Method for producing liquid-repellent fibers

Abstract

The present invention addresses the problem of providing a method capable of imparting liquid repellency to fibers even if the amount of water and / or a surfactant is reduced, preferably even if water and / or a surfactant are not used. According to the present invention, by means of a method for producing liquid-repellent fibers, which comprises a fiber treatment step in which supercritical carbon dioxide is used as a treatment medium, and which is capable of imparting liquid-repellent properties to fibers even if the amount of water and / or a surfactant is reduced, preferably even if water and / or a surfactant are not used, it is possible to provide a method for imparting liquid-repellent properties to fibers even if the amount of water and / or surfactant is reduced, preferably even if water and / or surfactant are not used. The fiber base material is treated with a liquid-repellent agent containing a liquid-repellent compound.

Description

Technical Field

[0001] The present invention relates to a method for producing liquid-repellent fibers, and in particular to a method for producing liquid-repellent fibers using supercritical carbon dioxide as a treatment medium. Background Art

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

[0003] Patent Document 1 discloses a fiber treatment method characterized in that, when treating fibers or fiber products, a fiber treatment agent containing supercritical carbon dioxide or liquefied carbon dioxide, water and a surfactant and forming reverse micelles is used.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2004-76190 Summary of the invention

[0007] Technical problem to be solved by the invention

[0008] However, Patent Document 1 does not specifically disclose imparting liquid repellency to fibers. In addition, water and a surfactant must be used simultaneously, which is industrially disadvantageous from the perspective of productivity. Furthermore, as environmental problems have become more serious in recent years, water is a precious resource, and reducing industrial usage and discharge is also an important issue.

[0009] The technical problem to be solved by the present invention is to provide a new method for imparting liquid repellency to fibers even when the amount of water and / or surfactant is reduced, preferably even when no water and / or surfactant is used.

[0010] Technical solutions for solving technical problems

[0011] The present invention includes the following aspects.

[0012] [Item 1] A method for producing liquid-repellent fibers, comprising a fiber treatment step in which a fiber substrate is treated with a repellent containing a liquid-repellent compound using supercritical carbon dioxide as a treatment medium.

[0013] [Item 2] The method for producing a liquid repellent fiber according to Item 1, wherein the water contact angle of the liquid repellent compound is 35° or more.

[0014] [Item 3] The method for producing a liquid repellent fiber according to Item 1 or 2, wherein the liquid repellent compound has the following formula: -X-R n The groups shown.

[0015] [Formula-X-R n middle,

[0016] X is a valence bond or a 1+n valence group,

[0017] R, when present, is independently an aliphatic hydrocarbon group or a polysiloxane group having 6 to 40 carbon atoms and optionally having a substituent,

[0018] n is greater than or equal to 1 and less than or equal to 3.]

[0019] [Item 4] The method for producing a liquid-repellent fiber as described in Item 3, wherein R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and the number of carbon atoms of R is 12 or more.

[0020] [Item 5] The method for producing a liquid-repellent fiber according to Item 3 or 4, wherein X is selected from X 1 and X 2 A 1+n-valent group composed of one or more of

[0021] X 1 It is composed of one or more selected from the group consisting of a valence bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence),

[0022] X 2 It is a hydrocarbon group having 1 to 40 carbon atoms.

[0023] [Item 6] The method for producing a liquid-repellent fiber according to any one of Items 3 to 5, wherein X is -X 1 -or-X 1 -X 2 -X 1 - the group shown.

[0024] [Formula-X 1 -, -X 1 -X 2 -X 1 -middle,

[0025] X 1 Independently at each occurrence is:

[0026] Valence bond,

[0027] -O-,

[0028] -O-C(=O)-,

[0029] -O-C(=O)-O-,

[0030] -O-C(=O)-NR'-,

[0031] -NR'-

[0032] -NR'-C(=O)-,

[0033] -NR'-C(=O)-O-,

[0034] -NR'-C(=O)-NR'-,

[0035] -C(=O)-,

[0036] -C(=O)-O-,

[0037] -C(=O)-NR'-,

[0038] -SO2-,

[0039] -SO2NR'-,

[0040] -C(OR')R'-, or

[0041] - a group represented by C(OR')(-)2,

[0042] (wherein, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence)

[0043] X 2 It is a hydrocarbon group having 1 to 40 carbon atoms.]

[0044] [Item 7] The method for producing a liquid repellent fiber according to any one of Items 1 to 6, wherein the liquid repellent compound has a compound derived from the following formula: CH2=C(-Q)-C(=O)-X-R n The repeating unit of the compound shown.

[0045] [Formula CH2=C(-Q)-C(=O)-X-R n middle,

[0046] Q is a hydrogen atom, a monovalent organic group or a halogen atom,

[0047] X is selected from X 1 and X 2 A 1+n-valent group composed of one or more of

[0048] X 1 It is composed of one or more selected from the group consisting of a valence bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence),

[0049] X 2 is a hydrocarbon group having 1 to 40 carbon atoms,

[0050] R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0051] n is 1 to 3.]

[0052] [Item 8] The method for producing a liquid-repellent fiber as described in Item 7, wherein X is the following formula: 1 -or-X 1 -X 2 -X 1 - the group shown.

[0053] [Formula-X 1 -, -X 1 -X 2 -X 1 -middle,

[0054] X 1 Each occurrence is independently -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 It is a hydrocarbon group having 1 to 40 carbon atoms.]

[0055] [Item 9] The method for producing a liquid-repellent fiber according to any one of Items 1 to 6, wherein the liquid-repellent compound is a base material compound modified with the following formula: -X-R n The compounds of the groups shown,

[0056] The matrix compound is at least one selected from monosaccharides, polysaccharides, alcohols, polyols, carboxylic acids, polycarboxylic acids and derivatives thereof.

[0057] [Formula-X-R n middle,

[0058] X is a valence bond or a 1+n valence group,

[0059] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0060] n is 1 to 3.]

[0061] [Item 10] A method for producing a liquid-repellent fiber as described in Item 9, wherein the matrix compound is selected from starch, cellulose, curdlan, pullulan, carrageenan, guar gum, chitin, chitosan, locust bean gum, κ-carrageenan, ι-carrageenan, isomaltodextrin, xanthan gum, gellan gum, tamarind gum, cyclostranded starch, glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, steviol, dextrin, cyclodextrin, glycerol, polyglycerol, menthol, xylitol, sucralose, fructose, maltose, trehalose, lactoligosaccharide, erythritol, vanillin, cholesterol, glucosamine, catechins, anthocyanins, 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 acid), uronic acid, aldaric acid, phytic acid, ascorbic acid and their derivatives.

[0062] [Item 11] The method for producing a liquid-repellent fiber according to Item 9 or 10, wherein the matrix compound is a glycerol polymer or a citric acid polymer.

[0063] [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 hydroxyl group,

[0064] The hydroxyl group forms a group represented by the following formula in the liquid repellent compound:

[0065] -O-,

[0066] -O-C(=O)-,

[0067] -O-C(=O)-NR'-, or

[0068] -O-C=S-NR'-.

[0069] [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]

[0070] [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 carboxyl group,

[0071] The carboxyl group forms a group represented by the following formula in the liquid repellent compound:

[0072] -C(=O)-,

[0073] -C(=O)-O-,

[0074] -C(=O)-NR'-, or

[0075] -C(=O)-S-.

[0076] [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]

[0077] [Item 14] The method for producing a liquid-repellent fiber according to any one of Items 1 to 6, wherein the liquid-repellent compound is of the following formula: A(-X-R n ) m The compounds shown.

[0078] [Formula A(-X-R n ) m middle,

[0079] A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocyclic ring which may have a substituent,

[0080] X is independently a bond or a 1+n valent group at each occurrence,

[0081] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0082] n is independently 1 or more and 3 or less at each occurrence,

[0083] m is greater than or equal to 1 and less than or equal to 6.]

[0084] [Item 15] The method for producing a liquid repellent fiber according to any one of Items 1 to 6, wherein the liquid repellent compound is a compound of the formula: A(-X-R n ) m The compound shown is a compound obtained by polymerizing the substituents possessed by A.

[0085] [Formula A(-X-R n ) m middle,

[0086] A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocyclic ring which may have a substituent,

[0087] X is independently a bond or a 1+n valent group at each occurrence,

[0088] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0089] n is independently 1 or more and 3 or less at each occurrence,

[0090] m is greater than or equal to 1 and less than or equal to 6.]

[0091] [Item 16] The method for producing a liquid-repellent fiber according to Item 14 or 15, wherein X is the following formula: 1 -or-X 1 -X2 -X 1 - the group shown.

[0092] [Formula-X 1 -, -X 1 -X 2 -X 1 -middle,

[0093] X 1 Independently at each occurrence is:

[0094] Valence bond,

[0095] -O-,

[0096] -O-C(=O)-,

[0097] -O-C(=O)-O-,

[0098] -O-C(=O)-NR'-,

[0099] -NR'-

[0100] -NR'-C(=O)-,

[0101] -NR'-C(=O)-O-,

[0102] -NR'-C(=O)-NR'-,

[0103] -C(=O)-,

[0104] -C(=O)-O-,

[0105] -C(=O)-NR'-,

[0106] -C(OR')R'-, or

[0107] -C(OR')(-)2,

[0108] (R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence)

[0109] X 2 It is a hydrocarbon group having 1 to 40 carbon atoms.]

[0110] [Item 17] The 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.

[0111] [Item 18] The 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.

[0112] [Item 19] The method for producing a liquid repellent fiber according to Item 18, wherein the liquid repellent compound has the polysiloxane group in a side chain.

[0113] [Item 20] The 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 one or more of the following formulas: -X N -R n An amine-modified form in which the aliphatic hydrocarbon-containing group is bonded to a nitrogen atom of the amine skeleton.

[0114] [Formula-X N -R n middle,

[0115] X N is a valence bond or a 1+n valence group,

[0116] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0117] n is an integer of 1 to 3.]

[0118] [Item 21] The expelling agent as described in Item 20, wherein the above-mentioned amine skeleton is composed of monovalent to trivalent amino groups and chain-like saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups which may be separated by oxygen atoms and / or sulfur atoms.

[0119] [Item 22] The method for producing a liquid-repellent fiber according to any one of Items 1 to 21, wherein the fiber is polyester or a polyester-blended fiber.

[0120] [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 treatment agent for treating the fiber base material is 0.001 mol / L or less.

[0121] [Item 24] A composition comprising the lyophobic compound defined in any one of Items 1 to 21 and supercritical carbon dioxide.

[0122] [Item 25] A repellent comprising the liquid repellent compound defined in any one of Items 1 to 21 and supercritical carbon dioxide.

[0123] [Item 26] A fiber treated with water repellency using a composition or a repellent containing the liquid repellent compound defined in any one of Items 1 to 21.

[0124] Effects of the Invention

[0125] According to the method for producing liquid repellent fibers of the present invention, liquid repellency can be imparted to fibers using various liquid repellent compounds even when the amount of water and / or surfactant is reduced, preferably even when no water and / or surfactant is used. DETAILED DESCRIPTION

[0126] <Definition of terms>

[0127] When used in this specification, "n-valent group" means a group having n valent bonds, i.e., a group forming n bonds. In addition, "n-valent organic group" means a carbon-containing n-valent group. Such an organic group is not particularly limited and may be a hydrocarbon group or a derivative thereof. The so-called hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide group, sulfonyl group, siloxane group, carbonyl group, carbonyloxy group, etc. at the end of the hydrocarbon group or in the molecular chain.

[0128] As used in this specification, "hydrocarbon group" is a group containing carbon and hydrogen, and refers to a group in which a hydrogen atom is separated from a hydrocarbon. The hydrocarbon group is not particularly limited, and examples thereof include C 1－20 Hydrocarbon groups, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc. The above-mentioned "aliphatic hydrocarbon groups" can be any of linear, branched or cyclic, and can also be any of saturated or unsaturated. In addition, the hydrocarbon group can contain one or more ring structures. The hydrocarbon group can also be substituted by one or more substituents.

[0129] In the present specification, regardless of whether "independently at each occurrence", "independently of each other", "independently of each other" or similar expressions are explicitly stated, unless otherwise stated, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition applies independently at each occurrence.

[0130] <Dipping agent>

[0131] The repellent of the present invention is a substance capable of imparting liquid repellency to a fiber substrate, and can exert at least one function selected from a water repellent, an oil repellent, an oil resistant agent, and a water resistant agent. According to the present invention, even if the amount of water and / or surfactant in the repellent is reduced, liquid repellency can be imparted to the fiber substrate well, which is advantageous from an industrial point of view and / or a view of environmental protection.

[0132] The repellent of the present invention contains a liquid repellent compound. The repellent of the present invention may be a liquid repellent compound alone. The repellent of the present invention may also contain supercritical carbon dioxide and / or other components as a treatment medium in addition to the liquid repellent compound.

[0133] The repellent of the present invention may not contain any one selected from the group consisting of a compound having a fluoroalkyl group with a carbon number of 8 or more, a compound having a perfluoroalkyl group with a carbon number of 8 or more, a compound having a fluoroalkyl group with a carbon number of 4 or more, a compound having a perfluoroalkyl group with a carbon number of 4 or more, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent of the present invention can impart liquid repellency to the substrate even if it does not contain these fluorine compounds.

[0134] 〔Lyophobic compounds〕

[0135] The liquid repellent compound of the present invention can be attached to a fiber substrate to impart liquid repellency to the fiber substrate.

[0136] 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. The liquid repellent compound having a water contact angle above the above lower limit can well impart liquid repellency (particularly water repellency) to the fiber substrate. The so-called water contact angle, as shown in the examples, refers to the static contact angle of the spin-coated film of the liquid repellent compound, which is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle after dropping for 1 second.

[0137] The solubility parameter (SP value) of the lyophobic 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, and more preferably 9 or more. The solubility parameter (SP value) of the lyophobic 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, and more preferably 12 or less. The solubility parameter is defined by the square root of the cohesive energy density obtained by dividing the cohesive energy by the molar molecular volume.

[0138] The amount of the lyophobic compound dissolved 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, and more preferably 0.01 mg / mL or more. The amount of the lyophobic compound dissolved 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, and more preferably 1 mg / mL or less.

[0139] 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, 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 the supercritical carbon dioxide during the treatment and multiplying it by 100.

[0140] The melting point of the lyophobic 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. Preferably, the melting point of the lyophobic compound is higher than the treatment temperature.

[0141] Examples of the liquid repellent compound include, but are not limited to, acrylic polymer liquid repellent compounds, matrix modified liquid repellent compounds, ring modified liquid repellent compounds, isocyanate liquid repellent compounds, polysiloxane group-containing liquid repellent compounds, etc. The liquid repellent compound may be a combination of multiple (e.g., 2 or 3) liquid repellent compounds.

[0142] In the present invention, 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, more preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, preferably linear. The number of carbon atoms of 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 of 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. Among them, the monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent mentioned here may correspond to R described below.

[0143] The hydrocarbon group having 6 to 40 carbon atoms which may have a substituent in the present invention may be a hydrocarbon group having a substituent, but may also be an unsubstituted hydrocarbon group. Here, as examples of substituents, -OR', -N(R')2, -COOR' and halogen atoms can be listed (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms each time it appears). The substituent may have active hydrogen or not. 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 hydrocarbon group having a substituent, 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 hydrocarbon group having a substituent, 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 (eg 1) -OR' (particularly -OH) as a substituent (eg excluding the terminal).

[0144] The lyophobic 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, preferably 10 or more hydrocarbon groups. The lyophobic 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.

[0145] The amount of the hydrocarbon group having 6 to 40 carbon atoms which may have a substituent (particularly an aliphatic hydrocarbon group) in the lyophobic 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, preferably 5% by weight or more. The amount of the hydrocarbon group having 6 to 40 carbon atoms which may have a substituent (particularly an aliphatic hydrocarbon group) in the lyophobic 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, preferably 70% by weight or less.

[0146] The liquid repellent compound in the present invention may not have any one selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the liquid repellent compound does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.

[0147] The liquid repellent compound in the present invention preferably has the following formula: -X-R n The groups shown.

[0148] [Formula-X-R n middle,

[0149] X is a valence bond or a 1+n valence group,

[0150] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0151] n is greater than or equal to 1 and less than or equal to 3.]

[0152] When the liquid repellent compound has this group, liquid repellency can be imparted to the fiber base material in a favorable manner.

[0153] [X]

[0154] X is a bond or a 1+n-valent group. n can be 1-3, 2-3, 1-2, 1, 2 or 3.

[0155] 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.

[0156] X may be selected from X 1 and X 2 A 1+n valent group composed of one or more of 1It is composed of one or more selected from a valence bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'- and -C(OR')(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence), X 2 It is a hydrocarbon group having 1 to 40 carbon atoms. In this specification, the right side of the group represented by X is bonded to R.

[0157] [X 1 ]

[0158] X 1 A non-hydrocarbon linking group.

[0159] X 1 is a bond or a divalent or higher group. 1 The valence of X may be 2 to 4, 2 to 3 or 2. 1 Not just for the price.

[0160] 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 The molecular weight may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0161] X 1 Selected from -O-, -C(=O)-, -S(=O)2-, -NR'-, -

[0162] It is composed of one or more of C(OR')R'- and -C(OR')(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence). 1 Examples include:

[0163] Valence bond,

[0164] -O-,

[0165] -O-C(=O)-,

[0166] -O-C(=O)-O-,

[0167] -O-C(=O)-NR'-,

[0168] -NR'-

[0169] -NR'-C(=O)-,

[0170] -NR'-C(=O)-O-,

[0171] -NR'-C(=O)-NR'-,

[0172] -C(=O)-,

[0173] -C(=O)-O-,

[0174] -C(=O)-NR'-,

[0175] -SO2-,

[0176] -SO2NR'-,

[0177] -C(OR')R'-,

[0178] -C(OR')(-)2, etc.

[0179] (In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence.)

[0180] [X 2 ]

[0181] X 2 It is a hydrocarbon linking group, which is a hydrocarbon group having 1 to 40 carbon atoms.

[0182] X 2 X is a divalent or higher group. 2 The valence of may be, for example, 2 to 4, 2 to 3, or 2.

[0183] X 2 The number of carbon atoms in 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 The number of carbon atoms may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0184] X 2 It can be a cyclic, branched or linear hydrocarbon group. 2 It may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, for example, it may be an aliphatic hydrocarbon group (for example, a saturated aliphatic hydrocarbon group).

[0185] As X 2 Examples include:

[0186] -(CH2) p - (p is 1 to 40, for example, 1 to 10),

[0187] a linear hydrocarbon group having 1 to 40 carbon atoms, for example 1 to 10 carbon atoms, and having an unsaturated bond;

[0188] A hydrocarbon group having 1 to 40 carbon atoms, for example, 1 to 10 carbon atoms and having a branched structure,

[0189] -(CH2)q -C6H4-(CH2) r -(q and r are each independently 0 to 40, for example, 1 to 10, -C6H4- is phenylene) and the like.

[0190] [Example of X]

[0191] Examples of X are described below. In the following, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence.

[0192] Preferred examples of X include -X 1 -or-X 1 -X 2 -X 1 -

[0193] X is preferably -X 1 -or-X 1 -X 2 -X 1 - the group shown.

[0194] [Wherein,

[0195] X 1 Independently at each occurrence is:

[0196] Valence bond,

[0197] -O-,

[0198] -O-C(=O)-,

[0199] -O-C(=O)-O-,

[0200] -O-C(=O)-NR'-,

[0201] -NR'-

[0202] -NR'-C(=O)-,

[0203] -NR'-C(=O)-O-,

[0204] -NR'-C(=O)-NR'-,

[0205] -C(=O)-,

[0206] -C(=O)-O-,

[0207] -C(=O)-NR'-,

[0208] -SO2-,

[0209] -SO2NR'-,

[0210] -C(OR')R'-, or

[0211] - a group represented by C(OR')(-)2,

[0212] (In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence.)

[0213] X 2 It is a hydrocarbon group having 1 to 40 carbon atoms.]

[0214] X may have an amide group, a urea group or a urethane group. Specific examples of such X include:

[0215] -O-C(=O)-NR'-,

[0216] -NR'-C(=O)-,

[0217] -NR'-C(=O)-O-,

[0218] -NR'-C(=O)-NR'-,

[0219] -C(=O)-NR'-, etc.

[0220] As an example of X, 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 -wait.

[0221] As an example of X, when X is trivalent, -X 1 (-)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.

[0222] As an example of X, when X is tetravalent, -X 1 -X 2 (-X 1 -)3. -X 2 (-X 1 -)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. -X2 (-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.

[0223] As a specific example of X, when X is divalent, -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR'-, -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-X 2 -NR'-X 2 -,-O-X 2 -O-,-O-X 2 -O-C(=O)-,-O-X 2 -O-C(=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'-X2 -NR'-C(=O)-NR'-, -NR'-X 2 -NR'-X 2 -, -NR'-X 2 -O-, -NR'-X 2 -O-C(=O)-, -NR'-X 2 -O-C(=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-, -SO2-, -SO2NR'-, -C(OR')(R')(-) 、 wait.

[0224] As specific examples of X, when X is trivalent, -X 2 (-O-)2-, -X 2 (-O-C(=O)-)2-,-X 2 (-O-C(=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-, -X2 (-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-、-X 2 (-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 (-SO2-)2-, -X 2 (-SO2NR'-)2-, -X 2 (-C(OR')(R')(-))2-, -C(OR')(-)2, etc.

[0225] Specific examples of X include -X when X is tetravalent. 2 (-O-)3-, -X 2 (-O-C(=O)-)3-,-X 2 (-O-C(=O)-O-)3-,-X 2 (-O-C(=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-, -X 2 (-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-X2 -)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'-X 2 -NR'-X 2 -)3-、-X 2 (-NR'-X 2 -O-)3-、-X 2 (-NR'-X 2 -O-C(=O)-)3-、-X 2 (-NR'-X 2 -O-C(=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-、-X2 (-SO2-)3-, -X 2 (-SO2NR'-)3-, -X 2 (-C(OR')(R')(-))3-etc.

[0226] [R]

[0227] 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, more preferably linear. R is preferably a saturated aliphatic hydrocarbon group (alkyl) which may have a substituent.

[0228] The number of carbon atoms of 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, and more preferably 12 or more. The number of carbon atoms of 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, and more preferably 25 or less.

[0229] [Acrylic polymer type liquid repellent compound]

[0230] 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 also contain repeating units derived from a crosslinking monomer, a halogenated olefin monomer and / or other monomers.

[0231] (Hydrocarbon Monomer)

[0232] The acrylic polymer type liquid repellent compound may have a formula derived from: CH2=C(-Q)-C(=O)-X-R n A polymer having repeating units of the hydrocarbon monomers shown.

[0233] [Formula CH2=C(-Q)-C(=O)-X-R n middle,

[0234] Q is a hydrogen atom, a monovalent organic group or a halogen atom,

[0235] X is selected from X 1 and X 2 A 1+n-valent group composed of one or more of

[0236] Among them, X 1 It is composed of one or more selected from the group consisting of a valence bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'-, and -C(OR')(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence),

[0237] X 2 is a hydrocarbon group having 1 to 40 carbon atoms,

[0238] R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0239] n is 1 to 3.]

[0240] Furthermore, the hydrocarbon-based monomer itself can be used as the lyophobic compound.

[0241] The explanations of X, R and n are the same as those in the above-mentioned [liquid-repellent compound].

[0242] In particular, in the acrylic polymer type liquid repellent compound, X may be of the following formula: 1 -or-X 1 -X 2 -X 1 - the group shown.

[0243] [Formula-X 1 -, -X 1 -X 2 -X 1 -middle,

[0244] X 1 Each occurrence is independently -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 It is a hydrocarbon group having 1 to 40 carbon atoms.]

[0245] Q is a hydrogen atom, a monovalent organic group or a halogen atom. Examples of monovalent organic groups include cyano, aliphatic hydrocarbon groups having 1 to 6 carbon atoms (e.g., alkyl, alkenyl, etc.), and aromatic groups having 5 to 12 carbon atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Q can 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, such as a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group, preferably a hydrogen atom, a methyl group, or a chlorine atom, and particularly preferably a hydrogen atom or a methyl group.

[0246] From the viewpoint of liquid repellency, the hydrocarbon monomer may include a hydrocarbon monomer having an amide group, urea group or urethane group in X. The hydrocarbon monomer may also be a combination of a hydrocarbon monomer having an amide group, urea group or urethane group and a hydrocarbon monomer not having an amide group, urea group or urethane group.

[0247] The hydrocarbon monomer may be only a non-cyclic hydrocarbon group-containing monomer or may 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.

[0248] The cyclic hydrocarbon group-containing monomer preferably has a (meth)acrylic group as an ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as an ethylenically unsaturated double bond.

[0249] 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, a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a straight-chain or branched hydrocarbon group).

[0250] The number of carbon atoms in the cyclic hydrocarbon group may be 4 or more, 6 or more, or 8 or more, and may be 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less.

[0251] Specific examples of cyclic hydrocarbon groups include cyclohexyl, tert-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, bornyl, isobornyl, norbornyl, dicyclopentyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-tert-butylphenyl, residues obtained by removing one or more hydrogen atoms from these groups (for example, cyclohexylene, adamantylene, phenylene, naphthylene, etc.), and groups as substitutes thereof.

[0252] Specific examples of the monomer containing a cyclic hydrocarbon group include cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, tricyclopentyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, compounds obtained by replacing these acrylates with acrylamide, etc. These may be used alone or in combination of two or more.

[0253] Specific examples of hydrocarbon monomers are as follows: The compound of the following chemical formula is an acrylic compound with a hydrogen atom at the α position, but the α position may be another Q, for example, a methacrylic compound with a methyl group at the α position and an α-chloroacrylic compound with a chlorine atom at the α position.

[0254] CH2=CHC(=O)OC p H 2p NHC(=O)C q H 2q+1

[0255] CH2=CHC(=O)OC2H4NHC(=O)C 17 H 35

[0256] CH2=CHC(=O)OC2H4NHC(=O)C 15 H 31

[0257] CH2=CHC(=O)OC2H4NHC(=O)C 17 H 35 and the mixture of CH2=CHC(=O)OC2H4NHC(=O)C 15 H 31

[0258] CH2=CHC(=O)OC q H 2q+1

[0259] CH2=CHC(=O)OC 18 H 37

[0260] CH2=CHC(=O)OC 16 H 33

[0261] CH2=CHC(=O)OC2H4OC(=O)NHC q H 2q+1

[0262] CH2=CHC(=O)OC2H4NHC(=O)OC q H 2q+1

[0263] CH2=CHC(=O)OC2H4NHC(=O)NHC q H 2q+1

[0264] CH2=CHC(=O)OC4H8OC(=O)NHC q H 2q+1

[0265] CH2=CHC(=O)OC2H4OC(=O)NHC 18 H 37

[0266] CH2=CHC(=O)OC2H4NHC(=O)OC 18 H 37

[0267] CH2=CHC(=O)NHC​p H 2p OC(=O)NHC q H 2q+1

[0268] CH2=CHC(=O)OC p H 2p－1 (NH(C=O)C q H q+1 )(NH(C=O)C q H q+1 )

[0269] CH2=CHC(=O)OC p H 2p－1 (NH(C=O)C 17 H 35 )(NH(C=O)C 17 H 35 )

[0270] CH2=CHC(=O)OC p H 2p－1 (O(C=O)NHC q H q+1 )(CH2O(C=O)NHC q H q+1 )

[0271] CH2=CHC(=O)OCH2CH(O(C=O)NHC 18 H 37 )(CH2O(C=O)NHC 18 H 37 )

[0272] [In the above formula, p is 1 to 40 (e.g., 1 to 6), and q is 6 to 40 (e.g., 12 to 30).]

[0273] (Haloolefin monomers)

[0274] 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 have a fluorine atom. The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin monomer is preferably a chlorinated olefin having 2 to 20 carbon atoms, especially an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin monomer include: vinyl halides, such as vinyl chloride, vinyl bromide, and vinyl iodide; vinylidene halides, such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride is preferred because the water repellency (especially the durability of the water repellency) is improved. The washing durability imparted by the acrylic polymer type liquid repellent compound is improved by the presence of repeating units derived from halogenated olefin monomers.

[0275] (Crosslinking monomer)

[0276] The acrylic polymer type liquid repellent compound may have a repeating unit derived from a crosslinking monomer. The crosslinking monomer is a monomer that can impart crosslinking properties to the polymer, and may have at least two selected from a reactive group and an olefinic carbon-carbon double bond. The crosslinking monomer may be a compound having at least two olefinic unsaturated double bonds, or a compound having at least one olefinic unsaturated double bond and at least one reactive group.

[0277] The crosslinkable monomer preferably has a (meth)acrylic group as an ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as an ethylenically unsaturated double bond.

[0278] 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.

[0279] Specific examples of crosslinking 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, neopentyl glycol di(meth) acrylate, etc. These may be used alone or in combination of two or more. These may be used alone or in combination of two or more.

[0280] (Other monomers)

[0281] The acrylic polymer-type liquid repellent compound may contain repeating units derived from monomers other than the above-mentioned monomers.

[0282] Specific examples of other monomers include acrylonitrile, alkoxypolyalkylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylate containing organosiloxane, vinyl acetate, vinyl alkyl ether, etc. Other monomers are not limited to these examples. They can be used alone or in combination of two or more.

[0283] (Composition, etc.)

[0284] The amount of repeating units derived from hydrocarbon monomers may be 5% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 35% by weight or more, 45% by weight or more, 55% by weight or more, or 65% by weight or more relative to the acrylic polymer type liquid repellent compound. The amount of repeating units derived from hydrocarbon monomers may be 98% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less relative to the acrylic polymer type liquid repellent compound. Among hydrocarbon monomers, hydrocarbon monomers having an amide group, a urea group, or a urethane group 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 hydrocarbon monomers, hydrocarbon monomers having an amide group, a urea group, or a 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. The amount of the monomer containing a cyclic hydrocarbon group in the hydrocarbon 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. The amount of the monomer containing a cyclic hydrocarbon group in the hydrocarbon monomer may be 80% by weight or less, 60% by weight or less, 40% by weight or less, or 20% by weight or less.

[0285] The amount of the repeating unit derived from the halogenated olefin monomer may be 3% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, or 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 the repeating unit derived from the halogenated olefin monomer 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 relative to the acrylic polymer type liquid repellent compound, and is preferably 60% by weight or less.

[0286] The amount of the repeating unit derived from the cyclic hydrocarbon group-containing monomer may be 0.5 wt % or more, 1 wt % or more, 3 wt % or more, or 4 wt % or more relative to the acrylic polymer type liquid repellent compound. The amount of the repeating unit derived from the halogenated olefin monomer may be 30 wt % or less, 20 wt % or less, 15 wt % or less, 10 wt % or less, 7.5 wt % or less, or 5 wt % or less relative to the acrylic polymer type liquid repellent compound.

[0287] The amount of the repeating unit derived from the cross-linking 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 relative to the acrylic polymer type liquid repellent compound. The amount of the repeating unit derived from the cross-linking 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 relative to the acrylic polymer type liquid repellent compound.

[0288] The amount of repeating units derived from other monomers may be 0.5 wt % or more, 1 wt % or more, 3 wt % or more, 5 wt % or more, 10 wt % or more, or 20 wt % or more relative to the acrylic polymer type liquid repellent compound. The amount of repeating units derived from other monomers may be 70 wt % or less, 60 wt % or less, 50 wt % or less, 40 wt % or less, 30 wt % or less, or 20 wt % or less relative to the acrylic polymer type liquid repellent compound.

[0289] 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 1000000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 25000 or less, or 10000 or less, and is preferably 100000 or less.

[0290] (Polymerization method)

[0291] The acrylic polymer type liquid repellent compound can be produced by a known polymerization method, and the polymerization reaction conditions can be arbitrarily selected. Examples of such a polymerization method include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0292] In solution polymerization, a method can be adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, heating and stirring are performed at a temperature in the range of 30 to 120° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The amount of the polymerization initiator used is in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, relative to 100 parts by weight of the monomer.

[0293] The organic solvent is a substance that is inactive to the monomers but can dissolve them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, and methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, and isopropanol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropanol, 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 amount of the organic solvent used is in the range of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, based on 100 parts by weight of the total monomers.

[0294] In the emulsion polymerization, a method can be adopted in which the monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the monomer is stirred at 50 to 80° C. for 1 to 20 hours to polymerize. The polymerization initiator can be a water-soluble substance such as benzoyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-dihydrochloride, sodium peroxide, potassium persulfate, ammonium persulfate, and an oil-soluble substance such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, etc. The amount of the polymerization initiator used is in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.

[0295] In order to obtain a polymer aqueous dispersion with excellent shelf stability, it is preferred to use an emulsifying device that can provide strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer, to micronize and polymerize the monomer in water. In addition, as an emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the amount used is in the range of 0.5 to 20 parts by weight relative to 100 parts by weight of the monomer. Anionic and / or nonionic and / or cationic emulsifiers are preferably used. In the case where the monomers are not completely compatible, it is preferred to add a compatibilizer that makes these monomers fully compatible, such as a water-soluble organic solvent or a low molecular weight monomer. By adding a compatibilizer, the emulsification and copolymerization properties can be improved.

[0296] As the water-soluble organic solvent, the above-mentioned organic solvents can be used. For example, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc. can be mentioned, and the amount thereof can be in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of water. In addition, as low molecular weight monomers, methyl methacrylate, glycidyl methacrylate, methacrylate-2,2,2-trifluoroethyl, etc. can be mentioned, and the amount thereof can be in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of the total amount of the monomers.

[0297] A chain transfer agent may be used during polymerization. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of chain transfer agents include thiol group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly (e.g., alkyl mercaptan (having 1 to 40 carbon atoms)), sodium hypophosphite, sodium bisulfite and other inorganic salts. The amount of the chain transfer agent used can be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, relative to 100 parts by weight of the total amount of the monomers.

[0298] [Base material modified liquid repellent compound]

[0299] The lyophobic compound may be a lyophobic compound in which a base material compound is modified with a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent (base material modified lyophobic compound).

[0300] The base material modified liquid repellent compound may be a base material compound modified with the following formula: -X-R n The matrix compound is one or more compounds selected from monosaccharides, polysaccharides, alcohols, polyols, carboxylic acids, polycarboxylic acids, and their derivatives.

[0301] [Formula-X-R n middle,

[0302] X is a valence bond or a 1+n valence group,

[0303] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0304] n is greater than or equal to 1 and less than or equal to 3.]

[0305] Examples of the matrix compound include starch, cellulose, curdlan, pullulan, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomaltodextrin, xanthan gum, gellan gum, tamarind gum, cyclostranded starch, glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, steviol, dextrin, cyclodextrin, glycerol, polyglycerol, mint Alcohol, xylitol, sucralose, fructose, maltose, trehalose, lactoligosaccharide, erythritol, vanillin, cholesterol, glucosamine, catechins, anthocyanins, 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 their derivatives.

[0306] The matrix compound may be a polymer (for example, a condensed product or a cross-linked product) of the above-exemplified compounds. Preferred examples of the polymer include a glycerol polymer and a citric acid polymer.

[0307] The condensation reaction or crosslinking reaction for obtaining the polymer is not limited, and a known method for polymerization at the functional group of the base material compound can be adopted, and a known catalyst, dehydration condensation agent, crosslinking agent, etc. can be used. Examples of the catalyst, dehydration condensation 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; acyl halides such as acetyl chloride, propionyl chloride, and benzoyl 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-benzotriazol-1-yloxytris(dimethylamino) Hexafluorophosphate (BOP), O-(7-azabenzotriazole-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HATU), 2-chloro-1,3-dimethylimidazole Chloride, tripyrrolidinyl bromide Condensation agents such as hexafluorophosphate (PyBrop), diethyl cyanophosphate (DEPC), diphenyl phosphoazide (DPPA), 4-(4,6-dimethoxy[1,3,5]triazine-2-yl)-4-methylmorpholine hydrochloride (DMTMM); Lawesson's reagent, etc.

[0308] The explanations about X, R and n are the same as those in the above-mentioned [liquid-repellent compound].

[0309] The parent material compound may have a hydroxyl group. In this case, the hydroxyl group may form a group represented by the following formula: -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] in the parent material modified liquid repellent compound.

[0310] The parent compound may have a carboxyl group. In this case, the carboxyl group may form a group represented by the following formula in the above-mentioned 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].

[0311] The weight average molecular weight of the matrix 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, 25000 or less, or 10000 or less.

[0312] (Method for producing a matrix-modified liquid-repellent compound)

[0313] There is no particular limitation on the method for modifying the hydrocarbon group having 6 to 40 carbon atoms which may have a substituent on the parent compound. For example, a reaction to form a urethane bond, a reaction to form a urea bond, a reaction to form an ester bond, a reaction to form an amide bond, and a reaction to form an ether bond can be used. In the reaction to form the bond, an acylating agent, a condensing agent, a catalyst, etc. can be used appropriately.

[0314] As a method for modifying a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent on a base compound, it can be carried out 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 that can react with the functional group of the base compound.

[0315] Examples of the hydrocarbon group-containing reactants are as follows.

[0316] H2N-R

[0317] HO-R

[0318] HO(O=)C-R

[0319] G(O=)C-R

[0320] RC(=O)OC(=O)R

[0321] O=C=N-R

[0322] S=C=N-R

[0323] (CH2OCH)CH2OR

[0324] G-R

[0325] [In the formula, R is an aliphatic hydrocarbon group having 6 or more and 40 or less which may have a substituent, as defined above. G is a halogen atom (particularly F, Cl, Br or I).]

[0326] · Formation of urethane bonds

[0327] The parent material compound and the hydrocarbon group can be bonded by an urethane bond. The urethane bond can be formed, for example, by reacting a hydroxyl-containing parent material compound with an isocyanate containing an aliphatic hydrocarbon. A tin catalyst or an amine can be used as a catalyst during the reaction. For example, by reacting a hydroxyl-containing parent material compound with an isocyanate containing an aliphatic hydrocarbon group in an organic solvent for a certain period of time, the hydroxyl group reacts with the isocyanate group, and a parent material modified liquid repellent compound in which the parent material compound and the hydrocarbon group are bonded by an urethane bond can be obtained.

[0328] Urea bond formation

[0329] The parent material compound and the hydrocarbon group can be bonded by a urea bond. The urea bond can be formed, for example, by reacting an amino-containing parent material compound with an isocyanate group containing an aliphatic hydrocarbon group (or reacting an isocyanate-containing parent material compound with an amine containing an aliphatic hydrocarbon group). A catalyst can be appropriately used during the reaction. For example, by reacting an amino-containing parent material compound with an isocyanate containing an aliphatic hydrocarbon in an organic solvent for a certain period of time, the amino group reacts with the isocyanate group, and a parent material modified liquid-repellent compound in which the parent material compound and the hydrocarbon group are bonded by a urea bond can be obtained.

[0330] ·Ester bond formation

[0331] The parent material compound and the hydrocarbon group can be bonded by an ester bond. The ester bond can be formed, for example, by reacting a hydroxyl-containing parent material compound with a carboxylic acid containing an aliphatic hydrocarbon group (or reacting a carboxylic acid-containing parent material compound with an alcohol containing an aliphatic hydrocarbon group). An acylation catalyst or a condensation agent can be used during the reaction. For example, by reacting a hydroxyl-containing parent material compound with a carboxylic acid containing an aliphatic hydrocarbon group in an organic solvent for a certain period of time, the hydroxyl group reacts with the carboxylic acid, and a parent material modified liquid repellent compound in which the parent material compound and the hydrocarbon group are bonded by an ester bond can be obtained.

[0332] Amide bond formation

[0333] The parent compound and the hydrocarbon group can be bonded by an amide bond. The amide bond can be formed, for example, by reacting an amino-containing parent compound with a carboxylic acid containing an aliphatic hydrocarbon group (or reacting a carboxylic acid-containing parent compound with an amine containing an aliphatic hydrocarbon group). An acylation catalyst or a condensation agent can be used during the reaction. For example, by reacting an amino-containing parent compound with a carboxylic acid containing an aliphatic hydrocarbon group in an organic solvent for a certain period of time, the amino group reacts with the carboxylic acid, and a parent modified liquid repellent compound in which the parent compound and the hydrocarbon group are bonded by an amide bond can be obtained.

[0334] ·Ether bond formation

[0335] The parent material compound and the hydrocarbon group can be bonded by an ether bond. The ether bond can be formed, for example, by reacting a halogen-containing parent material compound with an alcohol containing an aliphatic hydrocarbon group (or reacting a hydroxyl-containing parent material compound with a halide containing an aliphatic hydrocarbon group). Acid catalysts, base catalysts, etc. can be used during the reaction. For example, by reacting a halogen-containing parent material compound with an alcohol containing an aliphatic hydrocarbon group in an organic solvent under heating in the presence of a catalyst, the alcohol containing an aliphatic hydrocarbon group acts as a nucleophile, and a parent material-modified liquid-repellent compound in which the parent material compound and the hydrocarbon group are bonded by an ether bond can be obtained.

[0336] [Ring-modified lyophobic compounds]

[0337] The lyophobic compound may be a lyophobic compound in which an aromatic ring or a nitrogen-containing heterocyclic ring is modified with an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent (ring-modified lyophobic compound).

[0338] The ring-modified liquid-repellent compound may be of the following formula: A(-X-R n ) m The compounds shown.

[0339] [Formula A(-X-R n ) m middle,

[0340] A is an aromatic ring or a nitrogen-containing heterocyclic ring which may have a substituent and has an m-valent group from which m hydrogen atoms are removed,

[0341] X is independently a bond or a 1+n valent group at each occurrence,

[0342] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0343] n is independently 1 or more and 3 or less at each occurrence,

[0344] m is greater than or equal to 1 and less than or equal to 6.]

[0345] The explanations about X, R and n are the same as those in the above-mentioned [liquid-repellent compound].

[0346] 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, preferably 2 or more. m may be 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less, preferably 4 or less.

[0347] A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or nitrogen-containing heterocyclic ring which may have a substituent. Examples of aromatic rings include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring; aromatic heterocyclic rings such as a pyridine ring, a pyrimidine ring, a quinoline ring, a furan ring, a pyrrole ring, and a pyrazole ring. Examples of nitrogen-containing heterocyclic rings include non-aromatic nitrogen-containing heterocyclic rings such as pyrrolidine, pyrazolidine, triazolidine, oxazolidine, isoxazolidine, thiazolidine, isothiazolidine, piperidine, piperazine, and morpholine; aromatic nitrogen-containing heterocyclic rings 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.

[0348] The aromatic ring or nitrogen-containing heterocyclic ring may have a substituent. Examples of the aromatic ring or nitrogen-containing heterocyclic ring which may have a substituent are not particularly limited, and examples thereof include -OR', -N(R')2, -COOR' (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a halogen atom, a halogen atom which may be substituted with one or more halogen atoms, 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 unsaturated cycloalkyl, 5- to 10-membered heterocyclic group, 5- to 10-membered unsaturated heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0349] The aromatic ring or nitrogen-containing heterocyclic ring may be a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring or an 8-membered ring. The aromatic ring or nitrogen-containing heterocyclic ring may be a condensed polycyclic ring containing 2 to 5 (preferably 2 to 3) 4- to 8-membered rings.

[0350] The ring-modified lyophobic compound may be a polymer (eg, a condensate or a cross-linked product) of the above-mentioned ring-modified lyophobic compound. In the polymer, polymerization may occur via the substituents possessed by A.

[0351] The condensation reaction or cross-linking reaction for obtaining the polymer is not limited, and a known method for polymerization on the functional group possessed by A can be adopted, and a known catalyst, dehydration condensation agent, cross-linking agent, etc. can be used. Examples of the catalyst, dehydration condensation agent, and cross-linking agent that can be used include: acids such as p-toluenesulfonic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, sulfuric acid, and fluoroboric acid; acyl halides such as acetyl chloride, propionyl chloride, and benzoyl 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-benzotriazol-1-yloxytris(dimethylamino) Hexafluorophosphate (BOP), O-(7-azabenzotriazole-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HATU), 2-chloro-1,3-dimethylimidazole Chloride, tripyrrolidinyl bromide Condensation agents such as hexafluorophosphate (PyBrop), diethyl cyanophosphate (DEPC), diphenylphosphorocyanidate (DPPA), 4-(4,6-dimethoxy[1,3,5]triazine-2-yl)-4-methylmorpholine hydrochloride (DMTMM); Lawesson's reagent, etc.

[0352] In the ring-modified lyophobic compound, X may be of the following formula: 1 -or-X 1 -X 2 -X 1 - the group shown.

[0353] [Formula-X 1 -, -X 1 -X 2 -X 1 -middle,

[0354] X 1 Independently at each occurrence is:

[0355] Valence bond,

[0356] -O-,

[0357] -O-C(=O)-,

[0358] -O-C(=O)-O-,

[0359] -O-C(=O)-NR'-,

[0360] -NR'-

[0361] -NR'-C(=O)-,

[0362] -NR'-C(=O)-O-,

[0363] -NR'-C(=O)-NR'-,

[0364] -C(=O)-,

[0365] -C(=O)-O-,

[0366] -C(=O)-NR'-,

[0367] -C(OR')R'-, or

[0368] -C(OR')(-)2,

[0369] [R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence.]

[0370] X 2 It is a hydrocarbon group having 1 to 40 carbon atoms.]

[0371] Thereby, liquid repellency can be imparted to the base material satisfactorily.

[0372] (Method for producing ring-modified lyophobic compound)

[0373] There is no particular limitation on the method of modifying the hydrocarbon group having 6 to 40 carbon atoms which may have a substituent on the aromatic ring or nitrogen-containing heterocyclic ring. For example, a reaction to form a urethane bond, a reaction to form a urea bond, a reaction to form an ester bond, a reaction to form an amide bond, and a reaction to form an ether bond can be used. In the reaction to form the bond, an acylating agent, a condensing agent, a catalyst, etc. can be used as appropriate.

[0374] As a method for modifying a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent on an aromatic ring or a nitrogen-containing heterocyclic ring, it can be carried out 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 that can react with a functional group possessed by the aromatic ring or the nitrogen-containing heterocyclic ring.

[0375] Examples of the hydrocarbon group-containing reactants are as follows.

[0376] H2N-R

[0377] HO-R

[0378] HO(O=)C-R

[0379] G(O=)C-R

[0380] RC(=O)OC(=O)R

[0381] O=C=N-R

[0382] S=C=N-R

[0383] (CH2OCH)CH2OR

[0384] G-R

[0385] [In the formula, R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, as defined above. G is a halogen atom (particularly F, Cl, Br or I).]

[0386] · Formation of urethane bonds

[0387] The aromatic ring or nitrogen-containing heterocyclic ring and the hydrocarbon group may be bonded via an urethane bond. The urethane bond may be formed, for example, by reacting a hydroxyl-containing aromatic ring or a nitrogen-containing heterocyclic ring with an isocyanate containing an aliphatic hydrocarbon. A tin catalyst or an amine may be used as a catalyst during the reaction. For example, by reacting a hydroxyl-containing aromatic ring or a nitrogen-containing heterocyclic ring with an isocyanate containing a hydrocarbon group in an organic solvent for a certain period of time, the hydroxyl group reacts with the isocyanate group, and a ring-modified liquid-repellent compound in which the aromatic ring or the nitrogen-containing heterocyclic ring and the hydrocarbon group are bonded via an urethane bond can be obtained.

[0388] Urea bond formation

[0389] The aromatic ring or nitrogen-containing heterocycle can be bonded to the hydrocarbon group through a urea bond. The urea bond can be formed, for example, by reacting an amino-containing aromatic ring or a nitrogen-containing heterocycle with an isocyanate group containing a hydrocarbon group (or reacting an isocyanate-containing aromatic ring or a nitrogen-containing heterocycle with an amine containing a hydrocarbon group). A catalyst can be appropriately used during the reaction. For example, by reacting an amino-containing aromatic ring or a 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, and a ring-modified liquid-repellent compound in which the aromatic ring or the nitrogen-containing heterocycle is bonded to the hydrocarbon group through a urea bond can be obtained.

[0390] ·Ester bond formation

[0391] The aromatic ring or nitrogen-containing heterocycle can be bonded to the hydrocarbon group through an ester bond. The ester bond can be formed, for example, by reacting a hydroxyl-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon-containing carboxylic acid (or reacting a carboxylic acid-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon-containing alcohol). An acylation catalyst or condensation agent can be used during the reaction. For example, by reacting a hydroxyl-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon-containing carboxylic acid in an organic solvent for a certain period of time, the hydroxyl group reacts with the carboxylic acid, and a ring-modified lyophobic compound in which the aromatic ring or nitrogen-containing heterocycle is bonded to the hydrocarbon group through an ester bond can be obtained.

[0392] Amide bond formation

[0393] The aromatic ring or nitrogen-containing heterocycle can be bonded to the hydrocarbon group through an amide bond. The amide bond can be formed, for example, by reacting an amino-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon-containing carboxylic acid (or reacting a carboxylic acid-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon-containing amine). An acylation catalyst or condensation agent can be used during the reaction. For example, by reacting an amino-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon-containing carboxylic acid in an organic solvent for a certain period of time, the amino group reacts with the carboxylic acid, and a ring-modified liquid-repellent compound in which the aromatic ring or nitrogen-containing heterocycle is bonded to the hydrocarbon group through an amide bond can be obtained.

[0394] ·Ether bond formation

[0395] The aromatic ring or nitrogen-containing heterocycle can be bonded to the hydrocarbon group through an ether bond. The ether bond can be formed, for example, by reacting a halogen-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon-containing alcohol (or reacting a hydroxyl-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon-containing halide). Acid catalysts, base catalysts, etc. can be used during the reaction. For example, by reacting a halogen-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon-containing alcohol under heating in an organic solvent under a catalyst, the hydrocarbon-containing alcohol plays a role as a nucleophile, and a ring-modified lyophobic compound in which the aromatic ring or nitrogen-containing heterocycle is bonded to the hydrocarbon group through an ether bond can be obtained.

[0396] [Isocyanate-based liquid-repellent compound]

[0397] The liquid repellent compound may be a liquid repellent compound (isocyanate-based liquid repellent compound) which is a reaction product of an isocyanate group-containing compound and an isocyanate-reactive compound, and is preferably an isocyanate-based liquid repellent compound having an optionally substituted hydrocarbon group having 6 to 40 carbon atoms.

[0398] Examples of isocyanate group-containing compounds that are raw materials for isocyanate-based liquid-repellent compounds include high-functional isocyanates including isocyanates, diisocyanates, triisocyanates, and polymer 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-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diisocyanatodiphenyl ether, 3,3'-dichloro-4,4'-diisocyanatodiphenylmethane, 4,4'-diphenyl diisocyanate, 4,4'-diisocyanatobibenzyl, 3,3'-dimethoxy-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 2,2'-dichloro-5,5'-dimethoxy-4,4'-diisocyanatobiphenyl, 1 Alicyclic 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; 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 tris-(4-isocyanatophenyl)-methane. Examples of polymer isocyanates include polymethylene polyphenyl isocyanate (PAPI).

[0399] Isocyanate-reactive compounds are compounds having isocyanate-reactive groups, and examples thereof include monofunctional, difunctional, and polyfunctional alcohols, thiols, and amines. Examples of isocyanate-reactive compounds include: methyl alcohol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, tert-pentanol, 2-ethylhexanol, glycidol, (iso)stearyl alcohol, behenyl alcohol, and other alkanols; alkyl alcohols having C6 to C40 alkyl chains, such as straight-chain or branched long-chain alkanols; methyl ether or ethyl ether of polyethylene glycol, random copolymers or block copolymers of ethylene oxide and / or propylene oxide and alcohols containing polysiloxane (e.g., polydimethylsiloxane) groups, such as hydroxyl-terminated methyl ethers or ethyl ethers. As further examples, there can be mentioned diols, triols and polyols such as 1,4-butanediol, 1,6-hexanediol, 1-10-decanediol, 4,4'-isopropyldiphenol (bisphenol A), glycerol, pentaerythritol, dipentaerythritol, polycaprolactone diol, fatty acid dimer diol, and poly(oxy)alkylene glycols having oxyalkylene groups with 2 to 4 carbon atoms such as -OCH2CH2-, -O(CH2)4-, -OCH2CH2CH2-, -OCH(CH3)CH2- and -OCH(CH3)CH(CH3)- (the oxyalkylene units in the above poly(oxyalkylene) may be the same as those in polypropylene glycol, or may be present in the form of a mixture), and ester diols such as glyceryl monostearate and polysiloxane-containing diols (e.g., polydimethylsiloxane-containing diols). Examples of the isocyanate-reactive compound include amino group-containing compounds such as octadecylamine, dioctadecylamine, and 1,6-hexamethylenediamine, amino group-terminated polyethylene oxide or polypropylene oxide or copolymers thereof, amino group-terminated methyl ethers or ethyl ethers of polyethylene oxide or polypropylene oxide or copolymers thereof, and amino group-terminated polysiloxanes such as polydimethylsiloxane.

[0400] Regarding isocyanate-based compounds, the isocyanate-reactive compound preferably has, in addition to the 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 (equivalent to the above-mentioned R)).

[0401] The isocyanate-based compound may be a polymer obtained by a continuous reaction of an isocyanate and an isocyanate-reactive compound.

[0402] The isocyanate-based liquid repellent compound may be of the following formula: L(-X-R n ) m The compounds shown.

[0403] [Formula L(-X-R n )m middle,

[0404] L is the reaction product of (a) one or more isocyanate group-containing compounds selected from isocyanates, diisocyanates and polyisocyanates and (b) one or more isocyanate-reactive compounds selected from the compounds represented by the following general formulae (2a), (2b) and (2c), and is an m-valent urethane / amide skeleton,

[0405] X is independently a bond or a 1+n valent group at each occurrence,

[0406] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0407] n is independently 1 or more and 3 or less at each occurrence,

[0408] m is greater than or equal to 1 and less than or equal to 6.]

[0409]

[0410] [In general formulas (2a) and (2c),

[0411] Rr is independently -H, -*, -C(O)-*, -(CH2CH2O) at each occurrence p (CH(CH3)CH2O) q H, -(CH2CH2O) p (CH(CH3)CH2O) q -* or -(CH2CH2O) p (CH(CH3)CH2O) q C(O)-*,

[0412] p is independently 0 to 20 at each occurrence,

[0413] q is independently 0 to 20 at each occurrence,

[0414] p+q is greater than 0,

[0415] The symbol * is the valence bond of L,

[0416] When the isocyanate-reactive compound is represented by the general formula (2a) or (2c), at least one of Rr is -H or -(CH2CH2O). p (CH(CH3)CH2O) q H, at least one of the other Rr is -*, -C(O)-*, -(CH2CH2O) p (CH(CH3)CH2O) q -* or -(CH2CH2O) p(CH(CH3)CH2O) q C(O)-*,

[0417] In the general formula (2b),

[0418] Rr' is independently -H, -*, -C(O)-*, -(CH2CH2O) at each occurrence p' (CH(CH3)CH2O) q' H, -(CH2CH2O) p' (CH(CH3)CH2O) q' -* or -(CH2CH2O) p' (CH(CH3)CH2O) q' C(O)-*,

[0419] Rr" is independently -H, -*, -(CH2CH2O) at each occurrence p' (CH(CH3)CH2O) q' H, -(CH2CH2O) p' (CH(CH3)CH2O) q' -* or -(CH2CH2O) p' (CH(CH3)CH2O) q' C(O)-*,

[0420] p' is independently 0 to 20 at each occurrence,

[0421] q' is independently 0 to 20 at each occurrence,

[0422] p'+q' is greater than 0,

[0423] The symbol * is the valence bond of L,

[0424] When the isocyanate-reactive compound is represented by the general formula (2b), at least one of Rr' and Rr" is -H or -(CH2CH2O). p' (CH(CH3)CH2O) q' H, and at least one of Rr' and Rr" is -*, -C(O)-*, -(CH2CH2O) p' (CH(CH3)CH2O) q' -* or -(CH2CH2O) p' (CH(CH3)CH2O) q' C(O)-*.]

[0425] Here, p, q, p′ and q′ are integers of 0 to 20 in only one isocyanate-based liquid repellent compound, but may be expressed as an average value in the case of an aggregate of a plurality of isocyanate-based liquid repellent compounds.

[0426] At this time, L of the isocyanate-based liquid-repellent compound is an urethane skeleton obtained by a process including the step of reacting an isocyanate-containing compound (a) with an isocyanate-reactive compound (b), and the urethane / amide skeleton can generally be polyvalent, but is not limited thereto. When the isocyanate-reactive compound (b) is represented by the general formula (2a) or (2c), it has at least one -OH group; when it is represented by the general formula (2b), it has at least one -OH group or -COOH group. Therefore, by reacting the isocyanate-containing compound (a) with the isocyanate-reactive compound (b), a reaction product in which they are bonded by an urethane bond or an amide bond can be obtained. Such a reaction is known and can be carried out under any appropriate conditions.

[0427] In such an isocyanate-based liquid-repellent compound, each of the m valence bonds (indicated by the symbol *) existing in the portion derived from the isocyanate-reactive compound (b) is bonded to -X-R n (X and L are bonded by valence). “-X-R n The " portion is bonded to the valence bond (indicated by the symbol *) existing 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 compounds represented by the general formula (2a), (2b) and (2c), among which the compound represented by the general formula (2a) is preferred.

[0428] The isocyanate group-containing compound (a) may be one selected from isocyanate, diisocyanate and polyisocyanate, or a mixture of any two or more thereof. When the isocyanate group-containing compound (a) is a diisocyanate and / or a 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, but is not limited thereto.

[0429] The isocyanate, diisocyanate and polyisocyanate groups are preferably at least one selected from the group consisting of compounds represented by the following formulae (3a) to (3h).

[0430]

[0431]

[0432] Examples of the isocyanate-based liquid repellent compound include isocyanate-based liquid repellent compounds described in Japanese Patent Application Laid-Open No. 2022-33218 (WO2016 / 049278), Japanese Patent No. 6987847 (WO2018 / 031534), and WO2021 / 251302.

[0433] [Polysilicone-containing liquid repellent compound]

[0434] The liquid repellent compound may be a liquid repellent compound having a polysiloxane group (a liquid repellent compound containing a polysiloxane group). Like the aliphatic hydrocarbon group (R) having 6 to 40 carbon atoms which may have a substituent in the above other liquid repellent compounds, the polysiloxane group can impart liquid repellency to the substrate.

[0435] The polysiloxane group can be represented by the following formula: -[-Si(Rs 1 )2-O-] a -express.

[0436] [Formula - [-Si(Rs 1 )2-O-] a -middle,

[0437] Rs 1 Each occurrence is independently a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and a is 5 to 10,000.]

[0438] Rs 1 It is a hydrocarbon group having 1 to 40 carbon atoms or a reactive group.

[0439] 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 methyl, ethyl, propyl, butyl and pentyl, and hydrocarbon groups having 6 to 40 carbon atoms which may have a substituent.

[0440] The hydrocarbon group with a carbon number of 6 or more and 40 or less that 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, preferably linear. The number of carbon atoms of 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, and more preferably 12 or more. The number of carbon atoms of 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, and more preferably 25 or less. Among them, the hydrocarbon group with a carbon number of 6 or more and 40 or less that may have a substituent mentioned here may be equivalent to the R described above, and the description of the hydrocarbon group with a carbon number of 6 or more and 40 or less that may have a substituent is used.

[0441] Examples of reactive groups are groups having functional groups (e.g., hydroxyl, amino, mercapto, epoxy, carboxyl, halogenated alkyl, vinyl, (meth)acrylate and (meth)acrylamide groups, hydrogen atoms directly bonded to silicon atoms, etc.). These functional groups may be directly bonded to silicon atoms, or may be bonded to organic groups directly bonded to silicon atoms. The organic group may be a hydrocarbon group, for example, an alkylene group or a divalent aromatic group. The number of carbon atoms in the hydrocarbon group may be 2 to 12, and as an alkylene group, the number of carbon atoms is preferably 2 to 10. As a divalent aromatic group, the number of carbon atoms is preferably 6 to 12.

[0442] 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 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 100 or less, or 50 or less.

[0443] The amount of hydrocarbon groups having 1 to 40 carbon atoms relative to Rs 1 The total amount of the hydrocarbon groups having 1 to 40 carbon atoms relative to Rs 1 The total amount may be 100 mol % or less, 90 mol % or less, 80 mol % or less, or 70 mol % or less.

[0444] The amount of reactive groups (e.g., -OH, -COOH, or -NR'2) relative to Rs 1 The total amount of the reactive groups (eg, -OH, -COOH or -NR'2) relative to Rs 1 The total amount may be 50 mol % or less, 40 mol % or less, 30 mol % or less, or 20 mol % or less.

[0445] In the polysiloxane-containing liquid repellent compound, the polysiloxane group may be present in the main chain, the core or the side chain. For example, when the polysiloxane-containing liquid repellent compound has a side chain of the polysiloxane-containing liquid repellent compound, the polysiloxane-containing liquid repellent compound may be a compound in which part or all of the aliphatic hydrocarbon groups (R) having 6 to 40 carbon atoms and which may have a substituent in the above-mentioned other liquid repellent compounds (e.g., acrylic polymer liquid repellent compounds, matrix modified liquid repellent compounds, isocyanate liquid repellent compounds) are replaced with polysiloxane groups.

[0446] The polysiloxane group may be present in the main chain or core of the polysiloxane group-containing lyophobic compound.

[0447] The liquid repellent compound containing a polysiloxane group may not have a structure other than polysiloxane. The liquid repellent compound containing a polysiloxane group may be represented by the following formula: (Rs 2 )3Si-O-[-Si(Rs 1 )2-O-] a -Si(Rs 2 )3 indicates.

[0448] [Formula (Rs 2 )3Si-O-[-Si(Rs 1 )2-O-] a -Si(Rs 2 )3,

[0449] Rs 1 and a as above,

[0450] Rs 2 Each occurrence is independently a hydrocarbon group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a reactive group.]

[0451] The polysiloxane group may be present in the side chain of the liquid repellent compound containing the polysiloxane group (for example, the side chain of the acrylic polymer type liquid repellent compound). The so-called side chain is the structure of the part other than the main chain or the mother core of the compound, for example, it may be a terminal structure. In the case where the polysiloxane group is present in the side chain, the polysiloxane group may be represented by the following formula: -[-Si(Rs 1 )2-O-] a -Si(Rs 2 )3 indicates.

[0452] [Formula - [-Si(Rs 1 )2-O-] a -Si(Rs 2 )3,

[0453] Rs 1 and a as above,

[0454] Rs 2 Each occurrence is independently a hydrocarbon group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a reactive group.]

[0455] Rs 2 It 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 is preferably an aliphatic hydrocarbon group, preferably an alkyl group, and preferably has 1 to 5 carbon atoms. 2 The number of carbon atoms of the alkoxy group having 1 to 40 carbon atoms is preferably 1 to 5, 1 to 3 or 1 to 2 carbon atoms. 2In the case of a reactive group, examples of reactive groups are as follows: 1 same.

[0456] The polysiloxane-containing lyophobic compound can be synthesized according to a conventionally known method. For example, a polysiloxane-containing lyophobic compound having a hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent can be obtained by modifying an α-olefin on SiH in methylhydrogensilicone or a copolymer of dimethylsiloxane and methylhydrogensiloxane by a hydrosilylation reaction using a catalyst such as a compound of platinum or palladium as required. In addition, the polysiloxane-containing lyophobic compound can also be obtained by polymerizing an acrylic monomer containing a polysiloxane group or reacting a reactive group of polysiloxane with a parent core compound.

[0457] [Amine modified form]

[0458] The lyophobic compound may be an amine-modified compound.

[0459] The molecular weight of the amine-modified form 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 form 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.

[0460] The amine-modified body of the present invention may not have an active hydrogen-containing group. Examples of active hydrogen-containing groups include amino groups (amino groups not adjacent to a carbonyl group, such as primary amino groups or secondary amino groups), hydroxyl groups, and carboxyl groups. In particular, the amine-modified body of the present invention may not have a primary amino group or secondary amino group not adjacent to a carbonyl group.

[0461] The amine modified product may have an amine skeleton and one or more of the formula: -X N -R n A compound comprising the aliphatic hydrocarbon-containing group shown above, wherein at least one of the aliphatic hydrocarbon-containing groups is bonded to a nitrogen atom of the amine skeleton.

[0462] [Formula-X N -R n middle,

[0463] X N is a valence bond or a 1+n valence group,

[0464] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0465] n is an integer of 1 to 3.]

[0466] (Amine skeleton)

[0467] The amine modified body of the present invention has an amine skeleton. The so-called amine skeleton has one or more amino groups with a specified number of valence bonds (valence) obtained by removing a specified number of atoms or atomic groups (such as hydrogen) from an amine compound. The amino group in the amine skeleton means a group selected from -NH2, -NH- and -N(-)2, and also includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide group, etc. Among them, the amine skeleton can be an aliphatic group or an aromatic group having one or more amino groups, and the presence of heteroatoms other than nitrogen is not excluded.

[0468] The molecular weight of the amine skeleton 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 skeleton 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.

[0469] 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.

[0470] The amine skeleton has one or more amino groups. The amino group is a monovalent to trivalent amino group, and is one or more groups selected from -NH2, -NH- and -N(-)2. The number of amino groups possessed by the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more. The number of amino groups possessed by 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.

[0471] The amine skeleton has a hydrocarbon group (aliphatic hydrocarbon group or 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 disconnected by oxygen atoms and / or sulfur atoms, or may be composed only of carbon atoms, nitrogen atoms and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group that can be disconnected by oxygen atoms and / or sulfur atoms (e.g., a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings), or may be a general hydrocarbon group (e.g., a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings). When the hydrocarbon group is disconnected by oxygen atoms and / or sulfur atoms, it has an ether, thioether, polyether or polythioether structure. The number of hydrocarbon groups possessed by 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 possessed by 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.

[0472] The amine skeleton may be composed of a monovalent to trivalent amino group and a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be disconnected by an oxygen atom and / or a sulfur atom.

[0473] The molar ratio of carbon atoms to nitrogen atoms in the amine skeleton (C / N ratio) 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 in the amine skeleton (C / N ratio) 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, preferably 6 or less or 4 or less.

[0474] Raw material amine compounds

[0475] Examples of the precursor of the amine skeleton, i.e., the raw material amine compound, include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, cyclohexylenediamine, 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, bis[2- [3-aminopropoxy]ethyl] ether, spermine, spermidine and other polyalkylene polyamines; oxygen- or sulfur-containing aliphatic amines such as 1-aminopropylene glycol, 2-amino-1,3-propylene glycol, 3-amino-1,2-propylene glycol, polyoxypropylene diamine, polyoxyethylene diamine and the like; aromatic monoamines such as aniline, 1-naphthylamine or 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene or 9-aminoanthracene, 9-aminophenanthrene, 2-aminobiphenyl, 3-aminobiphenyl or 4-aminobiphenyl and the like; monocyclic Aromatic polyamines; diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, bisaminodi-trifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,a-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, diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenedianiline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, 4,4'-bis(aminophenyl)amine and the like polycyclic aromatic polyamines;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, 4,4'-diaminodiphenyl sulfide, etc.; hydroxyl-containing polyamines such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc.;

[0476] (Aliphatic hydrocarbon-containing group)

[0477] The amine modified substance in the present invention has one or more formulas: -X N -R n The aliphatic hydrocarbon-containing group shown.

[0478] [Formula-X N -R n middle,

[0479] X N is a valence bond or a 1+n valence group,

[0480] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0481] n is an integer of 1 to 3.]

[0482] The number of aliphatic hydrocarbon-containing groups possessed by 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 is preferably 2 or more. The number of aliphatic hydrocarbon-containing groups possessed by 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.

[0483] At least one aliphatic hydrocarbon-containing group in the amine-modified body is bonded to a nitrogen atom possessed by the amine skeleton. The ratio of the number of aliphatic hydrocarbon-containing groups bonded to the nitrogen atom possessed by the amine skeleton to the total number of aliphatic hydrocarbon-containing groups in the amine-modified body 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 the nitrogen atom possessed by the amine skeleton to the total number of aliphatic hydrocarbon-containing groups in the amine-modified body may be 75% or less, 50% or less, or 25% or less. The aliphatic hydrocarbon-containing group not bonded to the nitrogen atom possessed by the amine skeleton is bonded to another group (e.g., a hydrocarbon group) possessed by the amine skeleton.

[0484] ·X N

[0485] X N is a valent bond or a 1+n valent group, preferably a 1+n valent group. NIt plays the role of a linking group connecting the amine skeleton and n Rs.

[0486] n is the same as X N The number of bonded R may be an integer of 1 to 3. n may be 1 to 3, 2 to 3, or 3 to 3. n may be 3 to 3, 2 to 2, or 1 to 1, for example, 2 to 2.

[0487] X N It may be an aliphatic group (an unsaturated aliphatic group or a saturated aliphatic group) or an aromatic group.

[0488] 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 The molecular weight may be 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 300 or less.

[0489] X N It may have a carbonyl group. N It may have one or more selected from an amide group, a urea group, a urethane group and an imide group, or X N It can also form one or more selected from amide groups, urea groups, urethane groups and imides together with the amino group in the amine skeleton. Examples of such amide groups, urea groups, urethane groups and imides include:

[0490] -O-C(=O)-NR'-,

[0491] -NR'-C(=O)-,

[0492] -NR'-C(=O)-O-,

[0493] -NR'-C(=O)-NR'-

[0494] -C(=O)-NR'-

[0495] -C(=O)-NR'-C(=O)-.

[0496] [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]

[0497] X N It is preferably bonded to the nitrogen atom of the amine skeleton via a -(C=O)- group.

[0498] X NIt may be a 1+n-valent group composed of one or more selected from a bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2, a 2- to 4-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a 2- to 4-valent aromatic hydrocarbon ring, and a 2- to 4-valent heterocycle [wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms].

[0499] X N It can be selected from X N1 and X N2 A 1+n valent group composed of one or more of N1 It is composed of one or more selected from the group consisting of a valence bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, -N(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence); X N2 It is composed of one or more selected from a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent to tetravalent aromatic hydrocarbon ring, and a divalent to tetravalent heterocyclic ring. N The left side of the group is bonded to the amine skeleton, and the right side is bonded to R.

[0500] X N1

[0501] X N1 It is a non-hydrocarbon linking group.

[0502] X N1 is a bond or a divalent or higher group. N1 The valence of X may be 2 to 4, 2 to 3 or 2. N1 Not just for valence bonds.

[0503] X N1 The molecular weight of X can be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more. N1 The molecular weight may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0504] X N1 It is composed of one or more selected from a valence bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)2-, -NR'-, -C(OR')R'-, -C(OR')(-)2, and -N(-)2 (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence). N1 Examples include:

[0505] Valence bond,

[0506] -O-,

[0507] -O-C(=O)-,

[0508] -O-C(=O)-O-,

[0509] -O-C(=O)-NR'-,

[0510] -NR'-

[0511] -NR'-C(=O)-,

[0512] -NR'-C(=O)-O-,

[0513] -NR'-C(=O)-NR'-,

[0514] -C(=O)-,

[0515] -C(=O)-O-,

[0516] -C(=O)-NR'-,

[0517] -C(=O)-NR'-C(=O)-,

[0518] -C(=NR')-,

[0519] -S-,

[0520] -SO2-,

[0521] -SO2NR'-,

[0522] -C(OR')R'-,

[0523] -C(OR')(-)2,

[0524] -N(-)2, etc.

[0525] [In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence.]

[0526] Among them, in X N1 When the amino group is bonded to a nitrogen atom in the amine skeleton, the nitrogen atom is regarded as a part of the amine skeleton (amino group).

[0527] X N2

[0528] X N2 It is a hydrocarbon or aromatic linker.

[0529] X N2It can be a hydrocarbon group or a non-hydrocarbon group (containing heteroatoms). N2 It can be aliphatic or aromatic, preferably aliphatic. N2 It can be straight chain, branched chain or cyclic. N2 Preferably, it is in the form of a chain.

[0530] X N2 X is a divalent or higher group. N2 The valence of may be 2 to 4, 2 to 3 or 2, for example.

[0531] X N2 The number of carbon atoms in 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. N2 The number of carbon atoms may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0532] X N2 It is composed of one or more selected from a di- to tetra-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetra-valent aromatic hydrocarbon ring, and a di- to tetra-valent heterocyclic ring.

[0533] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a cyclic, branched or linear hydrocarbon group, preferably a chain hydrocarbon group (particularly a linear hydrocarbon group). The divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The aliphatic hydrocarbon group having 1 to 20 carbon atoms may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more carbon atoms. The aliphatic hydrocarbon group having 1 to 20 carbon atoms may have 15 or less, 10 or less, or 5 or less carbon atoms.

[0534] Examples of divalent to tetravalent aromatic hydrocarbon rings include groups obtained by removing 2 to 4 hydrogen atoms from aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (benzanthracene), pentacene, pyrene, and hexaphenylene. The number of ring atoms of the aromatic hydrocarbon ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The aromatic hydrocarbon 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, -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, or a halogen atom. The valence of the aromatic hydrocarbon ring may be 2 or more, 3 or more, or 4, or may be 4 or less, 3 or less, or 2.

[0535] The divalent to tetravalent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocyclic ring 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, imidazoline, thiazoline, etc. The number of ring atoms of the heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The heterocyclic 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, -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, or a halogen atom. The valence of the heterocyclic ring may be 2 or more, 3 or more, or 4 or less, 3 or less, or 2.

[0536] As X N2 Examples include:

[0537] -Ali-

[0538] -Cy-

[0539] -Ali(-)2

[0540] -Cy(-)2

[0541] -Ali-Cy-

[0542] -Cy-Ali-

[0543] -Cy-Ali-Cy-

[0544] -Ali-Cy-Ali-etc.

[0545] [In the formula, Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring.]

[0546] As X N2 Specific examples include:

[0547] -(CH2) p - (p is 1 to 20, for example, 1 to 10),

[0548] a linear hydrocarbon group having 1 to 40 carbon atoms, for example 1 to 10 carbon atoms, and having an unsaturated bond;

[0549] A hydrocarbon group having 1 to 40 carbon atoms, for example, 1 to 10 carbon atoms and having a branched structure,

[0550] -(CH2) q -Cy-(CH2) r-(q and r are each independently 0 to 20, for example, 1 to 10, and Cy is an aromatic hydrocarbon ring or a heterocyclic ring) and the like.

[0551] X N Example

[0552] X N Herein, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence.

[0553] As X N For example, in X N In the case of 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 -wait.

[0554] As X N For example, in X N In the case of 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 -X N2 (-)2, -X N1 -X N2 -X N1 -(X N2 -)2. -XN1 -X N2 -(X N1 -X N2 -)2. -X N1 -(X N2 -X N1 -X N2 -)2;

[0555] -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.

[0556] As X N For example, in X N In the case of 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 -XN1 -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;

[0557] -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 -X N2 -(X N1 -)3. -X N2 -X N1 -(X N2 -X N1 -)3. -X N2 -(X N1 -X N2 -X N1 -)3, etc.

[0558] As X N Preferred examples include -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 -XN1 -X N2 -, -X N2 -X N1 (-)2, etc. In the amine-modified form, one or more X N It is preferred that the amine skeleton-side terminal is -(C=O)- and is bonded to a nitrogen atom in the amine skeleton.

[0559] X N 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 represented by the group.

[0560] [Wherein,

[0561] X N1 Independently at each occurrence is:

[0562] Valence bond,

[0563] -O-,

[0564] -O-C(=O)-,

[0565] -O-C(=O)-O-,

[0566] -O-C(=O)-NR'-,

[0567] -NR'-

[0568] -NR'-C(=O)-,

[0569] -NR'-C(=O)-O-,

[0570] -NR'-C(=O)-NR'-,

[0571] -C(=O)-,

[0572] -C(=O)-O-, or

[0573] -C(=O)-NR'-

[0574] -C(=O)-NR'-C(=O)-,

[0575] (In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence.)

[0576] X N2 It 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 triazolyl group).]

[0577] Thereby, liquid repellency can be imparted to the base material satisfactorily.

[0578] As X N Further specific examples include:

[0579] *-(C=O)-

[0580] -O-(C=O)-NR'-, etc.

[0581] [wherein, * means bonding to the nitrogen atom of the amine skeleton,

[0582] R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]

[0583] ·R

[0584] R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms and may have a substituent. R is branched or straight chain, more preferably straight chain. R may be saturated or unsaturated. R is preferably a saturated aliphatic hydrocarbon group (alkyl group).

[0585] The number of carbon atoms of 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, and more preferably 12 or more. The number of carbon atoms of 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, and more preferably 25 or less.

[0586] The hydrocarbon group may have a substituent, but preferably no substitution. Examples of substituents include -OR', -N(R')2, -COOR' and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence). The substituent may have an active hydrogen or may not have one. 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 hydrocarbon group having a substituent, 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 hydrocarbon group having a substituent, 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 (eg 1) —OR′ (particularly —OH) as substituents (eg excluding the terminal).

[0587] (Example of amine-modified form)

[0588] ·Amine modification example 1

[0589] Examples of the amine-modified form include compounds represented by the following formula (amine-modified form example 1).

[0590] 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

[0591] [Wherein,

[0592] X N is independently a bond or a 1+n-valent group at each occurrence,

[0593] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0594] L 1 Each occurrence is independently 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,

[0595] n is independently an integer from 1 to 3 at each occurrence,

[0596] p is independently an integer from 0 to 2 at each occurrence,

[0597] q is independently an integer from 0 to 2 at each occurrence,

[0598] p+q in each N(-X N -R n ) p (-H) q The middle is 2,

[0599] r is independently 0 or 1 at each occurrence,

[0600] s is independently 0 or 1 at each occurrence,

[0601] r+s in each N(-X N -R n ) r (-H) s The middle is 1,

[0602] The sum of all p's and all r's is greater than 1.

[0603] t is an integer of 0 to 10.]

[0604] In amine modification example 1, X N The details of , R and n are the same as those described above.

[0605] In amine modification example 1, L 1 It is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be disconnected by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched or linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon. 1 The hydrocarbon group in the above description of the [amine skeleton] may be used, and the hydrocarbon group may be disconnected by oxygen atoms and / or sulfur atoms, or may be composed only of carbon atoms, nitrogen atoms, and hydrogen atoms. 1 For example, it may be a saturated or unsaturated (for example, saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. 1 It is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, sulfide sulfur), and specific examples thereof include 1,3-phenylenebisalkylene, 1,4-phenylenebisalkylene, diphenyl ether diyl, and diphenyl sulfide diyl. 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. 1The number of carbon atoms may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0606] In the amine modification example 1, p is independently an integer from 0 to 2 at each occurrence, q is independently an integer from 0 to 2 at each occurrence, and p+q is N -R n ) p (-H) q Preferably, p is independently 1 or more, for example, 2, at each occurrence.

[0607] In amine modification embodiment 1, r is independently 0 or 1 at each occurrence, s is independently 0 or 1 at each occurrence, and r+s is independently 0 or 1 at each N(-X N -R n ) r (-H) s Preferably, p is independently 1 or more, for example, 2, at each occurrence.

[0608] The sum of all p and all r is 1 or more, that is, the amine modification example 1 has one or more -X N -R n The sum of all p and all r can be greater than 1, greater than 3, greater than 5, greater than 7, greater than 9, or greater than 12 (the sum of all q and all s can be 0). The sum of all p and all r can be less than 14, less than 12, less than 10, less than 8, less than 6, or less than 4.

[0609] In amine modification example 1, t is an integer of 0 to 10. t may be 0 to 1, 2 to 4, or 6 to 6, preferably 0 to 2. t may be 8 to 8, 6 to 6, 4 to 3 or less.

[0610] ·Amine modification example 2

[0611] As other examples of amine-modified forms, there can be mentioned compounds represented by the following formula (amine-modified form example 2).

[0612] N(-X N -R n ) p (-H) q -L 2 (-X N -R n ) u

[0613] [Wherein,

[0614] X Nis independently a bond or a 1+n-valent group at each occurrence,

[0615] R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent,

[0616] L 2 is a 1+u-valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be disconnected by an oxygen atom and / or a sulfur atom,

[0617] n is independently an integer from 1 to 3 at each occurrence,

[0618] p is an integer from 0 to 2,

[0619] q is an integer from 0 to 2,

[0620] p+q is 2,

[0621] u is an integer from 1 to 3,

[0622] The total of p and u is greater than or equal to 1.]

[0623] In amine modification embodiment 2, X N The details of , R and n are the same as those described above.

[0624] In amine modification example 2, L 2 It is a 1+u-valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be disconnected by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched or linear hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon. 2 The hydrocarbon group in the above description of the [amine skeleton] may be used, and the hydrocarbon group may be disconnected by oxygen atoms and / or sulfur atoms, or may be composed only of carbon atoms, nitrogen atoms, and hydrogen atoms. 2 For example, it may be a saturated or unsaturated (for example, saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. 2 It is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, sulfide sulfur), and specific examples thereof include 1,3-phenylenebisalkylene, 1,4-phenylenebisalkylene, diphenyl ether diyl, and diphenyl sulfide diyl. 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. 2 The number of carbon atoms may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0625] 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 is 1 or more, for example, 2.

[0626] In the amine modification example 2, u is an integer of 1 to 3. u is 1, 2 or 3, for example, 2 or 3.

[0627] In the amine modified form 2, the sum of p and u is 1 or more, that is, the amine modified form 2 has one or more -X N -R n The total of all p and u may be greater than 1, greater than 2, greater than 3, greater than 4, or greater than 5 (the total of all q may be 0). The total of p and u may be less than 5, less than 4, less than 3, or less than 2.

[0628] The amine-modified wax may be a synthetic wax derived from animal or vegetable fats. Synthetic waxes may be obtained by condensing fatty acids derived from animal or vegetable fats with aliphatic amines or aromatic amines. Examples of synthetic waxes include fatty acid amide compounds such as hydroxy fatty acid amide compounds, palmitamide compounds, octadecylamide compounds, stearylamide compounds, eicosylamide compounds, behenylamide compounds, tetracosylamide compounds, oleamide compounds, linoleamide compounds, α-linolenamide compounds, γ-linolenamide compounds, eicosatetraenamide compounds, eicosapentaenamide compounds, and docosahexaenamide compounds.

[0629] (Method for producing amine-modified substance)

[0630] There are no limitations on the method for producing the amine-modified product, and examples thereof include: a method of synthesizing by reacting a carboxylic acid containing an R group with various amines in the presence of a condensing agent as required; a method of synthesizing by reacting an acid chloride, anhydride, isocyanate, etc. containing a carboxylic acid containing an R group with various amines, etc. The condensing agent may be a known condensing agent, and examples thereof include DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, etc.

[0631] [Amount of liquid repellent compound]

[0632] The amount of the liquid repellent compound may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more in the treatment agent. The amount of the liquid repellent compound may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less in the treatment agent.

[0633] 〔Supercritical Carbon Dioxide〕

[0634] The repellent in the present invention may contain supercritical carbon dioxide. Supercritical carbon dioxide refers to carbon dioxide at a temperature and pressure exceeding the critical temperature (31.1°C) and the critical pressure (7.38MPa). The supercritical carbon dioxide in the repellent acts as a treatment medium, and the repellent containing supercritical carbon dioxide can be used as a treatment agent for treating fiber substrates. Supercritical carbon dioxide is in a fluid state that cannot be said to belong to any state of gas phase or liquid phase. It has excellent solubility in various components and fluidity that can easily penetrate into the fine parts of fiber products. Therefore, the repellent (treatment agent) of the present invention can well impart liquid repellency to fiber products.

[0635] 〔Liquid medium〕

[0636] The dilution agent of the present invention may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. Since the dilution agent of the present invention uses supercritical carbon dioxide as a processing medium, the liquid medium in the dilution agent may be a small amount, and the dilution agent may not contain a liquid medium.

[0637] 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, solvent 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 hydroxyl group (e.g., polyols such as alcohols and glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). They may be used alone or in combination of two or more.

[0638] [Amount of liquid medium]

[0639] 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 lyophobic 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, and more preferably 10 parts by weight or less.

[0640] 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.

[0641] 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 lyophobic 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, 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, and more preferably 10 parts by weight or less.

[0642] 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.

[0643] 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 lyophobic 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, preferably 40 parts by weight or less, and more preferably 10 parts by weight or less.

[0644] 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.

[0645] 〔Surfactant〕

[0646] The expelling agent may contain a surfactant. The surfactant may contain one or more surfactants selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants. Since the expelling agent of the present invention uses supercritical carbon dioxide as a processing medium, the components can be well dispersed, so the surfactant in the expelling agent can be a small amount, and the expelling agent may not contain a surfactant.

[0647] [Nonionic surfactant]

[0648] Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0649] Examples of ethers include compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0650] Examples of esters include esters of alcohols and fatty acids. Examples of alcohols include 1-6 valent (particularly 2-5 valent) alcohols (e.g., aliphatic alcohols) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0651] Examples of ester ethers include compounds formed by the addition of alkylene oxides (especially ethylene oxide) to alcohols and fatty acids. Examples of alcohols include 1-6-valent (especially 2-5-valent) alcohols (such as aliphatic alcohols) having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms). Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0652] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolamides. Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 1 to 3 amino groups and 1 to 5 hydroxyl groups and having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0653] The polyol may be a di- to 5-valent alcohol having 10 to 30 carbon atoms.

[0654] The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example, having 5 to 50 carbon atoms).

[0655] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The carbon number of 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 usually preferably 2 to 100.

[0656] The nonionic surfactant is preferably a nonionic surfactant selected from ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides, and having an oxyalkylene group.

[0657] 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 an acetylene glycol, etc. Among these, a substance having a structure of a polyoxyethylene (POE), a polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) as the alkylene oxide adduct portion and the polyalkylene glycol portion is preferably used.

[0658] In addition, from the perspective of environmental issues (biodegradability, environmental hormones, etc.), the nonionic surfactant preferably has a structure that does not contain an aromatic group.

[0659] The nonionic surfactant may be of the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R3 The compounds shown.

[0660] [Formula R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 middle,

[0661] R 1 is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or an acyl group having 2 to 22 carbon atoms,

[0662] R 2 are each independently the same or different and is an alkylene group having 3 or more (e.g. 3 to 10) carbon atoms,

[0663] R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, and p is a number greater than or equal to 2.

[0664] q is a number greater than or equal to 0 or 1.]

[0665] R 1 The number of carbon atoms is preferably 8 to 20, particularly preferably 10 to 18. 1 Preferred specific examples include lauryl, tridecyl and oleyl.

[0666] R 2 Examples of are propylene, butylene.

[0667] In the nonionic surfactant, p may be a number greater than or equal to 3 (e.g., 5 to 200). q may be a number greater than or equal to 2 (e.g., 5 to 200). That is, -(R 2 O) q -Polyoxyalkylene chains can be formed.

[0668] The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether having a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include oxypropylene chains, oxybutylene chains, and styrene chains, among which oxypropylene chains are preferred.

[0669] Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkanes (C 12 -C 16 ) mercaptan, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 ) condensation products of amines, etc.

[0670] The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example, 30 to 75% by weight, and particularly 40 to 70% by weight, based on the total amount of the nonionic surfactant (copolymer).

[0671] The average molecular weight of the nonionic surfactant is usually 300 to 5,000, for example, 500 to 3,000.

[0672] The nonionic surfactant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly less than 5) and a compound having an HLB of 15 or more. Examples of compounds having an HLB of less than 15 include sorbitan fatty acid esters. Examples of compounds having an HLB of more than 15 include polyoxyethylene alkyl ethers. The weight ratio of the compound having an HLB of less than 15 to the compound having an HLB of more than 15 may be 90:10 to 20:80, for example 85:15 to 55:45.

[0673] The nonionic surfactant may be used alone or as a mixture of two or more.

[0674] [Cationic surfactant]

[0675] The cationic surfactant is preferably a compound having no amide group.

[0676] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an ethylene oxide addition type ammonium salt. Specific examples of cationic surfactants are not particularly limited, and include: amine salt-type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridine Salt, alkyl isoquinoline Quaternary ammonium salt surfactants such as benzalkonium chloride, benzethonium chloride, etc.

[0677] Preferred examples of cationic surfactants include compound R 21 -N + (-R 22 )(-R 23 )(-R 24 )X － .

[0678] [Where R 21 , R 22 , R 23 and R 24 is a hydrocarbon group having 1 to 40 carbon atoms,

[0679] X is an anionic group.]

[0680] R 21 , R 22, R 23 and -R 24 Specific examples of are alkyl (eg, methyl, butyl, stearyl, palmityl). Specific examples of X are halogen (eg, chlorine), acid (eg, hydrochloric acid, acetic acid).

[0681] The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (the alkyl group has 4 to 40 carbon atoms).

[0682] The cationic surfactant is preferably an ammonium salt. The cationic surfactant may be of the formula: R 1 p -N + R 2 q X － The ammonium salts shown.

[0683] [Formula R 1 p -N + R 2 q X － middle,

[0684] R 1 C12 or above (e.g. C 12 ~C 50 ) a straight-chain and / or branched aliphatic (saturated and / or unsaturated) group,

[0685] R 2 is H or a C1-4 alkyl group, benzyl, or polyoxyethylene (the number of oxyethylene groups is, for example, 1 (particularly 2, and especially 3) to 50) (particularly preferably CH3 or C2H5),

[0686] X is a halogen atom (for example), a C1-C4 fatty acid radical,

[0687] p is 1 or 2, q is 2 or 3, and p+q=4.]

[0688] R 1 The number of carbon atoms in can be 12-50, for example 12-30.

[0689] Specific examples of the cationic surfactant 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.

[0690] [Anionic surfactant]

[0691] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acylamino acid type surfactants, phosphoric acid monoester or diester type surfactants, and sulfosuccinates.

[0692] [Amphoteric surfactants]

[0693] Examples of amphoteric surfactants include alanine, imidazoline Betaines, amide betaines, betaine acetate, etc., specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline Betaine, lauryl dimethylaminoacetic acid betaine, fatty acid amide propyl dimethylaminoacetic acid betaine, etc.

[0694] The nonionic surfactant, the cationic surfactant, and the amphoteric surfactant among the surfactants may be one kind or a combination of two or more kinds.

[0695] [Amount of surfactant]

[0696] The amount of the surfactant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 parts 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 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, and more preferably 1 part by weight or less.

[0697] 〔Silicone〕

[0698] The repellent of the present invention may contain silicone (polyorganosiloxane). By containing silicone, in addition to good liquid repellency, good feel and durability can be achieved.

[0699] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane, modified silicones (amino-modified, epoxy-modified silicones, carboxyl-modified silicones, methyl hydrogen silicones, etc.). The silicone can be a silicone wax having waxy properties. These can be used alone or in combination of two or more.

[0700] 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.

[0701] [Amount of silicone]

[0702] 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, based on 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, based on 100 parts by weight of the liquid repellent compound.

[0703] 〔wax〕

[0704] The repellent of the present invention may contain wax. By containing wax, liquid repellency can be well imparted to the substrate.

[0705] 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 plant wax, and mineral wax. Paraffin wax is preferred. Specific examples of compounds constituting waxes include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontan, undecane, dotriacontan, tritriacontan, tetratriacontan, pentacontan, hexatriacontan), normal olefins (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontan, undecane, dotriacontan, tritriacontan, tetratriacontan, pentacontan, hexatriacontan). The number of carbon atoms of the compound constituting the wax is preferably 20 to 60, for example 25 to 45. The molecular weight of the wax may be 200 to 2000, for example 250 to 1500, 300 to 1000. These may be used alone or in combination of two or more.

[0706] 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, and more preferably 60° C. or higher. The melting point of the wax can be measured in accordance with JIS K2235-1991.

[0707] [Amount of wax]

[0708] The amount of the 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, based on 100 parts by weight of the liquid repellent compound. The amount of the 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, based on 100 parts by weight of the liquid repellent compound.

[0709] 〔Organic acid〕

[0710] The dispersing agent may contain an organic acid. As the organic acid, a known substance may be used. As the organic acid, carboxylic acid, sulfonic acid, sulfinic acid, etc. are preferably listed, and carboxylic acid is particularly preferred. As the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc. may be listed, and formic acid or acetic acid is particularly preferred. In the present invention, the organic acid may be used alone or in combination of two or more. For example, formic acid and acetic acid may be used in combination.

[0711] [Amount of organic acid]

[0712] The amount of the organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 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, based on 100 parts by weight of the liquid repellent compound. The amount of the 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, based on 100 parts by weight of the liquid repellent compound. The amount of the organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, and particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0713] 〔Curing agent〕

[0714] The exfoliant may contain a curing agent (an active hydrogen-reactive compound or a compound containing active hydrogen).

[0715] The curing agent (crosslinking agent) in the repellent can cure the liquid-repellent compound well. The curing agent can be an active hydrogen-reactive compound or a compound containing active hydrogen that reacts with the active hydrogen or active hydrogen-reactive group possessed by the liquid-repellent compound. Examples of active hydrogen-reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl-containing compounds, carboxyl-containing compounds and hydrazide compounds. Examples of active hydrogen-containing compounds include hydroxyl-containing compounds, amino-containing compounds and carboxyl-containing compounds, keto-containing compounds, hydrazide compounds and melamine compounds.

[0716] 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 acts as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (e.g., a blocked polyisocyanate compound). The blocked isocyanate compound is a compound that utilizes a blocking agent to block the isocyanate group of the isocyanate compound, thereby inhibiting the reaction.

[0717] 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-trimethylhexamethylene diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate. Aliphatic diisocyanates such as isocyanate methyl hexanoate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane, etc. These may be used alone or in combination of two or more.

[0718] 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.

[0719] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3-phenylenedimethyl diisocyanate or 1,4-phenylenedimethyl diisocyanate or a mixture thereof, 1,3-bis(1-isocyanate-1-methylethyl)benzene or 1,4-bis(1-isocyanate-1-methylethyl)benzene (tetramethylphenylenedimethyl diisocyanate) or a mixture thereof, and 1,3,5-triisocyanate methylbenzene. These may be used alone or in combination of two or more.

[0720] Examples of aromatic polyisocyanate groups 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'-diphenylmethane diisocyanate or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4-toluene diisocyanate or 2,6-toluene 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.

[0721] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds such as dimers, trimers, biuret, allophanate, carbodiimide, uretdione, uretimine, isocyanurate, and iminooxadiazinedione. These may be used alone or in combination of two or more.

[0722] These polyisocyanates may be used alone or in combination of two or more.

[0723] As the polyisocyanate compound, a compound in which the isocyanate group of the polyisocyanate compound is blocked by a blocking agent, i.e., a blocked polyisocyanate compound (blocked isocyanate) is preferably used. Blocked polyisocyanate compounds are preferably used because they are relatively stable in solution and can be used in the same solution as the dispersant.

[0724] The blocking agent blocks the free isocyanate group. By heating the blocked polyisocyanate compound to, for example, 100° C. or higher, for example, 130° C. or higher, the isocyanate group is regenerated and can easily react with the hydroxyl group. Examples of the blocking agent include phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, and the like. The polyisocyanate compound can be used alone or in combination of two or more.

[0725] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether, polypropylene glycol diglycidyl ether, and sorbitol polyglycidyl ether.

[0726] The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include chloromethyl polystyrene and the like.

[0727] The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid, (poly)methacrylic acid, and the like.

[0728] Specific examples of the ketone group-containing compound include (poly) diacetone acrylamide and diacetone alcohol.

[0729] Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid dihydrazide, and the like.

[0730] Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0731] [Amount of curing agent]

[0732] 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.

[0733] 〔Other ingredients〕

[0734] The repellent may contain other ingredients besides the above-mentioned ingredients. Examples of other ingredients include water-repellent and / or oil-repellent, anti-slip agents, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. They can be used alone or in combination of two or more. In addition to the above-mentioned ingredients, other ingredients include feel adjusters, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying speed adjusters, cross-linking agents, film-forming aids, volume extenders, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage preventers, anti-wrinkle agents for washing, shape retainers, drape retainers, ironing enhancers, whitening agents, whitening agents, fabric softening clay, anti-staining agents such as polyvinyl pyrrolidone, polymer dispersants, dirt stripping agents, scum dispersants, 4,4-bis(2-sulfonatostyryl)biphenyl disodium (TINOPAL produced by Ciba Specialty Chemicals) CBS-X) and the like, dye fixing agents, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, detergents, enzymes such as cellulase, amylase, protease, lipase, keratinase and the like as fiber surface modifiers, foam suppressants, silk protein powder as an additive capable of imparting the feel / function of silk such as water absorption and release, surface modified products thereof, emulsified dispersions, specifically K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (Ue Mao), SILKGEN G Soluble S (ICHIMARU PHARCOS), nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units, for example, antifouling agents such as FR627 manufactured by Huying Chemical Industry and SRC-1 manufactured by Clariant Japan, etc. These may be used alone or in combination of two or more.

[0735] [Antistatic Agent]

[0736] Examples of antistatic agents include quaternary ammonium salts, pyridine The invention can be used as cationic antistatic agents such as sulfonates, sulfates, phosphonates, phosphates, etc., which have cationic functional groups; anionic antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and their derivatives, etc.; nonionic antistatic agents such as amino alcohols and their derivatives, glycerol and their derivatives, polyethylene glycol and their derivatives, etc. It can also be an ion conductive polymer obtained by polymerizing or copolymerizing these cationic, anionic, and zwitterionic monomers with ion conductive groups. They can be used alone or in combination of two or more.

[0737] [preservative]

[0738] Preservatives are mainly used to enhance the antiseptic and bactericidal abilities and maintain the antiseptic properties during long-term storage. Examples of preservatives include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol.

[0739] [Ultraviolet light absorber]

[0740] Ultraviolet light absorbers are preparations that have the effect of protecting against ultraviolet light, and are components that absorb ultraviolet light, convert it into infrared light or visible light, and then release it. Examples of ultraviolet light absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-tert-butyl-4'-methoxybenzoylmethane.

[0741] [Antibacterial agent]

[0742] Antimicrobial agents are ingredients that inhibit bacterial proliferation on fibers and prevent the generation of odors due to microbial decomposition products. Examples of antimicrobial agents include cationic fungicides such as quaternary ammonium salts, zinc bis(2-pyridinium-1-oxide), polyhexamethylene biguanide hydrochloride, 8-hydroxyquinoline, and polylysine.

[0743] [Deodorant]

[0744] Examples of the deodorant include highly branched cyclodextrin (Cluster Dextrin), methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyl dimethylamine oxide, and aminocarboxylic acid-based metal complexes (zinc complex of trisodium methylglycine diacetate described in International Publication No. 2012 / 090580).

[0745] [Amount of other ingredients]

[0746] The amount of each or the total amount of other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, based on 100 parts by weight of the liquid repellent compound. The amount of each or the total amount of other components 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, based on 100 parts by weight of the liquid repellent compound.

[0747] <Method for producing liquid-repellent fiber>

[0748] The method for producing liquid-repellent fibers of the present invention includes a fiber treatment step of using supercritical carbon dioxide as a treatment medium and treating a fiber base material with a repellent containing a liquid-repellent compound.

[0749] The repellent (treating agent) for treating the fiber substrate contains a liquid repellent compound and supercritical carbon dioxide. Through the treatment, the liquid repellent compound as an active ingredient of the repellent penetrates into the interior of the substrate and / or adheres to the surface of the substrate.

[0750] The repellent of the present invention can also be used in combination with various additives such as water-repellent and / or oil-repellent, anti-slip agent, antistatic agent, feel adjuster, softener, antibacterial agent, flame retardant, paint fixative, anti-wrinkle agent, drying speed adjuster, cross-linking agent, film-forming aid, compatibilizer, antifreeze agent, viscosity adjuster, ultraviolet absorber, antioxidant, pH adjuster, insect repellent, defoamer, etc. as needed. As examples of various additives, they can be the same as those described in the "other ingredients" in the above-mentioned water-repellent composition. The concentration of the repellent in the treatment agent in contact with the substrate can be appropriately changed according to the purpose, and can be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0751] In the method for producing liquid-repellent fibers of the present invention, the treatment temperature in the treatment container is set to a critical temperature of carbon dioxide of 31.1°C or higher (preferably 40°C or higher), and the treatment pressure is set to a critical pressure of carbon dioxide of 7.38 MPa or higher (preferably 10 MPa or higher), supercritical carbon dioxide is used as the treatment medium, and a repellent containing a liquid-repellent compound is used to treat the fiber substrate arranged in the treatment tank.

[0752] 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. or lower. The treatment temperature also varies depending on the type of expelling agent used, the treatment conditions, the expected physical properties, and the like.

[0753] 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 also varies depending on the type of expelling agent used, the treatment conditions, the expected physical properties, etc.

[0754] 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 also varies depending on the type of the expelling agent used, the treatment conditions, the expected physical properties, etc.

[0755] 〔Fiber base material〕

[0756] Examples of fiber substrates in the present invention include natural fibers of animal and plant origin such as cotton, linen, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers, or mixed fibers thereof. Fiber products include woven fabrics, knitted fabrics, and non-woven fabrics, cloth in the form of clothing fabrics, and carpets, but fibers, yarns, and intermediate fiber products (such as cotton strips or rovings, etc.) in a state before being made into cloth may also be processed. Examples of preferred fiber substrates in the present invention include polyester or polyester blended fibers.

[0757] As fiber products, paper products can also be used. Examples of paper products include bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as wood pulp, mechanical pulp or thermomechanical pulp, old newspapers, old magazines, old corrugated paper or deinked old paper, etc., paper formed by old paper pulps, containers made of paper, and molded bodies made of paper. Specific examples of paper products include packaging paper, gypsum board base paper, coated base paper, medium-quality paper, ordinary lining paper and core, neutral pure white roll paper, neutral lining paper, rust-proof lining paper and metal-clad paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded container), etc.

[0758] 〔Pretreatment of fiber products〕

[0759] The fiber product may be pretreated before being treated with the repellent of the present invention. By pretreating the fiber product, excellent fastness can be imparted to the fiber product treated with the repellent.

[0760] Examples of pretreatment of fiber products include cationization treatment using reaction with reactive quaternary ammonium salts, anionization treatment such as sulfonation, carboxylation, and phosphorylation, acetylation treatment after anionization treatment, benzoylation, carboxymethylation, grafting treatment, tannic acid treatment, polymer coating treatment, etc.

[0761] There is no limitation on the method for pretreating fiber products, and fiber products can be pretreated by currently known methods. The pretreatment liquid can be dispersed in an organic solvent or water for dilution as needed, and attached to the surface of the fiber product by known methods such as dipping, spraying, and foaming, and then dried. The pH and temperature of the pretreatment liquid can be adjusted according to the degree of treatment required. As an example of a method for pretreating fiber products, a method for pretreating fiber products using a hydrocarbon-based water-repellent agent is described in detail.

[0762] The pretreatment method of fiber products may include providing the fiber with a selected from -SO3M 1 (Where M 1 represents a monovalent cation) represented by a monovalent group, -COOM 2 (Where M 2 represents a monovalent cation) and -O-P(O)(OX 1 )(OX 2 )(where X 1 and X 2 A step of each independently representing one or more functional groups (hereinafter also referred to as "specific functional groups") in a monovalent group represented by a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

[0763] As M 1 , H, K, Na or an ammonium ion which may have a substituent can be mentioned. 2 , H, K, Na or an ammonium ion which may have a substituent may be mentioned. 1 or X 2 When it 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.

[0764] The fiber containing the above-mentioned specific functional group (hereinafter also referred to as "functional group-containing fiber") can be prepared, for example, by the following method.

[0765] (i) The compound having the specific functional group is attached to the fiber material, wherein the compound may be attached in a state where part of the compound and part of the fiber are chemically bonded within a range where a sufficient amount of the specific functional group remains.

[0766] (ii) A fiber in which the above-mentioned specific functional group is directly introduced into a material constituting the fiber is prepared.

[0767] In the case of (i), for example, fibers containing a functional group can be obtained by a functional group introduction step of treating a fiber material with a pretreatment solution containing one or more compounds having the above-mentioned specific functional groups.

[0768] The raw materials of the fiber material are 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 fiber material may be in the form of fibers (fiber bundles, slivers, etc.), yarns, knitted fabrics (including mixed knitted fabrics), woven fabrics (including mixed woven fabrics), and nonwoven fabrics.

[0769] In the present embodiment, from the viewpoint of good water repellency of the obtained fiber product, it is preferred to use a fiber material comprising polyamide and polyester as raw materials, and it is particularly preferred to use nylons such as nylon 6 and nylon 6,6, polyethylene terephthalate (PET), polytrimethyl terephthalate, polyesters such as polylactic acid, and mixed fibers containing them.

[0770] As a having the above-mentioned -SO3M 1 As the compound, a phenolic polymer can be used. As such a phenolic polymer, for example, a polymer containing one or more compounds represented by the following general formula can be cited.

[0771]

[0772] [Wherein, X 2 Representation - SO3M 3 (Where M 3 represents a monovalent cation) or a group represented by the following general formula, wherein n is an integer of 20 to 3000.]

[0773]

[0774] [Wherein, M 4 Indicates a monovalent cation.]

[0775] As the above M 3 , H, K, Na or an ammonium ion which may have a substituent may be mentioned.

[0776] As the above M 4 , H, K, Na or an ammonium ion which may have a substituent may be mentioned.

[0777] The compound represented by the above general formula may be, for example, a formaldehyde condensate of phenolsulfonic acid or a formaldehyde condensate of sulfonated bisphenol S.

[0778] As a company with the above-mentioned 2 The compound includes polycarboxylic acid polymers.

[0779] Examples of the polycarboxylic acid polymer include polymers synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, and the like as monomers, and commercially available polymers.

[0780] As a method for producing a polycarboxylic acid polymer, for example, a method of adding a free radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt, and heating at 30 to 150° C. for 2 to 5 hours to react can be cited. At this time, an alcohol such as methanol, ethanol, isopropanol or an aqueous solvent such as acetone can be added to the aqueous solution of the above-mentioned monomer and / or its salt. As a free radical polymerization initiator, for example, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, a redox polymerization initiator of a combination of persulfate and sodium bisulfite, hydrogen peroxide, a water-soluble azo polymerization initiator, etc. can be cited. These free radical polymerization initiators can be used alone, or two or more can be used in combination. In addition, during free radical polymerization, a chain transfer agent (such as octyl thioglycolate) can also be added to adjust the degree of polymerization.

[0781] In addition to the above-mentioned monomers, copolymerizable monomers can also be used in free radical polymerization. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Acrylates and methacrylates preferably have a hydrocarbon group with 1 to 3 carbon atoms that 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 two or more thereof may be used in combination.

[0782] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by an alkali metal or 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.

[0783] The weight average molecular weight of the polycarboxylic acid polymer is preferably 1,000 to 20,000, more preferably 3,000 to 15,000, from the viewpoint of good water repellency of the obtained fiber product.

[0784] As the polycarboxylic acid-based polymer, commercially available products such as "NEOCRYSTAL 770" (trade name, manufactured by Nikka Chemical Co., Ltd.) and "Cellopole PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0785] As the above-mentioned -O-P(O)(OX 1 )(OX 2) compounds, for example, the phosphate compounds represented by the following general formula can be cited.

[0786]

[0787] [Wherein, X 1 or X 2 The meaning is the same as above, X 3 represents an alkyl group having 1 to 22 carbon atoms.]

[0788] As the phosphoric acid ester compound, phosphoric acid 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.

[0789] From the viewpoint of good water repellency of the obtained fiber product, lauryl phosphate and decyl phosphate are preferably used.

[0790] As the phosphoric acid ester compound, for example, a commercially available product such as "PHOSPHANOL ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0791] The pretreatment liquid containing one or more compounds having the above-mentioned specific functional groups can be prepared, for example, as an aqueous solution of the above-mentioned compounds. In addition, the pretreatment liquid can also contain an acid, an alkali, a surfactant, a chelating agent, and the like.

[0792] As a method for treating the fiber material with the above-mentioned pretreatment liquid, for example, filling treatment, impregnation treatment, spray treatment, and coating treatment can be listed. As a filling treatment, for example, a method using a filling device recorded in pages 396 to 397 of the Dictionary of Fiber Dyeing and Processing (published by Nikkan Kogyo Shimbun in 1975) and pages 256 to 260 of Color Dyeing Chemistry III (published by Jikyo Publishing Co., Ltd. in 1975) can be listed. As a coating treatment, for example, a method using a coating machine recorded on pages 473 to 477 of the Overview of Dyeing and Finishing Equipment (published by Textile Company in 1975) can be listed. As an immersion treatment, for example, a method using a batch dyeing machine recorded on pages 196 to 247 of the Overview of Dyeing and Finishing Equipment (published by Textile Company in 1975) can be listed, and a liquid flow dyeing machine, an air flow dyeing machine, a drum dyeing machine, a Wince dyeing machine, a washing dyeing machine, a bobbin yarn dyeing machine, etc. can be used. As spray treatment, for example, an air jet method using compressed air to blow out the treatment liquid in a mist form, or an air jet method using a hydraulic atomization method can be cited. At this time, the treatment conditions such as the concentration of the treatment liquid and the heat treatment after application can be appropriately adjusted in consideration of various conditions such as its purpose and performance. In addition, when the pretreatment liquid contains water, it is preferably dried to remove water after adhering to the fiber material. There is no particular restriction on the drying method, and it can be any method of dry heat method or wet heat method. There is no particular restriction on the drying temperature, and for example, it can be dried at room temperature to 200°C for 10 seconds to several days. If necessary, it can be heated at a temperature of 100 to 180°C for about 10 seconds to 5 minutes after drying.

[0793] Among them, when the fiber material is a dyed fiber, the treatment with the pretreatment liquid can be carried out before dyeing or in the same bath as the dyeing. However, when reducing soap washing is carried out, the compounds with the above-mentioned specific functional groups (such as phenolic polymer compounds, etc.) adsorbed in the process may fall off, so it is preferably carried out after the reducing soap washing after dyeing.

[0794] The treatment temperature during the immersion treatment can be set to 60 to 130° C. The treatment time can be set to 5 to 60 minutes.

[0795] In the step of introducing the functional group using the pretreatment liquid, the treatment is preferably performed in an amount of 1.0 to 7.0 parts by weight of the compound having the specific functional group relative to 100 parts by weight of the fiber material. Within this range, both durable water repellency and hand feel can be achieved at a high level.

[0796] The pH of the pretreatment liquid is preferably adjusted to 3 to 5. A pH adjuster such as acetic acid or malic acid can be used for pH adjustment.

[0797] In the pretreatment solution, a salt may be used in combination to make the fiber material more effectively adsorb the compound having the specific functional group by utilizing the salting-out effect. Examples of the salt that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0798] In the process of introducing the functional group using the pretreatment liquid, it is preferred to remove the compound having the above-mentioned specific functional group that has been overtreated. As a removal method, a method using water washing can be cited. By performing sufficient removal, it is possible to suppress the manifestation of water repellency in the subsequent water repellent processing from being hindered, and the texture of the obtained fiber product is good. In addition, the obtained fiber containing functional groups is preferably fully dried before contacting the hydrocarbon-based water repellent agent.

[0799] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into a material constituting the fibers include cationic dyeable polyester (CD-PET).

[0800] The surface zeta potential of the functional group-containing fiber is preferably -100 to -0.1 mV, more preferably -50 to -1 mV, from the viewpoint of good water repellency of the obtained fiber product. 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.).

[0801] Although the embodiments are described above, it should be understood that various changes may be made in the modes and details without departing from the gist and scope of the claims.

[0802] Example

[0803] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0804] <Test method>

[0805] The steps of the experiment are as follows.

[0806] [Water contact angle]

[0807] A solution of a liquid repellent compound having a solid content concentration 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 after 1 second of dropping was taken as the water contact angle of the liquid repellent compound.

[0808] [Adhesion rate]

[0809] The fiber base material is weighed before and after the treatment, the weight before the treatment is subtracted from the weight after the treatment, and the weight difference is divided by the weight before the treatment to calculate the adhesion amount.

[0810] [Water repellency]

[0811] A drop of water was added to the treated liquid-repellent fiber to determine whether the water droplet infiltrated and spread. The case where the water droplet did not infiltrate and spread was evaluated as "0", and the case where the water droplet infiltrated and spread was evaluated as "×".

[0812] <Compound 1>

[0813] Octadecyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used.

[0814] <Compound 2>

[0815] Polyglycerol fatty acid ester (TS-3S manufactured by Sakamoto Yakuin Kogyo Co., Ltd.) was used.

[0816] <Synthesis of Compound 3>

[0817] A stirring bar, 2.8 g of citric acid, and 9.5 g of dodecylamine were added to a reaction vessel equipped with a reflux cooler and a Dean-Stark, heated to 70°C, and 20 ml of toluene was added. The mixture was heated and stirred at 135°C for 64 hours. The reaction vessel was cooled to room temperature, and 20 ml of toluene was added. The mixture was washed with acetone and ethanol in sequence to obtain the compound 3 shown below.

[0818]

[0819] <Synthesis of Compound 4>

[0820] After dissolving 4.69 g of stearyl alcohol in 80.0 mL of dehydrated tetrahydrofuran, 0.69 g of sodium hydride was added and stirred at room temperature for 1 hour. After 1 hour, 1.0 g of cyanuric chloride was added and heated and stirred at an oil bath temperature of 66° C. overnight. The next morning, it was neutralized with 3N hydrochloric acid and filtered. The obtained solid was washed with water, methanol, and diethyl ether to obtain 3.32 g of compound 4 shown below.

[0821]

[0822] <Synthesis of Compound 5>

[0823] After dissolving 0.5 g of phloroglucinol in 20.0 mL of dehydrated tetrahydrofuran, 3.75 g of octadecyl isocyanate, 1.71 mL of triethylamine, and 3 drops of dibutyltin dilaurate were added in sequence, and heated and stirred at an oil bath temperature of 60° C. overnight. The next morning, the mixture was cooled and filtered. The obtained solid was washed with acetone, methanol, and dichloromethane to obtain 3.27 g of the compound 5 shown below.

[0824]

[0825] <Synthesis of Compound 6>

[0826] 0.82 g of melamine and 10 g of myristic anhydride were placed in a flask and heated and stirred at an oil bath temperature of 200° C. for 1 hour. After 1 hour, the mixture was cooled to room temperature and the obtained solid was washed with acetone and diethyl ether to obtain 4.33 g of the compound shown below.

[0827]

[0828] The water contact angles of Compounds 1 to 6 were measured.

[0829] <Example 1>

[0830] Polyethylene terephthalate cloth (weight per unit area 88g / m 2 , 70 denier, gray) cut off and measure weight (about 1g). Compound 1 is loaded on 40mg glass filter. Polyethylene terephthalate cloth and the glass filter loaded with compound 1 are contained in a 10mL processing container and installed in a supercritical carbon dioxide treatment device. Afterwards, supercritical carbon dioxide with a pressure of 25MPa is injected and treated at a temperature of 120°C for 30 minutes. After the prescribed time, supercritical carbon dioxide is discharged to obtain liquid-repellent fiber. Calculate the adhesion rate of the repellent on the cloth at this time to be 0.65 weight %.

[0831] <Example 2>

[0832] Liquid-repellent fibers were obtained in the same manner as in Example 1 except that Compound 2 was used instead of Compound 1. The attachment rate of the repellent to the cloth was calculated to be 0.87% by weight.

[0833] <Example 3>

[0834] Liquid-repellent fibers were 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 on the cloth was calculated to be 0.73% by weight.

[0835] <Example 4>

[0836] Liquid-repellent fibers were 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 on the cloth was calculated to be 0.62% by weight.

[0837] <Example 5>

[0838] Liquid-repellent fibers were 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 on the cloth was calculated to be 0.28% by weight.

[0839] <Example 6>

[0840] Liquid-repellent fibers were 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 on the cloth was calculated to be 0.27% by weight.

[0841] <Comparative Example 1>

[0842] Evaluations were conducted on untreated fiber substrates.

[0843] The fiber base materials of Examples 1 to 5 and Comparative Example 1 were evaluated for water repellency.

[0844] The test results are summarized in the following table.

[0845] Dipping agent Water contact angle / ° Adhesion rate / weight% Water repellency Example 1 Compound 1 39 0.65 〇 Example 2 Compound 2 66 0.87 〇 Example 3 Compound 3 75 0.73 〇 Example 4 Compound 4 82 0.62 〇 Example 5 Compound 5 87 0.28 〇 Example 6 Compound 6 108 0.27 〇 Comparative Example 1 - - - ×

Claims

1. A method for producing a liquid-repellent fiber, characterized in that: The invention comprises a fiber treatment process, in which supercritical carbon dioxide is used as a treatment medium and a repellent containing a liquid repellent compound is used to treat a fiber base material.

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

3. The method for producing a liquid-repellent fiber according to claim 1 or 2, wherein: The liquid repellent compound has the following formula: -X-R n The groups shown, Formula-X-R n middle, X is a valence bond or a 1+n valence group, R, when present, is independently an aliphatic hydrocarbon group or a polysiloxane group having 6 to 40 carbon atoms and optionally having a substituent, n is 1 or more and 3 or less.

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

6. The method for producing a liquid-repellent fiber according to any one of claims 3 to 5, wherein: X is -X 1 -or-X 1 -X 2 -X 1 - the group shown, Formula-X 1 -, -X 1 -X 2 -X 1 -middle, X 1 Independently at each occurrence is: Valence 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)-, -C(=O)-O-, -C(=O)-NR'-, -SO2-, -SO2NR'-, -C(OR')R'-or - a group represented by C(OR')(-)2, In the formula, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence, X 2 It is a hydrocarbon group having 1 to 40 carbon atoms.

7. The method for producing a liquid-repellent fiber according to any one of claims 1 to 6, wherein: The liquid repellent compound has a formula derived from: CH2=C(-Q)-C(=O)-X-R n The repeating unit of the compound shown, Formula CH2=C(-Q)-C(=O)-X-R n middle, Q is a hydrogen atom, a monovalent organic group or a halogen atom, X is selected from X 1 and X 2 A 1+n-valent group composed of one or more of X 1 It is composed of one or more selected from a valence bond, -O-, -C(=O)-, -S(=O)2-, -NR'-, -C(OR')R'- and -C(OR')(-)2, wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence, X 2 is a hydrocarbon group having 1 to 40 carbon atoms, R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, n is 1 to 3.

8. The method for producing a liquid-repellent fiber according to claim 7, wherein: X is the following formula: 1 -or-X 1 -X 2 -X 1 - the group shown, Formula-X 1 -, -X 1 -X 2 -X 1 -middle, X 1 Each occurrence is independently -O-, -NR'-, -C(=O)-NR'-, -NR'-C(=O)- or -NR'-C(=O)-NR'-, wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, X 2 It is a hydrocarbon group having 1 to 40 carbon atoms.

9. The method for producing a liquid-repellent fiber according to any one of claims 1 to 6, wherein: The liquid repellent compound is a base material compound modified with the following formula: -X-R n The compound of the group shown in The matrix compound is one or more selected from monosaccharides, polysaccharides, alcohols, polyols, carboxylic acids, polycarboxylic acids and their derivatives. Formula-X-R n middle, X is a valence bond or a 1+n valence group, R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, n is 1 to 3.

10. The method for producing a liquid-repellent fiber according to claim 9, wherein: The matrix compound is selected from starch, cellulose, curdlan, pullulan, carrageenan, guar gum, chitin, chitosan, locust bean gum, κ-carrageenan, ι-carrageenan, isomaltodextrin, xanthan gum, gellan gum, tamarind gum, cyclostranded starch, glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, steviol, dextrin, cyclodextrin, glycerol, polyglycerol, menthol, xylitol, sucralose, fructose, maltose, trehalose, lactoligosaccharide, 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 parent material compound is a glycerol polymer or a citric acid polymer.

12. The method for producing a liquid-repellent fiber according to any one of claims 9 to 11, wherein: The parent material compound has a hydroxyl group, The hydroxyl 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'-, In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

13. The method for producing a liquid-repellent fiber according to any one of claims 9 to 12, wherein: The parent material compound has a carboxyl group, The carboxyl 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-, In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

14. The method for producing a liquid-repellent fiber according to any one of claims 1 to 6, wherein: The liquid repellent compound is of the following formula: A(-X-R n ) m The compounds shown, Formula A(-X-R n ) m middle, A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocyclic ring which may have a substituent, X is independently a bond or a 1+n valent group at each occurrence, R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, n is independently 1 or more and 3 or less at each occurrence, m is 1 or more and 6 or less.

15. The method for producing a liquid-repellent fiber according to any one of claims 1 to 6, wherein: The liquid repellent compound is a compound of the following formula: A(-X-R n ) m The compound shown is obtained by polymerizing the substituent possessed by A, Formula A(-X-R n ) m middle, A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocyclic ring which may have a substituent, X is independently a bond or a 1+n valent group at each occurrence, R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, n is independently 1 or more and 3 or less at each occurrence, m is 1 or more and 6 or less.

16. The method for producing a liquid-repellent fiber according to claim 14 or 15, wherein: X is the following formula: 1 -or-X 1 -X 2 -X 1 - the group shown, Formula-X 1 -, -X 1 -X 2 -X 1 -middle, X 1 Independently at each occurrence is: Valence 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)-, -C(=O)-O-, -C(=O)-NR'-, -C(OR')R'-, or -C(OR')(-)2, wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence, X 2 It is a hydrocarbon group having 1 to 40 carbon atoms.

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 method for producing a liquid-repellent fiber according to any one of claims 1 to 6, wherein: The liquid repellent compound has an amine skeleton and one or more of the following formulas: -X N -R n an amine-modified product in which at least one of the aliphatic hydrocarbon-containing groups is bonded to a nitrogen atom of the amine skeleton, Formula-X N -R n middle, X N is a valence bond or a 1+n valence group, R, when present, is independently an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, n is an integer of 1 to 3.

21. The dilution agent according to claim 20, characterized in that: The amine skeleton is composed of monovalent to trivalent amino groups and chain-like saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups which may be separated by oxygen atoms and / or sulfur atoms.

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

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

24. A composition, characterized in that Containing the lyophobic compound defined in any one of claims 1 to 21 and supercritical carbon dioxide.

25. A dispensing agent, characterized in that: Containing the lyophobic compound defined in any one of claims 1 to 21 and supercritical carbon dioxide.

26. A fiber, characterized in that The fiber is treated with water repellency using a composition or a repellent containing the liquid repellent compound defined in any one of claims 1 to 21.

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