethylene oxide or propylene oxide or copolymers thereof, amino-terminated methyl or ethyl ethers of polyethylene oxide or polypropylene oxide or copolymers thereof, and amino-terminated polysiloxanes, for example, polydimethylsiloxane.

[0122] The isocyanate-based compound preferably has, in addition to an isocyanate-reactive group, a hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent (particularly an aliphatic hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent (corresponding to R above)).

[0123] The isocyanate-based compound may be a polymer formed by sequentially reacting an isocyanate with an isocyanate-reactive compound.

[0124] The isocyanate-based liquid repellent compound has the following formula: L(-X-R ｎ ) ｍ[wherein L is an m-valent urethane / amide skeleton which is a reaction product of (a) one or more isocyanate group-containing compounds selected from the group consisting of isocyanates, diisocyanates, and polyisocyanates, and (b) one or more isocyanate-reactive compounds selected from the group consisting of compounds represented by the following general formulas (2a), (2b), and (2c), X is, independently in each occurrence, a direct bond or a 1+n-valent group, R is, independently in each occurrence, an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, n is, independently in each occurrence, 1 to 3, and m is, independently in each occurrence, 1 to 6.] In the general formulas (2a) and (2c): Rr is independently, in each occurrence, —H, —*, —C(O)—*, —(CH ２ CH ２ O) ｐ (CH (CH ３ ) CH ２ O) ｑ H, -(CH ２ CH ２ O) ｐ (CH (CH ３ ) CH ２ O) ｑ -* or -(CH ２ CH ２ O) ｐ (CH (CH ３ ) CH ２ O) ｑ C(O)-*, p is independently 0 to 20 in each occurrence, q is independently 0 to 20 in each occurrence, p+q is greater than 0, and the symbol * represents a bond of L, provided that when the isocyanate-reactive compound is represented by general formula (2a) or (2c), at least one of Rr is -H or -(CH ２ CH ２ O) ｐ (CH (CH ３ ) CH ２ O) ｑ H, and at least one other of Rr is -*, -C(O)-*, -(CH ２ CH ２ O) ｐ (CH (CH３ ) CH ２ O) ｑ -* or -(CH ２ CH ２ O) ｐ (CH (CH ３ ) CH ２ O) ｑ In the general formula (2b): Rr' is independently in each occurrence -H, -*, -C(O)-*, -(CH ２ CH ２ O) ｐ’ (CH (CH ３ ) CH ２ O) ｑ’ H, -(CH ２ CH ２ O) ｐ’ (CH (CH ３ ) CH ２ O) ｑ’ -* or -(CH ２ CH ２ O) ｐ’ (CH (CH ３ ) CH ２ O) ｑ’ C(O)-*, and Rr″ is independently in each occurrence —H, —*, —(CH ２ CH ２ O) ｐ’ (CH (CH ３ ) CH ２ O) ｑ’ H, -(CH ２ CH ２ O) ｐ’ (CH (CH ３ ) CH ２ O) ｑ’ -* or -(CH ２ CH ２ O) ｐ’ (CH (CH ３ ) CH ２ O) ｑ’ C(O)-*, p' is independently 0 to 20 in each occurrence, q' is independently 0 to 20 in each occurrence, p'+q' is greater than 0, and the symbol * represents a bond of L, provided that when the isocyanate-reactive compound is represented by general formula (2b), at least one of Rr' and Rr'' is -H or -(CH２ CH ２ O) ｐ’ (CH (CH ３ ) CH ２ O) ｑ’ H, and at least one other of Rr' and Rr'' is -*, -C(O)-*, -(CH ２ CH ２ O) ｐ’ (CH (CH ３ ) CH ２ O) ｑ’ -* or -(CH ２ CH ２ O) ｐ’ (CH (CH ３ ) CH ２ O) ｑ’ C(O)-*.

[0125] Note that p, q, p', and q' are integers from 0 to 20 when there is only one isocyanate-based liquid-repellent compound, but when there is an aggregate of multiple isocyanate-based liquid-repellent compounds, they can be expressed as average values.

[0126] In this case, L in the isocyanate-based liquid repellent compound is a urethane skeleton prepared by a process including reacting an isocyanate group-containing compound (a) with an isocyanate-reactive compound (b). Such a urethane / amide skeleton can typically be polyvalent, but is not limited to this. When the isocyanate-reactive compound (b) is represented by general formula (2a) or (2c), it has at least one —OH group, and when represented by general formula (2b), it has at least one —OH group or —COOH group. Therefore, by reacting the isocyanate group-containing compound (a) with the isocyanate-reactive compound (b), a reaction product in which they are bonded by a urethane bond or an amide bond can be obtained. Such reactions are known and can be carried out under any suitable conditions.

[0127] In such an isocyanate-based liquid repellent compound, each of m bonds (indicated by the symbol *) present in the portion derived from the isocyanate-reactive compound (b) is -X-R ｎ is bonded (X is bonded to the bond of L). ｎ" is bonded to a bond (indicated by the symbol *) present in the isocyanate-reactive compound (b) before the reaction. The isocyanate-reactive compound (b) may be one or a mixture of any two or more selected from the group consisting of compounds represented by general formulas (2a), (2b), and (2c), and among these, the compound represented by general formula (2a) is preferred.

[0128] The isocyanate group-containing compound (a) may be one or a mixture of any two or more selected from the group consisting of isocyanates, diisocyanates, and polyisocyanates. When the isocyanate group-containing compound (a) is a diisocyanate and / or polyisocyanate and the isocyanate-reactive compound (b) has a total of two or more -OH groups and / or -COOH groups, the reaction product obtained therefrom may be a polymer in some cases, but is not limited thereto.

[0129] The isocyanate, diisocyanate, and polyisocyanate are preferably one or more selected from the group consisting of compounds represented by the following formulas (3a) to (3h):

[0130]

[0131]

[0132] Examples of isocyanate-based liquid-repellent compounds include those described in JP-A 2022-33218 (WO2016 / 049278), Japanese Patent No. 6987847 (WO2018 / 031534), and WO2021 / 251302.

[0133] [Polysiloxane Group-Containing Liquid-Repellent Compound] The liquid-repellent compound may be a liquid-repellent compound having a polysiloxane group (polysiloxane group-containing liquid-repellent compound). Like the aliphatic hydrocarbon group (R) having 6 to 40 carbon atoms and optionally having a substituent in the other liquid-repellent compounds described above, the polysiloxane group can impart liquid repellency to the substrate.

[0134] The polysiloxane group has the following formula: -[-Si(Rs １ ) ２ -O-] ａ- [wherein, Rs １ is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and a is 5 or more and 10,000 or less.

[0135] Rs １ is a hydrocarbon group having 1 to 40 carbon atoms or a reactive group.

[0136] Examples of hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms (particularly aliphatic hydrocarbon groups, particularly alkyl groups), such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, as well as hydrocarbon groups having from 6 to 40 carbon atoms, which may have a substituent.

[0137] The hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, 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, and is 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. The number of carbon atoms in the hydrocarbon group 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. Note that the hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, referred to here may correspond to R described above, and the description of the hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, is incorporated herein.

[0138] Examples of reactive groups include groups having a functional group (e.g., a hydroxyl group, an amino group, a mercapto group, an epoxy group, a carboxyl group, a halogen-substituted alkyl group, a vinyl group, a (meth)acrylate group, a (meth)acrylamide group, a hydrogen atom directly bonded to a silicon atom, 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, for example, 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.

[0139] a may be 5 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. a 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, 100 or less, or 50 or less.

[0140] The amount of hydrocarbon groups having 1 to 40 carbon atoms is Rs １ The amount of the hydrocarbon group having 1 to 40 carbon atoms may be 20 mol % or more, 40 mol % or more, 60 mol % or more, or 80 mol % or more based on the total of Rs １ may be 100 mol % or less, 90 mol % or less, 80 mol % or less, or 70 mol % or less based on the total of

[0141] The amount of reactive groups (e.g., —OH, —COOH, or —NR′ ２ The amount of Rs １ The amount of reactive groups (e.g., —OH, —COOH, or —NR′) may be 5 mol % or more, 10 mol % or more, 20 mol % or more, or 30 mol % or more, based on the total amount of the reactive groups (e.g., —OH, —COOH, or —NR′). ２ The amount of Rs １ may be 50 mol % or less, 40 mol % or less, 30 mol % or less, or 20 mol % or less based on the total of

[0142] In the polysiloxane group-containing liquid-repellent compound, the polysiloxane group may be present in the main chain, the mother nucleus, or the side chain. For example, when the polysiloxane group is present in the side chain of the polysiloxane group-containing liquid-repellent compound, the polysiloxane-containing liquid-repellent compound may be a compound in which a part or all of the aliphatic hydrocarbon groups (R) having 6 to 40 carbon atoms and optionally having a substituent in the other liquid-repellent compounds described above (for example, acrylic polymer-type liquid-repellent compounds, base-modified liquid-repellent compounds, isocyanate-based liquid-repellent compounds) are replaced with polysiloxane groups.

[0143] The polysiloxane group may be present in the main chain or the core of the polysiloxane group-containing liquid repellent compound.

[0144] The polysiloxane group-containing liquid repellent compound may have no structure other than polysiloxane, and the polysiloxane group-containing liquid repellent compound may have a structure represented by the following formula: (Rs ２ ) ３ Si-O-[-Si(Rs １ ) ２ -O-] ａ -Si(Rs ２ ) ３ [In the formula, Rs １ and a are as described above, and Rs ２ is independently in each occurrence a hydrocarbon group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a reactive group.

[0145] The polysiloxane group may be present in a side chain of a polysiloxane group-containing liquid repellent compound (for example, a side chain of an acrylic polymer type liquid repellent compound). The side chain is a partial structure other than the main chain or the mother nucleus of the compound, and may be, for example, a terminal structure. When the polysiloxane group is present in a side chain, the polysiloxane group is represented by the following formula: -[-Si(Rs １ ) ２ -O-] ａ -Si(Rs ２ ) ３ [In the formula, Rs １ and a are as described above, and Rs ２ is independently in each occurrence a hydrocarbon group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a reactive group.

[0146] Rs ２ may be a hydrocarbon group having 1 to 40 carbon atoms or an alkoxy group having 1 to 40 carbon atoms. ２ The hydrocarbon group having 1 to 40 carbon atoms in Rs is preferably an aliphatic hydrocarbon group, preferably an alkyl group, and preferably has 1 to 5 carbon atoms. ２ The alkoxy group having 1 to 40 carbon atoms in Rs preferably has 1 to 5, 1 to 3, or 1 to 2 carbon atoms. ２ is a reactive group, an example of the reactive group is Rs １ It may be similar to:

[0147] The polysiloxane group-containing liquid-repellent compound can be synthesized by a conventionally known method. For example, a polysiloxane group-containing liquid-repellent compound having a hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, can be obtained by modifying an α-olefin by a hydrosilylation reaction, optionally using a catalyst such as a platinum or palladium compound, on the SiH group in a methylhydrogensilicone or a copolymer of dimethylsiloxane and methylhydrogensiloxane. Alternatively, the polysiloxane group-containing liquid-repellent compound may be obtained by polymerizing an acrylic monomer containing a polysiloxane group, or by reacting the reactive group of the polysiloxane with a mother compound.

[0148] [Amine Modified Compound] The liquid repellent compound may be an amine modified compound.

[0149] The molecular weight of the amine-modified product may be 200 or more, 300 or more, 350 or more, 400 or more, 500 or more, 550 or more, or 750 or more. The molecular weight of the amine-modified product may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 900 or less, 800 or less, 750 or less, or 500 or less.

[0150] The amine-modified product of the present disclosure may not have an active hydrogen-containing group. Examples of the active hydrogen-containing group include an amino group (an amino group that is not adjacent to a carbonyl group, such as a primary or secondary amino group), a hydroxyl group, and a carboxyl group. In particular, the amine-modified product of the present disclosure may not have a primary or secondary amino group that is not adjacent to a carbonyl group.

[0151] The amine modification comprises an amine backbone and a compound represented by the following formula: -X Ｎ -R ｎ [In the formula, X Ｎ is a direct bond or a group having a valence of 1+n, R is, independently in each occurrence, an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, and n is an integer of from 1 to 3.], and at least one of the aliphatic hydrocarbon-containing groups is bonded to a nitrogen atom of the amine skeleton.

[0152] (Amine skeleton) The amine modified product in the present disclosure has an amine skeleton. The amine skeleton has one or more amino groups with a predetermined number of bonds (valence) obtained by removing a predetermined number of atoms or atomic groups (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton has one or more —NH ２ , -NH-, and -N(-) ２ and includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide group, etc. The amine skeleton may be an aliphatic or aromatic group having one or more amino groups, and does not exclude the presence of heteroatoms other than nitrogen.

[0153] The molecular weight of the amine backbone may be 30 or more, 50 or more, 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more. The molecular weight of the amine backbone may be 2800 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 600 or less, 450 or less, 300 or less, or 250 or less.

[0154] The number of carbon atoms in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more. The number of carbon atoms in the amine skeleton may be 100 or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less, preferably 50 or less, particularly 30 or less.

[0155] The amine skeleton has one or more amino groups. The amino group is a monovalent to trivalent amino group, and has the structure -NH ２ , -NH-, and -N(-) ２ The number of amino groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 2 or more. The number of amino groups in the amine skeleton may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0156] The amine skeleton has a hydrocarbon group (an aliphatic hydrocarbon group or an aromatic hydrocarbon group). The hydrocarbon group may be cyclic, branched, or linear. The hydrocarbon group may be saturated or unsaturated (e.g., saturated). Here, the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group that may be interrupted by oxygen atoms and / or sulfur atoms (e.g., a linear saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having one to two hydrocarbon aromatic rings), or may be a general hydrocarbon group (e.g., a linear saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having one to two hydrocarbon aromatic rings). When the hydrocarbon group is interrupted by oxygen atoms and / or sulfur atoms, it has an ether, thioether, polyether, or polythioether structure. The number of hydrocarbon groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more. The number of hydrocarbon groups in the amine skeleton may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0157] The amine skeleton may be composed of a monovalent to trivalent amino group and a chain saturated aliphatic hydrocarbon group or aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom.

[0158] The molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more. The molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton may be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, and is preferably 6 or less or 4 or less.

[0159] Raw Material Amine Compound Examples of raw material amine compounds that are precursors of the amine skeleton include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl)ether, bis[2-(2-aminoethoxy)ethyl]ether, and bis[2-(3-aminoprotoxy)ethyl]. polyalkylenepolyamines such as ether, spermine, and spermidine; oxygen- or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine, and polyoxyethylenediamine; aromatic monoamines such as aniline, 1- or 2-naphthylamine, 1-, 2-, or 9-aminoanthracene, 9-aminophenanthracene, and 2-, 3-, or 4-aminobiphenyl; monocyclic aromatic polyamines such as o-, m-, or p-phenylenediamine, o-, m-, or p-xylylenediamine, diaminotoluene, and 2,3-, 2,4-, or 2,5-tolylenediamine;Diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenyl phenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, bisaminoditrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α, α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, Polycyclic aromatic polyamines such as diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, and 4,4'-bis(aminophenyl)amine; oxygen- or sulfur-containing polycyclic aromatic polyamines such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfide;Examples of hydroxyl group-containing polyamines include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine;

[0160] (Aliphatic Hydrocarbon-Containing Group) The amine-modified product in the present disclosure is a compound represented by the following formula: -X Ｎ -R ｎ [In the formula, X Ｎ is a direct bond or a group having a valence of 1+n, R is independently in each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and n is an integer of 1 to 3.

[0161] The number of aliphatic hydrocarbon-containing groups in the amine-modified product may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and preferably 2 or more. The number of aliphatic hydrocarbon-containing groups in the amine-modified product may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0162] At least one aliphatic hydrocarbon-containing group in the amine modified product is bonded to a nitrogen atom of the amine skeleton. The ratio of the number of aliphatic hydrocarbon-containing groups bonded to nitrogen atoms of the amine skeleton to the total number of aliphatic hydrocarbon-containing groups in the amine modified product may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%. The ratio of the number of aliphatic hydrocarbon-containing groups bonded to nitrogen atoms of the amine skeleton to the total number of aliphatic hydrocarbon-containing groups in the amine modified product may be 75% or less, 50% or less, or 25% or less. The aliphatic hydrocarbon-containing groups not bonded to nitrogen atoms of the amine skeleton are bonded to other groups (e.g., hydrocarbon groups) on the amine skeleton.

[0163] ・X Ｎ X Ｎ represents a direct bond or a 1+n valent group, preferably a 1+n valent group. Ｎ functions as a linker connecting the amine skeleton and n Rs.

[0164] n is X Ｎ is the number of R's bonded to and may be an integer of 1 to 3. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0165] X Ｎ may be an aliphatic group (unsaturated or saturated) or an aromatic group.

[0166] X Ｎ The molecular weight of X may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more. Ｎ may have a molecular weight of 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 300 or less.

[0167] X Ｎ may have a carbonyl group. Ｎ may have one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group, or X Ｎ may form, together with the amino group in the amine skeleton, one or more groups selected from the group consisting of an amide group, a urea group, a urethane group, and an imide. Examples of such an amide group, a urea group, a urethane group, and an imide include: -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)- [wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms]. X Ｎ is preferably bonded to the nitrogen atom in the amine skeleton via a —(C═O)— group.

[0168] X Ｎ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , -N(-) ２, a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, and a di- to tetravalent heterocyclic ring [wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms].

[0169] X Ｎ represents a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ , -N(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), Ｎ１ and X is one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent to tetravalent hydrocarbon aromatic ring, and a divalent to tetravalent heterocycle. Ｎ２ and may be a 1+n valent group consisting of one or more selected from the group consisting of Ｎ The group written as follows is bonded to the amine skeleton on the left and to R on the right.

[0170] X Ｎ１ X Ｎ１ is a non-hydrocarbon linker.

[0171] X Ｎ１ is a direct bond or a divalent or higher valent group. Ｎ１ The valence of X may be 2 to 4, 2 to 3, or 2. Ｎ１ is preferably not only a direct bond.

[0172] X Ｎ１ The molecular weight of X may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more. Ｎ１ may have a molecular weight of 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0173] X Ｎ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , -N(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). X Ｎ１ Examples of include a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —C(═O)—NR′—, —C(═O)—NR′—C(═O)—NR′—, —C(═NR′)—, —S—, and —SO ２ -, -SO ２ NR'-, -C(OR')R'-, -C(OR')(-) ２ , -N(-) ２ and the like (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). Ｎ１ is bonded to a nitrogen atom of the amine skeleton, the nitrogen atom is considered to be part of the amine skeleton (amino group).

[0174] X Ｎ２ X Ｎ２ is a hydrocarbon or aromatic linker.

[0175] X Ｎ２ X may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). Ｎ２ X may be aliphatic or aromatic, preferably aliphatic. Ｎ２ may be linear, branched or cyclic. Ｎ２ is preferably linear.

[0176] X Ｎ２ is a divalent or higher valent group. Ｎ２ The valency of may be, for example, 2-4, 2-3, or 2.

[0177] X Ｎ２ The number of carbon atoms in X may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more. Ｎ２may have 40 or fewer, 35 or fewer, 30 or fewer, 25 or fewer, 20 or fewer, 15 or fewer, 10 or fewer, or 5 or fewer carbon atoms.

[0178] X Ｎ２ is composed of one or more selected from the group consisting of di- to tetravalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, di- to tetravalent hydrocarbon aromatic rings, and di- to tetravalent heterocycles.

[0179] The di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a chain hydrocarbon group (particularly a straight-chain hydrocarbon group). The di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be 15 or less, 10 or less, or 5 or less.

[0180] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The hydrocarbon aromatic ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and -N(R') ２ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, a halogen atom, etc. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4 or less, 3 or less, or 2.

[0181] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of divalent to tetravalent heterocycles include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The heterocycle may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') ２ (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, a halogen atom, etc. The valence of the heterocycle may be 2 or more, 3 or more, or 4 or less, 3 or less, or 2.

[0182] X Ｎ２ Examples of -Ali- -Cy- -Ali(-) ２ -Cy(-) ２ -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- (wherein Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.)

[0183] X Ｎ２ Specific examples of -(CH ２ ) ｐ -(p is 1 to 20, for example, 1 to 10), a linear hydrocarbon group having an unsaturated bond of 1 to 40 carbon atoms, for example, 1 to 10 carbon atoms, a hydrocarbon group having a branched structure of 1 to 40 carbon atoms, for example, 1 to 10 carbon atoms, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ-(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0184] X Ｎ Example of X Ｎ In the following, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms in each occurrence.

[0185] X Ｎ An example of Ｎ When is divalent, -X Ｎ１ -, -X Ｎ１ -X Ｎ２ -, -X Ｎ１ -X Ｎ２ -X Ｎ１ -, -X Ｎ１ -X Ｎ２ -X Ｎ１ -X Ｎ２ -, -X Ｎ２ -, -X Ｎ２ -X Ｎ１ -, -X Ｎ２ -X Ｎ１ -X Ｎ２ -, -X Ｎ２ -X Ｎ１ -X Ｎ２ -X Ｎ１ -, etc.

[0186] X Ｎ An example of Ｎ When is trivalent, -X Ｎ１ (-) ２ , -X Ｎ１ -X Ｎ２ (-) ２ , -X Ｎ１ -(X Ｎ２ -) ２ , -X Ｎ１ -X Ｎ２ -X Ｎ１ (-) ２ , -X Ｎ１ -X Ｎ２ (-X Ｎ１ -) ２ , -X Ｎ１ -(X Ｎ２ -X Ｎ１ -) ２ , -X Ｎ１ -X Ｎ２ -X Ｎ１ -XＮ２ (-) ２ , -X Ｎ１ -X Ｎ２ -X Ｎ１ -(X Ｎ２ -) ２、 -X Ｎ１ -X Ｎ２ -(X Ｎ１ -X Ｎ２ -) ２、 -X Ｎ１ -(X Ｎ２ -X Ｎ１ -X Ｎ２ -) ２ ; -X Ｎ２ (-) ２ , -X Ｎ２ -X Ｎ１ (-) ２ , -X Ｎ２ -(X Ｎ１ -) ２ , -X Ｎ２ -X Ｎ１ -X Ｎ２ (-) ２ , -X Ｎ２ -X Ｎ１ (-X Ｎ２ -) ２ , -X Ｎ２ -(X Ｎ１ -X Ｎ２ -) ２ , -X Ｎ２ -X Ｎ１ -X Ｎ２ -X Ｎ１ (-) ２ , -X Ｎ２ -X Ｎ１ -X Ｎ２ -(X Ｎ１ -) ２、 -X Ｎ２ -X Ｎ１ -(X Ｎ２ -X Ｎ１ -) ２、 -X Ｎ２ -(X Ｎ１ -X Ｎ２ -X Ｎ１ -) ２ etc.

[0187] X Ｎ An example of Ｎ When is tetravalent, -X Ｎ１ (-) ３ , -X Ｎ１-X Ｎ２ (-) ３ 、-X Ｎ１ -(X Ｎ２ -) ３ 、-X Ｎ１ -X Ｎ２ -X Ｎ１ (-) ３ 、-X Ｎ１ -X Ｎ２ (-X Ｎ１ -) ３ 、-X Ｎ１ -(X Ｎ２ -X Ｎ１ -) ３ 、-X Ｎ１ -X Ｎ２ -X Ｎ１ -X Ｎ２ (-) ３ 、-X Ｎ１ -X Ｎ２ -X Ｎ１ -(X Ｎ２ -) ３、 -X Ｎ１ -X Ｎ２ -(X Ｎ１ -X Ｎ２ -) ３、 -X Ｎ１ -(X Ｎ２ -X Ｎ１ -X Ｎ２ -) ３ ; -X Ｎ２ (-) ３ 、-X Ｎ２ -X Ｎ１ (-) ３ 、-X Ｎ２ -(X Ｎ１ -) ３ 、-X Ｎ２ -X Ｎ１ -X Ｎ２ (-) ３ 、-X Ｎ２ -X Ｎ１ (-X Ｎ２ -) ３ 、-X Ｎ２ -(X Ｎ１ -X Ｎ２ -) ３ 、-X Ｎ２ -X Ｎ１ -X Ｎ２ -X Ｎ１ (-) ３ 、-X Ｎ２ -X Ｎ１ -XＮ２ -(X Ｎ１ -) ３、 -X Ｎ２ -X Ｎ１ -(X Ｎ２ -X Ｎ１ -) ３、 -X Ｎ２ -(X Ｎ１ -X Ｎ２ -X Ｎ１ -) ３ ; etc.

[0188] X Ｎ Preferred examples of -X Ｎ１ -, -X Ｎ１ -X Ｎ２ -, -X Ｎ１ -X Ｎ２ -X Ｎ１ -, -X Ｎ１ -X Ｎ２ (-) ２ , -X Ｎ２ -, -X Ｎ２ -X Ｎ１ -, -X Ｎ２ -X Ｎ１ -X Ｎ２ -, -X Ｎ２ -X Ｎ１ (-) ２ In the amine-modified compound, one or more X Ｎ However, it is preferred that the terminal on the amine skeleton side is —(C═O)— and that it is bonded to a nitrogen atom in the amine skeleton.

[0189] X Ｎ is preferably -X Ｎ１ -, -X Ｎ１ -X Ｎ２ -, -X Ｎ１ -X Ｎ２ -X Ｎ１ -, -X Ｎ１ -X Ｎ２ (-) ２ , -X Ｎ２ -, -X Ｎ２ -X Ｎ１ -, -X Ｎ２ -X Ｎ１ -X Ｎ２ -, -X Ｎ２ -X Ｎ１ (-) ２ , [wherein, X Ｎ１is independently in each occurrence a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, or —C(═O)-NR′—, —C(═O)-NR′-C(═O)— (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), and X Ｎ２ is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group or a divalent triazole group). This makes it possible to impart good liquid repellency to the substrate.

[0190] X Ｎ Further specific examples include *-(C=O)- -O-(C=O)-NR'- (wherein * means that the group is bonded to the nitrogen atom of the amine skeleton, and R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms).

[0191] R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent. R is branched or linear, and more preferably linear. R may be saturated or unsaturated. R is preferably a saturated aliphatic hydrocarbon group (alkyl group).

[0192] The number of carbon atoms in R 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. The number of carbon atoms in R 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.

[0193] 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 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. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms 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).

[0194] (Examples of amine modified products) Amine modified product example 1 Examples of amine modified products include those of the following formula: N(-X N -R n ) p (-H) q -L 1 -[N(-X N -R n ) r (-H) s -L 1 -] t -N(-X N -R n ) p (-H) q [In the formula, X Ｎ is independently in each occurrence a direct bond or a group having a valence of (1+n), R is independently in each occurrence an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, L 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom; n is independently in each occurrence an integer of 1 to 3; p is independently in each occurrence an integer of 0 to 2; q is independently in each occurrence an integer of 0 to 2; and p+q is a substituted or unsubstituted N(-X N -Rn ) p (-H) q In the formula, r is 2, r is independently in each occurrence 0 or 1, s is independently in each occurrence 0 or 1, and r+s is a 0 or 1 group for each N(-X N -R n ) r (-H) s In the formula (Amine Modification Example 1), p is 1, the sum of all p's and all r's is 1 or more, and t is an integer of 0 or more and 10 or less.

[0195] In the amine modified example 1, X Ｎ , R, and n are described in detail above.

[0196] In the amine modified example 1, L １ is a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. １ The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. １ L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. １ is preferably a cyclic group having both a ring (for example, an aromatic ring) and a chain structure (for example, a linear structure, ether oxygen, or thioether sulfur), and specific examples include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. １ The number of carbon atoms in L may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more. １ may have 20 or fewer, 18 or fewer, 16 or fewer, 14 or fewer, 12 or fewer, 10 or fewer, 8 or fewer, 6 or fewer, 4 or fewer, or 3 or fewer carbon atoms.

[0197] In Amine Modification Example 1, p, in each occurrence, is independently an integer of 0 to 2, and q, in each occurrence, is independently an integer of 0 to 2, and p+q is equal to or less than each N(-X N -R n ) p (-H) q In the formula, p is 2. Preferably, p may be independently in each occurrence 1 or more, for example 2.

[0198] In Amine Modification Example 1, r is independently in each occurrence 0 or 1, s is independently in each occurrence 0 or 1, and r+s is independently in each occurrence 0 or 1. N -R n ) r (-H) s In the formula, p is 1. Preferably, p is independently in each occurrence 1 or more, for example 2.

[0199] The sum of all p's and all r's is 1 or more, that is, Amine Modification Example 1 contains one or more -X Ｎ -R ｎ The sum of all p's and all r's may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, or 12 or more (the sum of all q's and all s's may be 0). The sum of all p's and all r's may be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0200] In Amine Modification Example 1, t is an integer of 0 or more and 10 or less. t may be 0 or more, 1 or more, 2 or more, 4 or more, or 6 or more, and is preferably 0 or more or 2 or more. t may be 8 or less, 6 or less, 4 or less, or 3 or less.

[0201] Amine Modification Example 2: Other examples of amine modifications include those of the following formula: N(-X N -R n ) p (-H) q -L 2 (-X N -R n ) u [In the formula, X Nis independently in each occurrence a direct bond or a group having a valence of (1+n), R is independently in each occurrence an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may have a substituent, L ２ is a 1+u valent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, n is independently an integer of 1 or greater and 3 or less in each occurrence, p is an integer of 0 or greater and 2 or less, q is an integer of 0 or greater and 2 or less, p+q is 2, u is an integer of 1 or greater and 3 or less, and the sum of p and u is 1 or greater.] (Amine Modification Example 2)

[0202] In the amine modified example 2, X Ｎ , R and n are described in detail above.

[0203] In the amine modified example 2, L ２ is an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. ２ The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. ２ L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. ２ is preferably a cyclic group having both a ring (for example, an aromatic ring) and a chain structure (for example, a linear structure, ether oxygen, or thioether sulfur), and specific examples include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. ２ The number of carbon atoms in L may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more. ２may have 20 or fewer, 18 or fewer, 16 or fewer, 14 or fewer, 12 or fewer, 10 or fewer, 8 or fewer, 6 or fewer, 4 or fewer, or 3 or fewer carbon atoms.

[0204] In the amine modification example 2, p is an integer of 0 to 2, q is an integer of 0 to 2, and p+q is 2. Preferably, p may be 1 or more, for example, 2.

[0205] In the amine modification example 2, u is an integer of 1 or more and 3 or less. u is 1, 2, or 3, for example, 2 or 3.

[0206] In the amine modified example 2, the sum of p and u is 1 or more, that is, the amine modified example 2 has one or more -X Ｎ -R ｎ The sum of all p's and u's may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the sum of all q's may be 0). The sum of p's and u's may be 5 or less, 4 or less, 3 or less, or 2 or less.

[0207] The amine-modified wax may be a synthetic wax derived from animal or vegetable oils. The synthetic wax may be obtained by condensing a fatty acid derived from animal or vegetable oils with an aliphatic amine or an aromatic amine. Examples of the synthetic wax include fatty acid amide compounds such as hydroxy fatty acid amide compounds, palmitic acid amide compounds, octadecanoic acid amide compounds, stearic acid amide compounds, arachidic acid amide compounds, behenic acid amide compounds, lignoceric acid amide compounds, oleic acid amide compounds, linoleic acid amide compounds, α-linolenic acid amide compounds, γ-linolenic acid amide compounds, arachidonic acid amide compounds, eicosapentaenoic acid amide compounds, and docosahexaenoic acid amide compounds.

[0208] (Method for Producing Amine-Modified Compounds) Methods for producing amine-modified compounds include, but are not limited to, a synthesis method in which various amines are reacted with an R group-containing carboxylic acid, optionally in the presence of a condensing agent, and a synthesis method in which various amines are reacted with an R group-containing carboxylic acid acid chloride, acid anhydride, isocyanate, etc. The condensing agent may be a known condensing agent, and examples thereof include DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, and Py-Bop.

[0209] [Amount of Liquid-Repellent Compound] The amount of the liquid-repellent compound in the treatment agent may be 0.01 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. The amount of the liquid-repellent compound in the treatment agent 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.

[0210] [Supercritical Carbon Dioxide] The repellent of the present disclosure may contain supercritical carbon dioxide. Supercritical carbon dioxide refers to carbon dioxide that is kept at a temperature and pressure above its critical temperature (31.1°C) and critical pressure (7.38 MPa). The supercritical carbon dioxide in the repellent functions as a treatment medium, and the repellent containing supercritical carbon dioxide is used as a treatment agent for treating textile substrates. Supercritical carbon dioxide is in a fluid state that cannot be said to belong to either a gaseous or liquid phase, and has both excellent solubility for various components and fluidity that allows it to easily penetrate into the fine details of textile products. Therefore, the repellent (treatment agent) of the present disclosure can effectively impart liquid repellency to textile products.

[0211] [Liquid Medium] The repellent 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. Because the repellent of the present disclosure uses supercritical carbon dioxide as a treatment medium, the amount of the liquid medium in the repellent may be small, or the repellent may not contain a liquid medium.

[0212] 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., polyhydric alcohols such as alcohols and glycol-based solvents, ethers of polyhydric alcohols (e.g., monoethers), etc.). These may be used alone or in combination.

[0213] [Amount of Liquid Medium] The amount of the liquid medium may be 0.1 parts by weight or more, 0.5 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, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight of the liquid repellent compound). The amount of the liquid medium may be 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, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, 0.1 parts by weight or less, or 0, preferably 40 parts by weight or less, more preferably 10 parts by weight or less, relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight of the liquid repellent compound).

[0214] The amount of the liquid medium in the treatment agent may be 0.000001 mol / L or more, 0.000003 mol / L or more, 0.000005 mol / L or more, or 0.00001 mol / L or more. The amount of the liquid medium in the treatment agent may be 0.001 mol / L or less, 0.0005 mol / L or less, 0.0001 mol / L or less, 0.00005 mol / L or less, 0.00001 mol / L or less, or 0, preferably 0.0001 mol / L or less.

[0215] The amount of water may be 0.1 parts by weight or more, 0.5 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, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the liquid-repellent compound. The amount of organic solvent may be 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, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, 0.1 parts by weight or less, or 0, preferably 40 parts by weight or less, more preferably 10 parts by weight or less, relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the liquid-repellent compound.

[0216] The amount of water in the treatment agent may be 0.000001 mol / L or more, 0.000003 mol / L or more, 0.000005 mol / L or more, or 0.00001 mol / L or more. The amount of water in the treatment agent may be 0.001 mol / L or less, 0.0005 mol / L or less, 0.0001 mol / L or less, 0.00005 mol / L or less, 0.00001 mol / L or less, or 0, preferably 0.0001 mol / L or less.

[0217] The amount of the 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, or 50 parts by weight or more relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the liquid-repellent compound. The amount of the organic solvent may be 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, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 0 relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the liquid-repellent compound, and is preferably 40 parts by weight or less, and more preferably 10 parts by weight or less.

[0218] The amount of the organic solvent in the treatment agent may be 0.000001 mol / L or more, 0.000003 mol / L or more, 0.000005 mol / L or more, or 0.00001 mol / L or more. The amount of the organic solvent in the treatment agent may be 0.001 mol / L or less, 0.0005 mol / L or less, 0.0001 mol / L or less, 0.00005 mol / L or less, 0.00001 mol / L or less, or 0, preferably 0.0001 mol / L or less.

[0219] [Surfactant] The repellent may contain a surfactant. The surfactant may contain one or more surfactants selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. The repellent of the present disclosure uses supercritical carbon dioxide as a treatment medium, and therefore can disperse components well, so the amount of surfactant in the repellent may be small, or the repellent may not contain a surfactant.

[0220] [Nonionic Surfactant] Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.

[0221] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0222] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to hexa-hydric (particularly di- to penta-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.

[0223] 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 hexa-hydric (particularly di- to penta-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.

[0224] 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.

[0225] The polyhydric alcohol may be a dihydric to pentahydric 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).

[0226] The nonionic surfactant is preferably a nonionic surfactant 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 surfactant is generally preferably 2 to 100. The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

[0227] The nonionic surfactant 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 polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct moiety and the polyalkylene glycol moiety is polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, due to environmental concerns (biodegradability, endocrine disrupters, etc.), it is preferable that the nonionic surfactant have a structure that does not contain an aromatic group.

[0228] The nonionic surfactant 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, 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.

[0229] R 1 R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. 1 Preferred specific examples of R include a lauryl group, a tridecyl group, and an oleyl group. 2 Examples of the nonionic surfactant are a propylene group and a butylene group. In the nonionic surfactant, 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 surfactant 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, and among these, an oxypropylene chain is preferred.

[0230] Specific examples of nonionic surfactants 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.

[0231] 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 surfactant (copolymer). The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example 500 to 3,000. The nonionic surfactant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. An example of a compound having an HLB of less than 15 is a sorbitan fatty acid ester. An example of a compound having an HLB of 15 or more is a polyoxyethylene alkyl ether. The weight ratio of the compound having an HLB of less than 15 to the compound having an HLB of 15 or more may be 90:10 to 20:80, for example 85:15 to 55:45. The nonionic surfactant may be a single type or a mixture of two or more types.

[0232] [Cationic Surfactant] The cationic surfactant is preferably a compound having no amide group.

[0233] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene adduct ammonium salt.Specific examples of the cationic surfactant include, but are not limited to, amine salt surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, and quaternary ammonium salt surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride.

[0234] Preferred examples of cationic surfactants include: ２１ -N ＋ (-R ２２ ) (-R ２３ ) (-R ２４ ) X － [In the formula, R ２１ , R ２２ , R ２３ and R２４ is 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 are alkyl groups (e.g., methyl, butyl, stearyl, and palmityl). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0235] The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula: １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g. C １２ ~C ５０ ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, 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), X is a halogen atom (for example), 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.

[0236] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0237] [Anionic Surfactants] Examples of anionic surfactants 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 surfactants, phosphate mono- or diester surfactants, and sulfosuccinate esters.

[0238] [Amphoteric Surfactant] Examples of amphoteric surfactants 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.

[0239] The surfactant may be a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant, each of which may be one type or a combination of two or more types.

[0240] [Amount of Surfactant] The amount of surfactant 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, 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 liquid-repellent compound. The amount of surfactant 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, 75 parts by weight or less, 50 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, 1 part by weight or less, 0.5 parts by weight or less, 0.3 parts by weight or less, 0.1 parts by weight or less, or 0, preferably 10 parts by weight or less, more preferably 1 part by weight or less, relative to 100 parts by weight of the liquid-repellent compound.

[0241] [Silicone] The repellent agent according to the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

[0242] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0243] The weight average molecular weight of the silicone may be 300 or more, 1000 or more, 10000 or more, or 50000 or more. The weight average molecular weight of the silicone may be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

[0244] [Amount of Silicone] The amount of silicone 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 liquid repellent compound. The amount of silicone 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, 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 liquid repellent compound.

[0245] [Wax] The repellent agent according to the present disclosure may contain wax. By including wax, it is possible to impart good liquid repellency to the substrate.

[0246] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, mineral wax, etc. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane), and normal alkenes (e.g., 1-eicosane, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane). The number of carbon atoms in the compounds constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be from 200 to 2000, for example, from 250 to 1500, or from 300 to 1000. These may be used alone or in combination of two or more.

[0247] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0248] [Amount of Wax] The amount of wax 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 liquid repellent compound. The amount of wax 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, 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 liquid repellent compound.

[0249] [Organic Acid] The repellent 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 type of organic acid may be used, or two or more types may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0250] [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, 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 liquid-repellent compound. The amount of organic acid 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, 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 liquid-repellent compound. The amount of organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0251] [Hardening Agent] The repellent agent may contain a hardening agent (active hydrogen reactive compound or active hydrogen containing compound).

[0252] The curing agent (crosslinking agent) in the repellent agent can effectively cure the liquid-repellent compound. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of the liquid-repellent compound. 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, and melamine compounds.

[0253] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. A 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). A blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

[0254] 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.

[0255] 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), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0256] 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.

[0257] 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.

[0258] 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.

[0259] 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 repellent.

[0260] 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, and oxime compounds. The polyisocyanate compounds can be used alone or in combination of two or more.

[0261] 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.

[0262] 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 resins and methyl etherified melamine resins.

[0263] [Amount of Curing Agent] 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, 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 liquid repellent compound. The amount of the curing agent 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, 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 liquid repellent compound.

[0264] [Other Components] The repellent may contain other components in addition to the above components. Examples of other components include water and / or oil repellents, antislip agents, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other ingredients may include texture adjusters, fabric softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle-resistant agents, drying speed adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, anti-wrinkle agents when washed, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Chiba Specialty Chemicals), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, and stain removers. Fiber surface modifiers include enzymes such as cellulase, amylase, protease, lipase, and keratinase, foam inhibitors, and silk protein powders, surface-modified products thereof, and emulsified dispersions that can impart silk texture and functionality such as moisture absorption and release, and specific examples include K-50, K-30, K-10, A-705, S-702, L-710, and FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos), and stain inhibitors such as nonionic polymeric compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, such as FR627 manufactured by GOO Chemical Industry and SRC-1 manufactured by Clariant Japan. These may be used alone or in combination of two or more.

[0265] [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. Ion-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.

[0266] [Preservatives] Preservatives can be used mainly to enhance antiseptic and bactericidal properties and maintain antiseptic 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.

[0267] [Ultraviolet Absorber] An ultraviolet absorber is a chemical agent that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0268] [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.

[0269] [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).

[0270] [Amount of Other Components] The amount of each of the other components or the total amount thereof 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 liquid repellent compound. The amount of each of the other components or the total amount thereof 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, 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 liquid repellent compound.

[0271] <Method for manufacturing liquid-repellent fiber> The method for manufacturing a liquid-repellent fiber in the present disclosure includes a fiber treatment step in which a fiber substrate is treated with a repellent agent containing a liquid-repellent compound using supercritical carbon dioxide as a treatment medium. The repellent agent (treatment agent) used to treat the fiber substrate contains the liquid-repellent compound and supercritical carbon dioxide. Through the treatment, the liquid-repellent compound, which is the active ingredient of the repellent agent, penetrates into the interior of the substrate and / or adheres to the surface of the substrate.

[0272] The repellent of the present disclosure may further contain various additives, such as water and / or oil repellents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and antifoaming agents, if necessary. Examples of the various additives may be the same as those described above in the "other components" section of the water repellent composition. The concentration of the repellent in the treatment agent to be brought into contact with the substrate may be varied as appropriate depending on the application, but may be 0.01 to 10 wt %, for example, 0.05 to 5 wt %.

[0273] In the method for producing a liquid-repellent fiber of the present disclosure, the treatment temperature in the treatment vessel is set to 31.1°C or higher (preferably 40°C or higher), which is the critical temperature of carbon dioxide, and the treatment pressure is set to 7.38 MPa or higher (preferably 10 MPa or higher), which is the critical pressure of carbon dioxide, and a fiber substrate placed in a treatment tank is treated with a repellent agent containing a liquid-repellent compound using supercritical carbon dioxide as a treatment medium.

[0274] The treatment temperature may be 31.1° C. or higher, 40° C. or higher, 50° C. or higher, 60° C. or higher, 70° C. or higher, 80° C. or higher, or 100° C. or higher. The treatment temperature may be 200° C. or lower, 150° C. or lower, 120° C. or lower, 100° C. or lower, 80° C. or lower, or 60° C. The treatment temperature may vary depending on the type of repellent used, the treatment conditions, the desired physical properties, etc.

[0275] The treatment pressure may be 7.38 MPa or more, 8 MPa or more, 10 MPa or more, 15 MPa or more, 20 MPa or more, or 25 MPa or more. The treatment pressure may be 100 MPa or less, 75 MPa or less, 50 MPa or less, 30 MPa or less, 25 MPa or less, or 20 MPa or less. The treatment pressure may vary depending on the type of repellent used, the treatment conditions, the desired physical properties, etc.

[0276] The treatment time may be 10 seconds or more, 1 minute or more, 3 minutes or more, 5 minutes or more, 10 minutes or more, 20 minutes or more, or 30 minutes or more. The treatment time may be 300 minutes or less, 240 minutes or less, 180 minutes or less, 120 minutes or less, 60 minutes or less, 30 minutes or less, 15 minutes or less, or 5 minutes or less. The treatment temperature may vary depending on the type of repellent used, the treatment conditions, the desired physical properties, etc.

[0277] [Fiber Substrate] Examples of fiber substrates in the present disclosure include natural fibers of animal or plant origin, such as cotton, hemp, 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, or mixed fibers thereof. Fiber products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as clothing and carpets. Fibers, yarns, and intermediate fiber products (e.g., slivers or rovings) before being made into fabrics may also be processed. Examples of suitable fiber substrates in the present disclosure include polyester or polyester blended fibers.

[0278] Paper products may be used as the fiber substrate. 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 newspaper, magazine, corrugated cardboard, or deinked recycled paper, paper containers, and molded articles made of paper. Specific examples of paper products include packaging paper, gypsum board base paper, coated base paper, medium-grade paper, general liners and corrugating media, 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, neutral information paper, and molded paper (molded containers).

[0279] [Pretreatment of Textile Products] The textile product may be pretreated before being treated with the repellent of the present disclosure. Pretreatment of the textile product can impart excellent durability to the textile product after treatment with the repellent.

[0280] 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.

[0281] 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.

[0282] 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 "specific functional groups").

[0283] 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.

[0284] 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.

[0285] 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.

[0286] The 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 form such as fiber (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, etc.

[0287] 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.

[0288] Above -SO ３ M １ A phenolic polymer can be used as the compound having the formula:

[0033] Such a phenolic polymer can include, for example, one or more compounds represented by the following general formula:

[0289] [In the formula, 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.

[0290] [In the formula, M ４ represents a monovalent cation.

[0291] The above M ３ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0292] The above M ４ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0293] 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.

[0294] Above - COOM ２ Examples of compounds having the formula include polycarboxylic acid polymers.

[0295] 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.

[0296] 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.

[0297] 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.

[0298] 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.

[0299] 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.

[0300] 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.

[0301] 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.

[0302] 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.

[0303] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0304] 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.

[0305] 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.

[0306] 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 treatments include air spraying, in which compressed air is used to spray the treatment liquid in the form of a mist, 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 of the treatment liquid. Furthermore, if the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after application to the fiber material 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.

[0307] 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.

[0308] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0309] 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.

[0310] 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.

[0311] 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.

[0312] 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.

[0313] (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).

[0314] 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.).

[0315] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0316] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0317] <Test Method> The test procedure is as follows.

[0318] [Water Contact Angle] A solution of a liquid-repellent compound with a solid content of 1.0% was spin-coated on a silicon wafer to obtain a smooth spin-coated film. 2 μL of water was dropped on the spin-coated film, and the contact angle 1 second after the drop was dropped was recorded as the water contact angle of the liquid-repellent compound.

[0319] [Deposition Rate] The weight of the fiber substrate was measured before and after treatment, the weight before treatment was subtracted from the weight after treatment, and the weight difference was divided by the weight before treatment to calculate the deposition amount.

[0320] [Water-repellent performance] A drop of water was placed on the treated liquid-repellent fiber, and the performance was evaluated based on whether the water droplet spread or not. If the water droplet did not spread, it was evaluated as "Good", and if the water droplet spread, it was evaluated as "Poor".

[0321] <Compound 1> Octadecyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used.

[0322] <Compound 2> Polyglycerol fatty acid ester (TS-3S, manufactured by Sakamoto Pharmaceutical Co., Ltd.) was used.

[0323] <Synthesis of Compound 3> A stirrer, 2.8 g of citric acid, and 9.5 g of dodecylamine were placed in a reaction vessel equipped with a reflux condenser and a Dean-Stark cap, and the mixture was heated to 70°C, followed by the addition of 20 ml of toluene. The mixture was heated and stirred at 135°C for 64 hours. The reaction vessel was cooled to room temperature, and an additional 20 ml of toluene was added. The mixture was washed with acetone and then ethanol, yielding Compound 3 shown below.

[0324] <Synthesis of Compound 4> 4.69 g of stearyl alcohol was dissolved in 80.0 mL of dehydrated tetrahydrofuran, and then 0.69 g of sodium hydride was added and stirred at room temperature for 1 hour. After 1 hour, 1.0 g of cyanuric acid chloride was added, and the mixture was heated and stirred overnight at an oil bath temperature of 66°C. The next morning, the mixture was neutralized with 3N hydrochloric acid and then filtered. The resulting solid was washed with water, methanol, and diethyl ether to obtain 3.32 g of Compound 4 shown below.

[0325] <Synthesis of Compound 5> 0.5 g of phloroglucinol was dissolved in 20.0 mL of dehydrated tetrahydrofuran, and then 3.75 g of octadecyl isocyanate, 1.71 mL of triethylamine, and 3 drops of dibutyltin dilaurate were added in this order. The mixture was heated and stirred overnight in an oil bath at 60°C. The next morning, the mixture was cooled and filtered. The resulting solid was washed with acetone, methanol, and dichloromethane to obtain 3.27 g of Compound 5 shown below.

[0326] <Synthesis of Compound 6> 0.82 g of melamine and 10 g of myristic anhydride were placed in a flask and heated with stirring for 1 hour in an oil bath at 200° C. After 1 hour, the mixture was cooled to room temperature, and the resulting solid was washed with acetone and diethyl ether to obtain 4.33 g of the compound shown below.

[0327] The water contact angles of Compounds 1 to 6 were measured.

[0328] Example 1 A polyethylene terephthalate fabric (basis weight 88 g / m2, 70 denier, gray) was cut and weighed (approximately 1 g). 40 mg of Compound 1 was supported on a glass filter. The polyethylene terephthalate fabric and the glass filter supporting Compound 1 were placed in a 10 mL treatment container and set in a supercritical carbon dioxide treatment device. Supercritical carbon dioxide at a pressure of 25 MPa was then injected, and treatment was carried out at a temperature of 120°C for 30 minutes. After a predetermined time, the supercritical carbon dioxide was discharged, and liquid-repellent fibers were obtained. The repellent adhesion rate on the fabric at this time was calculated to be 0.65 wt%.

[0329] Example 2 A liquid-repellent fiber was obtained in the same manner as in Example 1, except that Compound 2 was used instead of Compound 1. The adhesion rate of the repellent agent to the fabric was calculated to be 0.87% by weight.

[0330] Example 3 A liquid-repellent fiber was obtained in the same manner as in Example 1, except that Compound 3 was used instead of Compound 1. The adhesion rate of the repellent agent to the fabric was calculated to be 0.73% by weight.

[0331] Example 4 A liquid-repellent fiber was obtained in the same manner as in Example 1, except that Compound 4 was used instead of Compound 1. The adhesion rate of the repellent agent to the fabric was calculated to be 0.62% by weight.

[0332] Example 5 A liquid-repellent fiber was obtained in the same manner as in Example 1, except that Compound 5 was used instead of Compound 1. The adhesion rate of the repellent agent to the fabric was calculated to be 0.28% by weight.

[0333] Example 6 A liquid-repellent fiber was obtained in the same manner as in Example 1, except that Compound 6 was used instead of Compound 1. The adhesion rate of the repellent agent to the fabric was calculated to be 0.27% by weight.

[0334] Comparative Example 1 An untreated fiber substrate was evaluated.

[0335] The water repellency of the fiber substrates of Examples 1 to 5 and Comparative Example 1 was evaluated.

[0336] The test results are summarized in the table below.

Claims

1. A method for producing a liquid-repellent fiber, comprising a fiber treatment step of treating a fiber substrate with a repellent agent containing a liquid-repellent compound using supercritical carbon dioxide as a treatment medium, The liquid repellent compound does not have a fluorine atom, When the liquid-repellent compound has a polysiloxane group, the liquid-repellent fiber has the polysiloxane group in a side chain.

2. The method for producing a liquid-repellent fiber according to claim 1 , wherein the liquid-repellent compound has a water contact angle of 35° or more.

3. The liquid repellent compound has the following formula: -X-R ｎ [In the formula, X is a direct bond or a group having a valence of 1+n; R independently in each occurrence represents an optionally substituted aliphatic hydrocarbon group or polysiloxane group having from 6 to 40 carbon atoms; n is 1 or more and 3 or less. The method for producing a liquid-repellent fiber according to claim 1 or 2, wherein the liquid-repellent fiber has a group represented by the formula:

4. 4. The method for producing a liquid-repellent fiber according to claim 3, wherein R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and R has 12 or more carbon atoms.

5. X, Direct bond, -O-, -C(=O)-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein, R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). １ and, X is a hydrocarbon group having 1 to 40 carbon atoms. ２ and, The method for producing a liquid-repellent fiber according to claim 3 or 4, wherein the valence of the group is 1+n and the group is one or more selected from the group consisting of:

6. X, -X １ -or- -X １ -X ２ -X １ - [In the formula, X １ but, independently for each occurrence, direct binding, -O-, -O-C(=O)-, -O-C(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO ２ -、 -SO ２ NR'-、 -C(OR')R'-, or -C(OR’)(-) ２ (In the formula, R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. is a group represented by X ２ is a hydrocarbon group having 1 to 40 carbon atoms. The method for producing a liquid-repellent fiber according to any one of claims 3 to 5, wherein the group is represented by:

7. The liquid repellent compound has the following formula: CH ２ =C(-Q)-C(=O)-X-R ｎ [In the formula, Q is a hydrogen atom, a monovalent organic group or a halogen atom; X is a direct bond, -O-, -C(=O)-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein, R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). １ and, X is a hydrocarbon group having 1 to 40 carbon atoms. ２ and, is a 1+n valent group consisting of one or more selected from the group consisting of R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, n is 1 to 3. The method for producing the liquid-repellent fiber according to any one of claims 1 to 6, which has a repeating unit derived from a compound represented by the following formula:

8. X is of the following formula: -X １ - or -X １ -X ２ -X １ - [In the formula, X １ is independently in each occurrence -O-, -NR'-, -C(=O)-NR'-, -NR'-C(=O)-, or -NR'-C(=O)-NR'- (R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms); X ２ is a hydrocarbon group having 1 to 40 carbon atoms. The method for producing a liquid-repellent fiber according to claim 7, wherein the group is represented by the following formula:

9. The liquid repellent compound is a compound represented by the following formula: -X-R ｎ [In the formula, X is a direct bond or a group having a valence of 1+n; R independently in each occurrence represents an optionally substituted aliphatic hydrocarbon group having from 6 to 40 carbon atoms; n is 1 to 3. The method for producing a liquid-repellent fiber according to any one of claims 1 to 6, wherein the compound is a compound modified with a group represented by the following formula:

10. The base compound may be starch, cellulose, curdlan, pullulan, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, xanthan gum, gelatin gum, tamarind seed gum, cycloamylose, glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, stephoxide, dextrin, cyclodextrin, glycerin, polyglycerin, menthol, xylitol, sucrose, glycerol, polyglycerin, glycerol ... The method for producing a liquid-repellent fiber according to claim 9, wherein the sugar is one or more selected from the group consisting of lactose, fructose, maltose, trehalose, lactosucrose, erythritol, vanillin, cholesterol, glucosamine, catechin, anthocyanin, quercetin, citric acid, malic acid, gluconic acid, alginic acid, butyric acid, lactic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, chlorogenic acid, aldonic acid, uronic acid, aldaric acid, phytic acid, ascorbic acid, and derivatives thereof.

11. The method for producing a liquid-repellent fiber according to claim 9 or 10, wherein the matrix compound is a glycerin polymer or a citric acid polymer.

12. the base compound has a hydroxy group; The hydroxy group in the liquid repellent compound is represented by the following formula: -O-, -OC(=O)-, -O-C(=O)-NR'-, or -OC=S-NR'- [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.] The method for producing a liquid-repellent fiber according to any one of claims 9 to 11, wherein a group represented by the following formula is formed:

13. The base compound has a carboxy group; The carboxy group in the liquid repellent compound The following formula: -C(=O)- -C(=O)-O- -C(=O)-NR'-, or -C(=O)-S- [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.] The method for producing a liquid-repellent fiber according to any one of claims 9 to 12, wherein a group represented by the following formula is formed:

14. The liquid repellent compound is represented by the following formula: A(-X-R ｎ ) ｍ [In the formula, A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocycle which may have a substituent, X is independently in each occurrence a direct bond or a group having a valence of 1+n; R independently in each occurrence represents an optionally substituted aliphatic hydrocarbon group having from 6 to 40 carbon atoms; n is independently in each occurrence 1 to 3, m is 1 or more and 6 or less. The method for producing the liquid-repellent fiber according to any one of claims 1 to 6, wherein the compound is represented by the formula:

15. The liquid repellent compound is represented by the following formula: A(-X-R ｎ ) ｍ [In the formula, A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocycle which may have a substituent, X is independently in each occurrence a direct bond or a group having a valence of 1+n; R independently in each occurrence represents an optionally substituted aliphatic hydrocarbon group having from 6 to 40 carbon atoms; n is independently in each occurrence 1 to 3, m is 1 or more and 6 or less. The method for producing a liquid-repellent fiber according to any one of claims 1 to 6, wherein the compound is obtained by polymerizing a compound represented by the following formula (I) via a substituent possessed by A:

16. X is of the following formula: -X １ -or- -X １ -X ２ -X １ - [In the formula, X １ but, independently for each occurrence, direct binding, -O-, -O-C(=O)-, -O-C(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -C(OR')R'-, or -C(OR’)(-) ２ wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; X ２ is a hydrocarbon group having 1 to 40 carbon atoms. The method for producing a liquid-repellent fiber according to claim 14 or 15, wherein the group is represented by the following formula:

17. The method for producing a liquid-repellent fiber according to any one of claims 1 to 6, wherein the liquid-repellent compound is a reaction product of an isocyanate group-containing compound and an isocyanate-reactive compound.

18. The method for producing a liquid-repellent fiber according to any one of claims 1 to 6, wherein the liquid-repellent compound has a polysiloxane group.

19. The method for producing a liquid-repellent fiber according to claim 18, wherein the liquid-repellent compound has the polysiloxane group in a side chain.

20. The liquid repellent compound is an amine backbone, and The following formula: -X Ｎ -R ｎ [In the formula, X Ｎ is a direct bond or a group having a valence of 1+n, R independently in each occurrence represents an optionally substituted aliphatic hydrocarbon group having from 6 to 40 carbon atoms; n is an integer of 1 to 3. The compound has one or more aliphatic hydrocarbon-containing groups represented by the formula:

7. The method for producing a liquid-repellent fiber according to claim 1, wherein the liquid-repellent fiber is an amine-modified fiber in which at least one aliphatic hydrocarbon-containing group is bonded to a nitrogen atom of the amine skeleton.

21. The method for producing a liquid-repellent fiber according to claim 20, wherein the amine skeleton is composed of a monovalent to trivalent amino group, and a linear saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom.

22. The method for producing a liquid-repellent fiber according to any one of claims 1 to 21, wherein the fiber is a polyester or polyester blend fiber.

23. The method for producing a liquid-repellent fiber according to any one of claims 1 to 22, wherein a water concentration in a treatment agent for treating the fiber substrate is 0.001 mol / L or less.

24. A composition comprising a liquid repellent compound as defined in any one of claims 1 to 21 and supercritical carbon dioxide.

25. A repellent comprising a liquid repellent compound as defined in any one of claims 1 to 21 and supercritical carbon dioxide.

26. A fiber treated for water repellency with a composition or a repellent comprising a liquid repellent compound defined in any one of claims 1 to 21 and supercritical carbon dioxide.