Fiber structure

Abstract

The present invention addresses the problem of providing a novel fiber structure exhibiting water repellency, or a novel water repellent agent that can be used to produce the fiber structure. The solution is a fiber structure in which a water-repellent compound having a hydrocarbon group having 6-40 carbon atoms is adhered to a fiber base material, the air permeability of the fiber structure being greater than 20 cc / cm2 / sec, and the fabric density being greater than 100 g / m2.

Description

Technical Field

[0001] The invention relates to a fiber structure, in particular to a fiber structure treated with water repellency. Background Art

[0002] Patent document 1 discloses a water repellent composition, which comprises a polyurethane resin compound, a non-fluorine water repellent compound, a surfactant, and a liquid medium. However, the air permeability and fabric density of the specific substrate used are not recorded. In addition, the permeability resistance of the treated substrate (especially the balance between water repellency and permeability resistance) is not discussed.

[0003] Prior art literature

[0004] Patent Document 1: International Publication No. 2021 / 132172 Summary of the invention

[0005] Problems to be solved by the invention

[0006] An object of the present invention is to provide a novel fiber structure showing water repellency or a novel water repellent agent that can be used to produce the fiber structure.

[0007] Technical solutions to solve problems

[0008] The present invention includes the following solutions:

[0009] [Item 1]

[0010] A fiber structure, wherein a hydrophobic compound having a hydrocarbon group having 6 or more and 40 or less carbon atoms is attached to a fiber base material, and the air permeability of the fiber structure is greater than 20 cc / cm 2 / sec, and the fabric density is greater than 100g / m 2 .

[0011] [Item 2]

[0012] The fiber structure according to item 1, wherein

[0013] The hydrophobic compound is at least one selected from acrylic polymers and isocyanate derivatives.

[0014] [Item 3]

[0015] The fiber structure according to item 2, wherein

[0016] The hydrophobic compound comprises the acrylic polymer.

[0017] The acrylic polymer has a repeating unit derived from a polycarbonyl monomer, and the repeating unit has one ethylenically unsaturated double bond and two or more carbonyl groups.

[0018] [Item 4]

[0019] The fiber structure according to item 2 or 3, wherein

[0020] The hydrophobic compound comprises the isocyanate derivative,

[0021] The isocyanate derivative has a moiety derived from a cationic active hydrogen compound.

[0022] [Item 5]

[0023] The fiber structure according to item 2 or 3, wherein

[0024] The hydrophobic compound includes the acrylic polymer and the isocyanate derivative.

[0025] [Item 6]

[0026] The fiber structure according to item 2 or 3, wherein

[0027] The hydrophobic compound includes the acrylic polymer and the isocyanate derivative having a water contact angle of 100° or more and having a moiety derived from a cationic active hydrogen compound.

[0028] [Item 7]

[0029] The fiber structure according to item 2 or 3, wherein

[0030] The weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20.

[0031] [Item 8]

[0032] The fiber structure according to item 1 or 2, wherein

[0033] The water repellency obtained by the spray test method specified in JIS L1092:2009 is above level 4, and the penetration rate obtained by the DIN53924 test method is less than 10mm / 2h.

[0034] [Item 9]

[0035] A water repellent comprising a water repellent compound having a hydrocarbon group having 6 or more and 40 or less carbon atoms, wherein:

[0036] The hydrophobic compound comprises an acrylic polymer and an isocyanate derivative,

[0037] The isocyanate derivative has a water contact angle of 100° or more and has a portion derived from a cationic active hydrogen compound.

[0038] The weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20.

[0039] [Item 10]

[0040] The water repellent according to item 9, wherein

[0041] The hydrophobic compound comprises the acrylic polymer.

[0042] The acrylic polymer has a repeating unit derived from a polycarbonyl monomer, and the repeating unit has one ethylenically unsaturated double bond and two or more carbonyl groups.

[0043] [Item 11]

[0044] A method for manufacturing a fiber structure, comprising the following steps:

[0045] The air permeability is greater than 20cc / cm 2 / sec and the fabric density is greater than 100g / m 2 The fiber base material is treated with a water-repellent agent containing a water-repellent compound having a hydrocarbon group having 10 to 40 carbon atoms.

[0046] [Item 12]

[0047] A method for manufacturing a fiber structure, comprising: 2 / sec fiber base material is treated with a water repellent, wherein:

[0048] The water repellent comprises a water repellent compound having a hydrocarbon group having 6 to 40 carbon atoms.

[0049] The hydrophobic compound comprises an acrylic polymer and an isocyanate derivative,

[0050] The isocyanate derivative has a water contact angle of 100° or more and has a portion derived from a cationic active hydrogen compound.

[0051] [Item 13]

[0052] The method for producing a fiber structure according to item 12, wherein:

[0053] The weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20.

[0054] [Item 14]

[0055] The method for producing a fiber structure according to item 12 or 13, wherein

[0056] The hydrophobic compound comprises the acrylic polymer.

[0057] The acrylic polymer has a repeating unit derived from a polycarbonyl monomer, and the repeating unit has one ethylenically unsaturated double bond and two or more carbonyl groups.

[0058] Effects of the Invention

[0059] According to the present invention, it is possible to provide a novel fiber structure showing water repellency or a novel water repellent agent that can be used for producing the fiber structure. DETAILED DESCRIPTION

[0060] <Definition of terms>

[0061] In the case of use in this specification, "n-valent group" means a group having n bonding bonds, i.e., a group forming n bonds. In addition, "n-valent organic group" means an n-valent group containing carbon. As the organic group, it is not particularly limited and can be a hydrocarbon group or a derivative thereof. The derivative of the hydrocarbon group means a group having one or more N, O, S, Si, amide group, sulfonyl group, siloxane, carbonyl group, carbonyloxy group, halogen, etc. at the end of the hydrocarbon group or in the molecular chain.

[0062] As used in this specification, "hydrocarbon group" means a group containing carbon and hydrogen, wherein a hydrogen atom is removed from a hydrocarbon. The hydrocarbon group is not particularly limited, and examples thereof include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and the like. 1-20 Hydrocarbon group. The above-mentioned "aliphatic hydrocarbon group" may be any one of linear, branched or cyclic, and may be any one of saturated or unsaturated. In addition, the hydrocarbon group may also contain one or more ring structures. The hydrocarbon group may also be substituted by one or more substituents.

[0063] In this specification, regardless of whether "independently at each occurrence", "independently of each other", "independently of each other" or similar expressions are explicitly stated, unless it is stated as an exception, when defining a term (symbol) that can appear multiple times in a chemical structure, the definition applies independently at each occurrence.

[0064] It should be understood that the chemical structures described in this specification do not include chemical structures that are considered chemically impossible or extremely unstable by those skilled in the art.

[0065] <Hydro-repellent compounds>

[0066] The hydrophobic compound in the present invention is a substance that can adhere to a substrate and impart hydrophobicity to the substrate, and may be a hydrophobic compound having a hydrocarbon group having 6 to 40 carbon atoms.

[0067] [Characteristics, etc.]

[0068] The water contact angle of the hydrophobic compound may be 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, 100° or more, 105° or more, 110° or more, or 115° or more, preferably 100° or more. The water contact angle of the hydrophobic 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. By making the hydrophobic compound have a water contact angle above the above lower limit, the substrate can be well endowed with hydrophobicity. The water contact angle refers to the static contact angle of the hydrophobic compound to the spin-coated film, which is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle after 1 second of dropping.

[0069] The hydrophobic 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. The hydrophobic compound may impart liquid repellency to the substrate even if it does not include these fluorine-containing groups.

[0070] (Hydrocarbon group having 6 or more and 40 or less carbon atoms)

[0071] The hydrophobic compound may have a hydrocarbon group, particularly a hydrocarbon group having 6 to 40 carbon atoms. The hydrocarbon group having 6 to 40 carbon atoms contributes to imparting hydrophobicity to the substrate.

[0072] The hydrocarbon group may be a monovalent hydrocarbon group. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic or straight-chain, more preferably chain-shaped, especially straight-chain.

[0073] The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, and preferably 10 or more, 12 or more, or 16 or more. The number of carbon atoms in the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and preferably 30 or less, 25 or less, or 20 or less.

[0074] As an example of a hydrophobic compound, it is not particularly limited and may be at least one selected from an acrylic polymer and an isocyanate derivative, preferably a combination of an acrylic polymer and an isocyanate derivative. The amount of the acrylic polymer may be 10% by weight or more, 30% by weight or more, 50% by weight or more, 70% by weight or more, or 90% by weight or more relative to the total of the acrylic polymer and the isocyanate derivative. The amount of the acrylic polymer may be 95% by weight or less, 75% by weight or less, 55% by weight or less, 35% by weight or less, or 15% by weight or less relative to the total of the acrylic polymer and the isocyanate derivative. The weight ratio of the acrylic polymer to the isocyanate derivative is preferably 50 / 50 to 80 / 20.

[0075] <Acrylic polymer>

[0076] In the present invention, an acrylic polymer can be used as the hydrophobic compound. The acrylic polymer has a hydrocarbon group having 6 to 40 carbon atoms.

[0077] The weight average molecular weight of the acrylic polymer may be 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more. The weight average molecular weight of the acrylic polymer may be 5000000 or less, 3000000 or less, 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 300000 or less, 100000 or less, or 5000 or less.

[0078] The water contact angle of the acrylic polymer may be 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, 100° or more, 105° or more, 110° or more, or 115° or more. The water contact angle of the acrylic polymer may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By making the acrylic polymer have a water contact angle above the above lower limit, the substrate can be well endowed with water repellency. The water contact angle refers to the static contact angle of the acrylic polymer to the spin-coated film, which is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle after 1 second of dropping.

[0079] [(a) Hydrocarbon group-containing monomer]

[0080] The acrylic polymer has a repeating unit derived from a monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms.

[0081] The hydrocarbon group possessed by the monomer (a) can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, in particular a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group is branched or straight-chain, more preferably straight-chain. The hydrocarbon group can be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms of the hydrocarbon group can be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more. The number of carbon atoms of the hydrocarbon group can be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0082] Monomer (a) may contain an amide group, a urea group or a carbamate group. The hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group or a carbamate group and a hydrocarbon monomer not having an amide group, a urea group or a carbamate group. By making monomer (a) contain these groups, the effect of the present invention can be well achieved.

[0083] The monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms is preferably a monomer represented by the following formula.

[0084] Mode:

[0085] CH2=C(-X a )-C(=O)-Y a (R a ) k

[0086] [Where R a are each independently a hydrocarbon group having 6 to 40 carbon atoms,

[0087] X a is a hydrogen atom, a monovalent organic group or a halogen atom,

[0088] Y a is a divalent to tetravalent group,

[0089] k is 1 to 3.]

[0090] X a X may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. a Examples of are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, cyano group. a Preferably, it is a hydrogen atom, a methyl group or a chlorine atom. a A hydrogen atom is particularly preferred.

[0091] Y a Y is a divalent to tetravalent group. aA divalent group is preferred.

[0092] Y a Preferably, it is a group consisting of at least one selected from a hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2- or -NH- (but not including a hydrocarbon group). Examples of hydrocarbon groups having 1 carbon atom include -CH2-, -CH= having a branched structure or -C≡ having a branched structure.

[0093] Y a Can be -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)

[0094] -Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'-.

[0095] [wherein, Y' is a valence bond, -O-, -NH- or -S(=O)2-,

[0096] R' is -(CH2) m -(m is an integer of 1 to 5) or -C6H4-(phenylene).]

[0097] Y a Specific examples are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m-NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH-[wherein, m is 1 to 5, especially 2 or 4.].

[0098] Y a Preferred are -O-, -NH-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -NH-C

[0099] (=O)-、-O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH-. [wherein, m is an integer of 1 to 5, especially 2 or 4.] Y a More preferably -O- or -O-(CH2) m -NH-C(=O)-, especially -O-(CH2) m -NH-C(=O)-.

[0100] R aPreferably, it is a straight-chain or branched hydrocarbon group. The hydrocarbon group may be a straight-chain hydrocarbon group in particular. The hydrocarbon group is preferably an aliphatic hydrocarbon group, in particular a saturated aliphatic hydrocarbon group, and more particularly an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26 or 15 to 26, in particular 18 to 22 or 17 to 22.

[0101] Examples of the monomer (a) are monomers represented by formula (a1) and formula (a2).

[0102] Formula (a1):

[0103] CH2=C(-X a1 )-C(=O)-Y a1 -R a1

[0104] [Where R a1 is a hydrocarbon group having 6 to 40 carbon atoms,

[0105] X a1 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0106] Y a1 is -O- or -NH-.]

[0107] Formula (a2):

[0108] CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n

[0109] [Where R a2 are each independently a hydrocarbon group having 6 to 40 carbon atoms,

[0110] X a2 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0111] Y a21 is -O- or -NH-,

[0112] Y a22 are each independently a valence bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH- or -CH2-,

[0113] Z is a bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,

[0114] n is 1 or 2.]

[0115] ((a1) Monomer)

[0116] The monomer (a1) is a compound represented by the following formula.

[0117] CH2=C(-X a1 )-C(=O)-Y a1 -R a1

[0118] [Where R a1 is a hydrocarbon group having 6 to 40 carbon atoms,

[0119] X a1 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0120] Y a1 is -O- or -NH-.]

[0121] Monomer (a1) is Y a1 It is a long-chain acrylate monomer of -O- or Y a1 It is a long-chain acrylamide monomer with -NH-.

[0122] R a1 Preferably, it is an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and more particularly an alkyl group. a1 In the hydrocarbon group, the number of carbon atoms is preferably 12-30, for example 16-26, particularly 18-22.

[0123] X a1 It may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. It is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0124] Preferred specific examples of the long-chain acrylic acid ester monomer include dodecyl (meth)acrylate, octadecyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, octadecyl α-chloroacrylate, eicosyl α-chloroacrylate, and behenyl α-chloroacrylate.

[0125] Preferred specific examples of the long-chain acrylamide monomer include octadecyl(meth)acrylamide, eicosyl(meth)acrylamide, and docosyl(meth)acrylamide.

[0126] ((a2) Monomer)

[0127] Monomer (a2) is a monomer different from monomer (a1). Monomer (a2) is a (meth)acrylate or (meth)acrylamide having a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-.

[0128] The monomer (a2) may be a compound represented by the following formula.

[0129] CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n

[0130] [Where R a2 are each independently a hydrocarbon group having 6 to 40 carbon atoms,

[0131] X a2 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0132] Y a21 is -O- or -NH-,

[0133] Y a22 are each independently a valence bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH- or -CH2-,

[0134] Z is a bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,

[0135] n is 1 or 2.]

[0136] Y a22 and / or Z may not be a bond. a22 and Z may not be bonds at the same time.

[0137] R a2 Preferably, it is an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and particularly preferably an alkyl group. a2 In the above, the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22 carbon atoms.

[0138] X a2 It may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. It is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0139] Y a22 Can be -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y' -, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'-.

[0140] [wherein, Y' is independently a valence bond, -O-, -NH- or -S(=O)2-,

[0141] R' is -(CH2) m -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond and having 1 to 5 carbon atoms, a branched hydrocarbon group having 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l -(l is an integer of 0 to 5 independently, -C6H4- is phenylene)]

[0142] Y a22 Specific examples are valence bonds, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-.

[0143] [In the formula, m is an integer from 1 to 5.]

[0144] Y a22 Preferred are -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-. Y a22 More preferably, it is -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O- or -NH-C(=O)-NH-. a22 It doesn't have to be a valence bond.

[0145] Z is a bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a straight chain structure or a branched structure. The number of carbon atoms of Z is preferably 2 to 4, particularly 2. Specific examples of Z are a bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH= with a branched structure, -CH2(CH-)CH2- with a branched structure, -CH2CH2CH= with a branched structure, -CH2CH2CH2CH2CH= with a branched structure, -CH2CH2(CH-)CH2- with a branched structure, and -CH2CH2CH2CH= with a branched structure. Z may not be a bond.

[0146] Monomer (a2) is preferably CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 、CH2=C(-X a2 )-C(=O)-O-(CH2) m -OC(=O)-NH-R a2 、CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-OR a2 、CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a2 [Among them, R 3 and X a2 Same meaning as above. ].

[0147] Monomer (a2) is particularly preferably CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 .

[0148] Monomer (a2) can be produced by reacting hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate, such as dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, oleyl isocyanate, behenyl isocyanate, and the like.

[0149] Alternatively, the monomer (a2) can also be produced by reacting a (meth)acrylate having an isocyanate group in a side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of the long-chain alkylamine include dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, and behenylamine. Examples of the long-chain alkyl alcohol include dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0150] Preferred examples of the monomer (a) are as follows.

[0151] Octadecyl (meth)acrylate, behenyl (meth)acrylate, octadecyl α-chloroacrylate, behenyl α-chloroacrylate;

[0152] Octadecyl (meth) acrylamide, docosyl (meth) acrylamide.

[0153]

[0154]

[0155]

[0156] [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.]

[0157] The compound of the above chemical formula is an acrylic acid compound in which the α-position is a hydrogen atom, and specific examples thereof include a methacrylic acid compound in which the α-position is a methyl group and an α-chloroacrylic acid compound in which the α-position is a chlorine atom.

[0158] The monomer (a2) is preferably an amide group-containing monomer represented by the following formula.

[0159] R a22 -C(=O)-NH-R a23 -OR a21

[0160] [Where Ra21 is an organic residue having an ethylenically unsaturated polymerizable group,

[0161] R a22 is a hydrocarbon group having 6 to 40 carbon atoms,

[0162] R a23 It is a hydrocarbon group having 1 to 5 carbon atoms.]

[0163] R a21 It is an organic residue having an ethylenically unsaturated polymerizable group and is not particularly limited as long as it has a double bond between carbon atoms. Specific examples thereof include: -C(=O)CR a211 =CH2, -CHR a211 =CH2, -CH2CHR a211 = an organic residue having an ethylenically unsaturated polymerizable group such as CH2, R a211 Examples include a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 21 In addition to the ethylenically unsaturated polymerizable group, it may have various organic groups, for example, organic groups such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. a21 Preferably -C(=O)CR a211 =CH2.

[0164] R a22 It is a hydrocarbon group having 6 to 40 carbon atoms, preferably an alkyl group, and examples thereof include a chain hydrocarbon group and a cyclic hydrocarbon group. Among them, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred. a22 The carbon number of the moiety is 6 or more and 40 or less, preferably 11-27, particularly preferably 15-23.

[0165] R a23 is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be straight-chain or branched, may have an unsaturated bond, and is preferably straight-chain. a23 The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. a23 An alkylene group is preferred.

[0166] The amide-containing monomer may be R a22 A monomer (for example, only R a22 is a compound with 17 carbon atoms) or R a22 A monomer that is a combination of multiple monomers (for example, R a22 The compound with 17 carbon atoms and R a22 A mixture of compounds having 15 carbon atoms).

[0167] An example of the amide group-containing monomer is formamide alkyl (meth)acrylate.

[0168] Specific examples of the amide group-containing monomer include: palmitamide ethyl (meth)acrylate, stearamide ethyl (meth)acrylate, behenamide ethyl (meth)acrylate, myristamide ethyl (meth)acrylate, lauramide ethyl (meth)acrylate, isostearic acid acetamide (meth)acrylate, oleic acid acetamide (meth)acrylate, tert-butylcyclohexylhexanamide ethyl (meth)acrylate, adamantanecarboxylic acid acetamide (meth)acrylate, naphthamide ethyl (meth)acrylate, anthracenecarboxamide ethyl (meth)acrylate, palmitamide propyl (meth)acrylate, stearamide propyl (meth)acrylate, palmitamide ethyl vinyl ether, stearamide ethyl vinyl ether, palmitamide ethyl allyl ether, stearamide ethyl allyl ether or a mixture thereof.

[0169] The amide-containing monomer is preferably stearamide ethyl (meth)acrylate. The amide-containing monomer can be a mixture containing stearamide ethyl (meth)acrylate. In the mixture containing stearamide ethyl (meth)acrylate, the amount of stearamide ethyl (meth)acrylate relative to the weight of the amide-containing monomer as a whole can be, for example, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more. The amount of stearamide ethyl (meth)acrylate relative to the weight of the amide-containing monomer as a whole can be 90% by weight or less, 80% by weight or less, or 70% by weight or less. The remaining monomer can be, for example, palmitamide ethyl (meth)acrylate.

[0170] In monomer (a), the amount of monomer (a2) can be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more or 80% by weight or more, preferably 30% by weight or more.

[0171] [(b) Polycarbonyl monomers]

[0172] The acrylic polymer may have a repeating unit derived from a polycarbonyl monomer (b), wherein the repeating unit has one ethylenically unsaturated double bond and has two or more carbonyl groups.

[0173] The polycarbonyl monomer (b) is represented by the following formula.

[0174] CH2=C(-X b1 )-C(=O)-Y b1 -R b1 -R b2

[0175] [Wherein,

[0176] Xb1 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0177] Y b1 is -O- or -NH-,

[0178] R b1 is a divalent hydrocarbon group having 1 to 10 carbon atoms,

[0179] R b2 is a group having more than one carbonyl group.]

[0180] X b1 It may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. It is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0181] Y b1 It is -O- or -NH-, for example, it is -O-.

[0182] R b1 It is a divalent hydrocarbon group having 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms). b1 Preferably it is an aliphatic group. b1 It may be in the form of a chain (straight chain, branched chain) or a ring, preferably in the form of a chain, particularly in the form of a straight chain. b1 It may be unsaturated or saturated, and is preferably saturated.

[0183] R b1 It is a divalent hydrocarbon group having 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms). b1 Preferably it is an aliphatic group. b1 It may be in the form of a chain (straight chain, branched chain) or a ring, preferably in the form of a chain, particularly in the form of a straight chain. b1 It may be unsaturated or saturated, and is preferably saturated.

[0184] R b2 is a group having more than one carbonyl group. b2 The number of carbonyl groups may be 1 or more, 2 or more, or 3 or more, and 4 or less, 3 or less, 2 or less, or 1, and is preferably 1 or 2. b2 The number of carbon atoms in R may be 1 to 20, and may be 1 or more, 3 or more, or 5 or more, and 20 or less, 15 or less, 10 or less, or 5 or less. b2 As a specific example, -CO-R b21 (Among them, R b21 A group represented by a monovalent hydrocarbon group having 1 to 6 carbon atoms (e.g., 1 to 4 or 1 to 2)), a group represented by -NH-CO-NH2, or a 2-(2-oxo-1-imidazolidinyl) group.

[0185] Specific examples of the monomer (b) include diacetone acrylamide, 2-methacrylate [2-(2-oxo-2-imidazolidinyl)ethyl] ester, N-[2-(2-oxoimidazolidin-3-yl)ethyl] methacrylamide, and (meth)acrylate-2-acetoacetoxyethyl ester. Among them, from the viewpoint of durable water repellency of the fiber product, diacetone acrylamide and 2-methacrylate [2-(2-oxo-2-imidazolidinyl)ethyl] ester are preferred as the component (A2).

[0186] [(c) Halogenated olefin monomers]

[0187] The acrylic polymer may have repeating units derived from a halogenated olefin monomer (c). The halogenated olefin monomer (c) may 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 (c) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin monomer are vinyl halides, such as vinyl chloride, vinyl bromide, and vinyl iodide; vinylidene halides, such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred due to its high water repellency (particularly water repellency durability). The presence of repeating units derived from the halogenated olefin monomer (c) can improve the washing durability imparted by the water repellent compound.

[0188] [(d) Cross-linking monomer]

[0189] In the acrylic polymer, the crosslinking monomer (d) has at least two reactive groups and / or ethylenically unsaturated double bonds (preferably (meth)acrylate groups), and the crosslinking monomer (e) may be a monomer that does not contain fluorine atoms. It may be a compound that does not contain fluorine atoms. The crosslinking monomer (d) may be a compound that has at least two ethylenically unsaturated double bonds (preferably (meth)acrylate groups) or a compound that has at least one ethylenically unsaturated double bond and at least one reactive group. Examples of reactive groups are hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino, carboxyl, and the like.

[0190] The crosslinkable monomer (d) may be a mono(meth)acrylate, a di(meth)acrylate, or a di(meth)acrylamide having a reactive group.

[0191] One example of the crosslinkable monomer (d) is a vinyl monomer having a reactive group.

[0192] Examples of the crosslinkable monomer (d) include, but are not limited to, 3-chloro-2-hydroxypropyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0193] [(e) Cyclic hydrocarbon group-containing monomer]

[0194] The acrylic polymer may contain a cyclic hydrocarbon group-containing monomer (e). The cyclic hydrocarbon group-containing monomer (e) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0195] The cyclic hydrocarbon group-containing monomer (e) 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.

[0196] 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 chain hydrocarbon group).

[0197] 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.

[0198] Specific examples of cyclic hydrocarbon groups include cyclohexyl, tert-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, bornyl, isobornyl, norbornyl, dicyclopentanyl, 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 which are substitutes thereof.

[0199] Specific examples of the cyclic hydrocarbon group-containing monomer (e) include: cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentane (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, tricyclopentane (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.

[0200] [(f) Monomer containing a hydrophilic group]

[0201] The acrylic polymer may contain a monomer (f) containing a hydrophilic group. The monomer (f) is a monomer having a hydrophilic group. The hydrophilic group is preferably an oxyalkylene group (the number of carbon atoms of the alkylene group is 2 to 6). In particular, an oxyethylene group. In particular, the monomer (f) is preferably an oxyalkylene (meth)acrylate, such as a polyalkylene (or monoalkylene) glycol mono (meth)acrylate and / or a polyalkylene (or monoalkylene) glycol di (meth)acrylate, or a polyalkylene (or monoalkylene) glycol mono (meth)acrylamide.

[0202] The monomer (f) is preferably an oxyalkylene (meth)acrylate represented by the following formula.

[0203] CH2=CX f C(=O)-Y f -(R f O) n -A f

[0204] [Wherein,

[0205] X f is a hydrogen atom or a methyl group,

[0206] Y f is -O- or -NH-,

[0207] R f are each independently an alkylene group having 2 to 6 carbon atoms,

[0208] A f A hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH2=CX f C(=O)-,

[0209] n is an integer from 1 to 90.]

[0210] Examples of the monomer (f) are preferably monomers represented by the following formula.

[0211] CH2=CX f C(=O)-O-(R f O) n -A fi (f1)

[0212] CH2=CX f C(=O)-O-(R f O) n -C(=O)CX f =CH2(f2)

[0213] CH2=CX f C(=O)-NH-(R f O) n -A fi (f3)

[0214] [Wherein,

[0215] X f are each independently a hydrogen atom or a methyl group,

[0216] A fi are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms,

[0217] R f are each independently an alkylene group having 2 to 6 carbon atoms,

[0218] n is an integer from 1 to 90.]

[0219] n may be, for example, 1 or more, 2 or more, or 3 or more, and may be 50 or less, 30 or less, or 15 or less. Alternatively, n may be 1, for example.

[0220] R f It can be a straight chain or branched alkylene group, for example, the formula -(CH2) x -or-(CH2) x1 -(CH(CH3)) x2 - represented by a group [wherein, x1 and x2 are 0 to 6, for example, 2 to 5, and the total of x1 and x2 is 1 to 6. -(CH2) x1 - and -(CH(CH3)) x2 -The order is not limited to the formula described, and can be random. ].

[0221] In-(R f O) n -, R may be two or more (for example, 2 to 4, especially two), -(R f O) n - can be, for example, -(R 1 O)n1 -and-(R 2 O) n2 -combination [where R 1 and R 2 are mutually different alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers greater than or equal to 1, and the total of n1 and n2 is 2 to 90. ].

[0222] R in formula (f1), (f2) and (f3) f In particular, ethylene, propylene or butylene is preferred, and butylene is particularly preferred. f It may also be a combination of two or more alkylene groups. In this case, at least one R is preferably an ethylene group, a propylene group or a butylene group. f The monomer (f) may be a mixture of two or more. In this case, in at least one monomer (f), R in formula (f1), (f2) or (f3) is f Preferably, it is ethylene, propylene or butylene. In addition, when using the polyalkylene glycol di(meth)acrylate represented by formula (f2), it is not preferred to use it alone as monomer (f), but it is preferably used in combination with monomer (f1). In this case, it is also preferred that the compound represented by formula (f2) is less than 30% by weight in the monomer (f) used.

[0223] As monomer (f), X 2 The monomer (f) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or hydroxyethyl acrylamide.

[0224] [(g) Monomers containing ion-donating groups]

[0225] The acrylic polymer may contain a monomer (g) containing an ion-donating group. The monomer (g) is preferably a monomer (particularly an acrylic monomer) containing an olefinic carbon-carbon double bond and an ion-donating group. The ion-donating group is an anion-donating group and / or a cation-donating group.

[0226] As the monomer having an anion-donating group, a monomer having a carboxyl group, a sulfonic acid group or a phosphoric acid group can be cited. Specific examples of the monomer having an anion-donating group are (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, phosphoric acid (meth) acrylate, vinylbenzenesulfonic acid, acrylamide tert-butyl sulfonic acid, etc. or their salts.

[0227] Examples of the salt providing an anion group include alkali metal salts, alkaline earth metal salts, and ammonium salts such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0228] In the monomer having a cation-donating group, an example of a cation-donating group is an amino group, preferably a tertiary amine group and a quaternary ammonium group. In the tertiary amine group, the two groups bonded to the nitrogen atom are the same or different, preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group (aryl group) having 6 to 20 carbon atoms, or an aromatic aliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as benzyl (C6H5-CH2-)). In the quaternary ammonium group, the three groups bonded to the nitrogen atom are the same or different, preferably an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group (aryl group) having 6 to 20 carbon atoms, or an aromatic aliphatic group having 7 or more and 25 or less carbon atoms (especially an aralkyl group, such as benzyl (C6H5-CH2-)). In the tertiary amine group and the quaternary ammonium group, the remaining one group bonded to the nitrogen atom may have a carbon-carbon double bond. The cation-donating group may be in the form of a salt.

[0229] The cation-donating group as a salt is a salt with an acid (organic acid or inorganic acid). Preferably, it is an organic acid, such as a carboxylic acid having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid). Preferably, dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and their salts are used.

[0230] As the monomer (c) containing an ion donating group, methacrylic acid, acrylic acid or dimethylaminoethyl methacrylate is preferred, and methacrylic acid or dimethylaminoethyl methacrylate is more preferred.

[0231] [(h) Other monomers]

[0232] Other monomers are not limited to these examples, and include acrylonitrile, (meth)acrylate containing organosiloxane, short-chain alkyl (meth)acrylate, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, vinyl alkyl ether, etc. Other monomers (h) may be used alone or in combination of two or more.

[0233] 〔Polymer composition〕

[0234] The combination of monomers (a) to (h) constituting the repeating unit of the acrylic polymer is not particularly limited. The acrylic polymer preferably contains a repeating unit derived from monomer (b) and / or a repeating unit derived from monomer (c) in addition to the repeating unit derived from monomer (a). When used for fiber products, the monomers preferably use monomer (a), monomer (d), monomer (e) and monomer (g) together.

[0235] The amount of the repeating unit derived from the monomer (a) relative to the acrylic polymer may be 1 wt % or more, 5 wt % or more, 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, or 90 wt % or more, preferably 25 wt % or more, and more preferably 50 wt % or more.

[0236] The amount of repeating units derived from monomer (a) relative to the acrylic polymer may be 95 wt % or less, 85 wt % or less, 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, 15 wt % or less, or 5 wt % or less.

[0237] The amount of repeating units derived from monomer (b) relative to the acrylic polymer may be 1 wt % or more, 5 wt % or more, 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, or 90 wt % or more.

[0238] The amount of repeating units derived from monomer (b) relative to the acrylic polymer may be 95 wt % or less, 85 wt % or less, 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, 15 wt % or less, or 5 wt % or less.

[0239] Relative to 100 parts by weight of the repeating units derived from monomer (a), the amount of repeating units derived from monomer (b) can 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, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more.

[0240] The amount of repeating units derived from monomer (b) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0241] The amount of repeating units derived from monomer (c) relative to the acrylic polymer may be 1 wt % or more, 5 wt % or more, 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, or 90 wt % or more.

[0242] The amount of repeating units derived from monomer (c) relative to the acrylic polymer may be 95 wt % or less, 85 wt % or less, 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, 15 wt % or less, or 5 wt % or less.

[0243] Relative to 100 parts by weight of the repeating units derived from monomer (a), the amount of repeating units derived from monomer (c) can 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, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more.

[0244] The amount of repeating units derived from monomer (c) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0245] The amount of the repeating units derived from the monomer (d) relative to the acrylic polymer may be 1 wt % or more, 5 wt % or more, 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, or 90 wt % or more.

[0246] The amount of repeating units derived from monomer (d) relative to the acrylic polymer may be 95 wt % or less, 85 wt % or less, 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, 15 wt % or less, or 5 wt % or less.

[0247] Relative to 100 parts by weight of the repeating units derived from monomer (a), the amount of repeating units derived from monomer (d) can 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, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more.

[0248] The amount of repeating units derived from monomer (d) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0249] The amount of repeating units derived from monomer (e) relative to the acrylic polymer may be 1 wt % or more, 5 wt % or more, 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, or 90 wt % or more.

[0250] The amount of repeating units derived from monomer (e) relative to the acrylic polymer may be 95 wt % or less, 85 wt % or less, 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, 15 wt % or less, or 5 wt % or less.

[0251] Relative to 100 parts by weight of the repeating units derived from monomer (a), the amount of repeating units derived from monomer (e) can 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, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more.

[0252] The amount of repeating units derived from monomer (e) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0253] The amount of repeating units derived from monomer (f) relative to the acrylic polymer may be 1 wt % or more, 5 wt % or more, 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, or 90 wt % or more.

[0254] The amount of repeating units derived from monomer (f) relative to the acrylic polymer may be 95 wt % or less, 85 wt % or less, 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, 15 wt % or less, or 5 wt % or less.

[0255] The amount of repeating units derived from monomer (f) 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, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0256] The amount of repeating units derived from monomer (f) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0257] The amount of the repeating units derived from the monomer (g) relative to the acrylic polymer may be 1 wt % or more, 5 wt % or more, 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, or 90 wt % or more.

[0258] The amount of repeating units derived from monomer (g) relative to the acrylic polymer may be 95 wt % or less, 85 wt % or less, 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, 15 wt % or less, or 5 wt % or less.

[0259] The amount of repeating units derived from monomer (g) 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, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0260] The amount of repeating units derived from monomer (g) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0261] The amount of repeating units derived from monomer (h) relative to the acrylic polymer may be 1 wt % or more, 5 wt % or more, 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, 70 wt % or more, 80 wt % or more, or 90 wt % or more.

[0262] The amount of repeating units derived from monomer (h) relative to the acrylic polymer may be 95 wt % or less, 85 wt % or less, 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, 15 wt % or less, or 5 wt % or less.

[0263] The amount of repeating units derived from monomer (h) relative to 100 parts by weight of the repeating units derived from monomer (a) can 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, 75 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more.

[0264] The amount of repeating units derived from monomer (h) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the repeating units derived from monomer (a).

[0265] 〔Polymerization method〕

[0266] The acrylic polymer can be produced by a known polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such a polymerization method include solution polymerization, suspension polymerization, emulsion polymerization, and polycondensation.

[0267] In the case of solution polymerization, the following method is adopted: in the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, and after nitrogen substitution, the mixture is heated and stirred at 30 to 120° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, etc. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, relative to 100 parts by weight of the monomer.

[0268] The organic solvent is a solvent that is inactive with respect to the monomers and dissolves the monomers, and may be, for example, an ester (for example, an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (for example, a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (for example, an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, 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, tetrachloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in an amount within a 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.

[0269] In the emulsion polymerization, the following method is adopted: in the presence of a polymerization initiator and an emulsifier, the monomer is emulsified in water, and after nitrogen substitution, the polymerization is carried out by stirring at a temperature of 50 to 80° C. for 1 to 20 hours. The polymerization initiator used is 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, or an oil-soluble substance such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.

[0270] In order to obtain a polymer aqueous dispersion with excellent shelf stability, it is preferred to use an emulsifying device such as a high-pressure homogenizer and an ultrasonic homogenizer that can apply strong crushing energy to form the monomer into particles in water for polymerization. In addition, as an emulsifier, various anionic, cationic or non-ionic emulsifiers can be used, and the emulsifier is used 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 miscible, it is preferred to add a solubilizing agent that makes the monomers fully miscible, such as a water-soluble organic solvent and a low molecular weight monomer. By adding a solubilizing agent, the emulsification and copolymerization properties can be improved.

[0271] As the water-soluble organic solvent, the above-mentioned organic solvent can also be used. For example, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc. can be listed. The organic solvent can be used 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 listed. The low molecular weight monomer is used 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.

[0272] During polymerization, a chain transfer agent may also be used. The molecular weight of the polymer can be changed by the amount of the chain transfer agent used. Examples of chain transfer agents include thiol-containing compounds such as dodecyl mercaptan, thiodiol, 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 is 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.

[0273] <Isocyanate derivatives>

[0274] In the present invention, an isocyanate derivative may be used as the hydrophobic compound. The isocyanate derivative has a hydrocarbon group having 6 to 40 carbon atoms.

[0275] Isocyanate derivatives are compounds obtained by the reaction of an active hydrogen compound and a raw material isocyanate, and have a portion derived from the active hydrogen-containing compound and a portion derived from the raw material isocyanate. It should be noted that isocyanate derivatives, unlike isocyanate curing agents, generally do not have an isocyanate group.

[0276] Isocyanate derivatives have -NHCO- (wherein -NHCO- is a part of a urethane group or a urea group) formed by the reaction of an active hydrogen compound and a raw material isocyanate. -NHCO- is a group formed by the reaction of an active hydrogen-containing group (typically a hydroxyl group) possessed by an active hydrogen compound and an active hydrogen-reactive group (typically an isocyanate group) possessed by a raw material isocyanate. Isocyanate derivatives are typically urethanes (particularly polyurethanes).

[0277] In the isocyanate derivatives, the hydrocarbon group having a carbon number of 6 or more and 40 or less may be a monovalent hydrocarbon group. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, in particular a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched, cyclic or linear, more preferably chain-like, in particular 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, 18 or more, 20 or more or 22 or more, preferably 10 or more, 12 or more or 16 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, 25 or less or 20 or less.

[0278] The weight average molecular weight of the isocyanate derivative may be 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more. The weight average molecular weight of the isocyanate derivative may be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 100000 or less, or 5000 or less.

[0279] The water contact angle of the isocyanate derivative can be 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, 100° or more, 105° or more, 110° or more, or 115° or more. The water contact angle of the isocyanate derivative can be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By making the isocyanate derivative have a water contact angle above the above lower limit, the substrate can be well endowed with water repellency. The water contact angle refers to the static contact angle of the isocyanate derivative to the spin-coated film, which is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle after 1 second of dropping.

[0280] 〔Active hydrogen compounds〕

[0281] The active hydrogen compound contains an active hydrogen group that reacts with an isocyanate group.

[0282] Examples of the active hydrogen group include a hydroxyl group, an amino group, and a carboxyl group, and a hydroxyl group is typical.

[0283] [(α1) Hydrocarbon alcohol]

[0284] The active hydrogen compound may be an active hydrogen compound (α1) composed of a hydrocarbon group and a hydroxyl group.

[0285] The hydrocarbon group in the active hydrogen compound (α1) is the above-mentioned hydrocarbon group having 6 to 40 carbon atoms, and the above description applies.

[0286] Furthermore, the active hydrogen compound (α1) preferably has one hydroxyl group per molecule.

[0287] Examples of active hydrogen compounds (α1) include: alcohols containing straight-chain saturated hydrocarbon groups such as n-tridecyl alcohol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, and eicosanol; alcohols containing branched saturated hydrocarbon groups such as isotetradecanol, isohexadecanol, isostearyl alcohol, and isoeicosanol; alcohols containing straight-chain unsaturated hydrocarbon groups such as tetradecanol, hexadecanol, oleyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, and octacosanol; and active hydrogen compounds containing branched unsaturated hydrocarbon groups such as phytol.

[0288] Here, an alcohol containing a linear saturated hydrocarbon group and an alcohol containing a linear unsaturated hydrocarbon group may be used in combination. When the alcohol containing a linear saturated hydrocarbon group and an alcohol containing a linear unsaturated hydrocarbon group are used in combination, the proportion of the alcohol containing a linear saturated hydrocarbon group is, for example, 40 parts by mass or more, preferably 55 parts by mass or more, more preferably 70 parts by mass or more, and for example, 90 parts by mass or less, preferably 80 parts by mass or less, relative to 100 parts by mass of the total amount of the alcohol containing a linear saturated hydrocarbon group and the alcohol containing a linear unsaturated hydrocarbon group. In addition, the proportion of the alcohol containing a linear unsaturated hydrocarbon group is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and for example, 60 parts by mass or less, preferably 45 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the total amount of the alcohol containing a linear saturated hydrocarbon group and the alcohol containing a linear unsaturated hydrocarbon group. When the blending ratio of the linear saturated hydrocarbon group-containing alcohol is not less than the above lower limit, the crystallinity of the hydrocarbon group is improved, thereby improving the water repellency of the water repellent treated material treated with the water repellent composition.

[0289] [(α2)Sugar alcohol / hydroxy acid modified form]

[0290] The active hydrogen compound may be a modified sugar alcohol / hydroxy acid (α2), which is a sugar alcohol / hydroxy acid (sugar alcohol and / or hydroxy acid) modified with a hydrocarbon group having 6 to 40 carbon atoms. The type of sugar alcohol / hydroxy acid is not particularly limited, and may be cyclic or acyclic. Examples of sugar alcohols include monosaccharides, reducing sugars, amino sugars, aldonic acids, and aldonic acid lactones, and examples of hydroxy acids include hydroxy polycarboxylic acids. Sugar alcohols / hydroxy acids may be substances existing in living organisms. Examples of sugar alcohols / hydroxy acids include compounds derived from aldoses and ketoses, such as tetrasaccharides, pentasaccharides, hexasaccharides, and heptasaccharides, but are not limited thereto. Specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, gulose, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, mannopyranose, Talopyranose, allose, pyranose, idose, pyrangulose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol, pentaerythritol, dipentaerythritol, heptyl alcohol, gluconic acid, glyceric acid, xylic acid, galactaric acid, ascorbic acid, citric acid, gluconolactone, glycerol lactone, xylonolactone, glucosamine, galactosamine or a mixture thereof. The number of carbon atoms of the sugar alcohol / hydroxy acid is 2 or more, 4 or more or 6 or more, and may be 30 or less, 20 or less or 10 or less. The average OH value of compound (α2) is greater than 0 to about 230, preferably about 10 to about 175, and most preferably about 25 to about 140.

[0291] The number of hydrocarbon groups having 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modification (α2) may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more. The number of hydrocarbon groups having 6 to 40 carbon atoms in the sugar alcohol / hydroxy acid modification (α2) may be 12 or less, 9 or less, 6 or less, or 3 or less.

[0292] In the sugar alcohol / hydroxy acid modified body (α2), at least one active hydrogen (e.g., hydrogen in an OH group or a carboxyl group) possessed by the sugar alcohol and / or the hydroxy acid can be selected from -R α2 、-C(O)R α2 、-(CH2CH2O) n (CH(CH3)CH2O) m R α2 、-(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 or a mixture thereof. α2is a hydrogen atom or a hydrocarbon group having 6 to 40 carbon atoms, each n is independently 0 to 20, each m is independently 0 to 20, and m+n is greater than 0. It should be noted that compound (α2) has at least one active hydrogen. For example, in the sugar alcohol / hydroxy acid modified form, at least one (one or more than two) of the active hydrogens of the sugar alcohol / hydroxy acid is unmodified, and the active hydrogen (e.g., -OH group) can react with the active hydrogen reactive group (especially isocyanate group) of compound (b) to form -NHCO-.

[0293] ((α21) Sorbitan modified form)

[0294] The sugar alcohol / hydroxy acid modified substance (α2) may be a sorbitan modified substance (α21) obtained by modifying sorbitan with a hydrocarbon group having 6 to 40 carbon atoms, and in particular, may be an alkyl sorbitan, or may be a sorbitan modified substance (α21) obtained by modifying sorbitan with a hydrocarbon group having 6 to 40 carbon atoms. α2 、-C(O)R α2 、-(CH2CH2O) n (CH(CH3)CH2O) m R α2 、-(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 or a mixture thereof, wherein R α2 It is a hydrocarbon group having 6 or more and 40 carbon atoms. For example, sorbitan may be replaced by -C(O)R α2 The alkyl sorbitan may be a monosubstituted, disubstituted or trisubstituted compound. The sorbitan may contain a certain amount of sorbitol, isosorbide or other intermediates or by-products. Commercially available sorbitan such as SPAN may be used as the alkyl sorbitan.

[0295] In one embodiment, at least one active hydrogen substituent may be -C(O)R α2 , R α2 The carbon number may be a linear or branched alkyl group having 6 to 40 carbon atoms, more preferably 7 to 21 carbon atoms, and most preferably 11 to 21 carbon atoms. Preferred compounds include mono-, di- and tri-substituted sorbitans derived from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and mixtures thereof. Particularly preferred compounds include mono-, di- and tri-substituted sorbitan stearates or sorbitan behenates.

[0296] In one scenario, R α2 may contain at least one unsaturated bond. As an example of such a compound (at least one active hydrogen substituent is selected from -C(O)R α2 , Rα2 contains at least one unsaturated bond), and sorbitan trioleate (i.e., wherein R α2 -C7H 14 CH=CHC8H 17 As other examples, mono-, di- and tri-substituted sorbitans derived from palmitoleic acid, linoleic acid, arachidonic acid and erucic acid may be cited, but are not limited thereto.

[0297] In one embodiment, the modified sorbitan (α21) has at least one active hydrogen substituent, and the active hydrogen substituent can be independently -(CH2CH2O) n (CH(CH3)CH2O) m R α2 or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 , m is independently 0 to 20, n is independently 0 to 20, and m+n is greater than 0. Such compounds are known as polysorbates and are sold under the trade name TWEEN. α2 It is known that commercially available polysorbates contain R 2 Various polysorbates from H (unsubstituted) to R α2 A mixture of polysorbates having a linear or branched alkyl group with 6 to 40 carbon atoms (completely substituted), and a mixture of various substitution products of these substances. Examples of the modified sorbitan (α21) include polysorbates such as polysorbate tristearate and polysorbate monostearate. As m+n is greater than 0, and R α2 Examples of modified sorbitan (α21) containing at least one unsaturated bond include polysorbate trioleate (wherein R α2 For C7H 14 CH=CHC8H 17 ), but not limited thereto, it is marketed as polysorbate 80. The modified sorbitan (α21) may contain a mixture of various compounds having active hydrogen substituents, and may also contain R α2 Compounds containing at least one unsaturated bond and R α2 A mixture of completely saturated compounds.

[0298] ((α22) Citric acid modified form)

[0299] The sugar alcohol / hydroxy acid modification (α2) may be a citric acid modification (α22) in which a hydrocarbon group having 6 or more and 40 or less carbon atoms is modified on citric acid, and in particular, may be an alkyl citrate. For example, the citric acid modification (α22) may exist as a monosubstituted, disubstituted, or trisubstituted citric acid having an alkyl group. A mixture of citric acid esters having various values ​​of active hydrogen substituents may also be used. In addition, R α2 A compound comprising a hydrocarbon group having at least one unsaturated bond and R α2 is a mixture of compounds of completely saturated hydrocarbons. The citric acid modified body (α22) may have a compound selected from -(CH2CH2O) n (CH(CH3)CH2O) m R α2 or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R α2 An active hydrogen substituent, wherein R α2 It is a hydrocarbon group having a carbon number of 6 or more and 40 or less. Examples of the modified citric acid (α22) include trialkyl citrates, but are not limited thereto.

[0300] ((α23) Pentaerythritol modified form)

[0301] The sugar alcohol / hydroxy acid modified product (α21) may be a pentaerythritol modified product (α23) in which a hydrocarbon group having 6 to 40 carbon atoms is modified on pentaerythritol, or may be a mono-, di- or tri-substituted product having a hydrocarbon group (particularly an alkyl group) having 6 to 40 carbon atoms, such as a dipentaerythritol ester. The active hydrogen substituent may include -CH2C[CH2OR α2 ]3, where R α2 is a hydrocarbon group having 6 to 40 carbon atoms. The modified pentaerythritol (α23) may contain a mixture of compounds having hydrocarbon groups having different chain lengths or R α2 Compounds containing at least one unsaturated bond and R α2 A mixture of completely saturated compounds.

[0302] [(α3) Cationic active hydrogen compound]

[0303] The active hydrogen compound may be a cationic active hydrogen compound (α3) having an active hydrogen group and a cationic group.

[0304] Furthermore, the cationic active hydrogen compound (α3) preferably has two or more hydroxyl groups per molecule.

[0305] As the cationic group, for example, a tertiary amine group can be mentioned.

[0306] That is, the cationic active hydrogen compound (α3) preferably has both two or more hydroxyl groups per molecule as active hydrogen groups and a tertiary amine group as a cationic group.

[0307] Such a cationic active hydrogen compound can impart good dispersibility to a liquid medium (eg, water), and in a fiber product (described later), can introduce a cationic group having affinity to the resin, thereby improving washing durability.

[0308] More preferably, the cationic active hydrogen compound has both two hydroxyl groups per molecule as active hydrogen groups and a tertiary amine group as a cationic group.

[0309] Examples of such cationic active hydrogen compounds include alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, and propanolamine, and trialkanolamines such as N-triethanolamine and N-triisopropanolamine. Preferably, N-methyldiethanolamine is used.

[0310] The cationic active hydrogen compound (or the portion derived from the cationic active hydrogen compound in the hydrophobic compound) may form a salt with an acid compound.

[0311] As the acid compound, for example, organic acids, inorganic acids, etc. can be cited. As the organic acid, for example, acetic acid, lactic acid, tartaric acid, malic acid, etc. can be cited, preferably acetic acid, lactic acid, and more preferably acetic acid. As the inorganic acid, for example, hydrochloric acid, sulfuric acid, phosphoric acid, etc. can be cited, preferably hydrochloric acid. As the acid compound, preferably organic acids are cited. If the acid compound contains an organic acid, the acid is volatilized by heat treatment, thereby improving the water repellency of the water repellent treated product treated with the water repellent composition. In addition, the acid is volatilized by heat treatment, thereby improving the washing durability of the fiber product from the viewpoint that the cationic group is easily adsorbed on the fiber product.

[0312] [(α4) Other active hydrogen-containing compounds]

[0313] The active hydrogen compound (α) may further contain other active hydrogen compounds (α4).

[0314] ((α41) compound)

[0315] The active hydrogen compound (α4) may be a compound (α41) represented by the following formula.

[0316] R α41 -X α41

[0317] [Where R α41 is a C1-C130 Straight or branched alkyl, hydroxyl functional C1~C 30 Straight chain or branched alkyl, hydroxyl functional straight chain or branched C1~C 30 Polyether, hydroxyl functional linear or branched polyester, hydroxyl functional linear or branched organosiloxane, thiol functional C1~C 30 Straight chain or branched alkyl, amine functional C1~C 30 Straight or branched alkyl, Y - R α411 R α412 R α413 N + -R α414 -(wherein, Y is a halide ion, such as Cl - )HOS(=O)2-R α414 - or R α411 R α412 C=N-(where R α411 , R α412 , R α413 are independently -H, C1-C6 alkyl, R α414 is a divalent alkyl group having 1 to 20 carbon atoms. ),

[0318] X α41 -OH, -C(O)OH, -SH, -NH(R'), -O-(CH2CH2O) s (CH(CH3)CH2O) t- H or -C(O)-O-(CH2CH2O) s (CH(CH3)CH2O) t- H or other isocyanate-reactive functional groups, wherein R' is -H or a monovalent organic group, s is an integer from 0 to 50, t is an integer from 0 to 50, and s+t is greater than 0.]

[0319] Compound (α41) may be a hydrophilic water-soluble material comprising at least one hydroxyl-terminated polyether, wherein X α41 -O-(CH2CH2O) s (CH(CH3)CH2O) t -H or -C(O)-O-(CH2CH2O)s(CH(CH3)CH2O) t -H. -(CH2CH2O)- represents ethylene oxide (EO), and -(CH(CH3)CH2O)- represents propylene oxide (PO). These polyethers may contain only EO groups, only PO groups, or a mixture thereof. In addition, these polyethers may also exist as a designated PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) triblock copolymer.

[0320] In one scenario, X α41 is -OH, -C(O)OH, -SH, -NH(R'), R α41 Selected from C1 to C2 optionally containing at least one unsaturated group 30 Straight or branched alkyl, hydroxyl functional C1~C 30 Straight chain or branched alkyl, hydroxyl functional straight chain or branched C1~C 30 Polyether, hydroxyl-functional linear or branched polyester, hydroxyl- or amine-functional linear or branched organosiloxane, thiol-functional C1~C 30 Straight chain or branched alkyl, amine functional C1~C 30 Straight chain or branched chain alkyl.

[0321] X α41 It may be -OH. Examples of the compound (α41) include alkanols such as propanol and butanol, and aliphatic alcohols including stearyl alcohol (R α41 is a C1-C ... 30 straight-chain or branched-chain alkyl), alkyl glycols or polyols such as ethylene glycol, propylene glycol, butylene glycol or hexanediol (R α41 For hydroxyl functional C1~C 30 Alkylene glycol ethers such as straight-chain or branched alkyl), triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or glycol ethers of a mixture having PEG, PPG or THF units (R α41 A hydroxyl-functional straight or branched C1-C 30 Polyether), polyester polyol (R α41 is a hydroxyl functional linear or branched polyester), silicone prepolymer polyol (R α41 is a hydroxyl-functional straight-chain or branched organosiloxane), N,N-dimethylaminoethanol (R α41 Amine functional C1~C 30 straight chain or branched alkyl), choline chloride or betaine HCl (R α41 Y - R α411 R α412 R α413 N + -R α414 -), butanone oxime (R α41 For R α411 R α412C=N-), but is not limited thereto. The polyether polyol may contain only EO groups, only PO groups, only THF groups, or a mixture thereof. In addition, these polyethers may exist as block copolymers of substances defined by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). The polyether diol preferably has an average molecular weight of about 200 or more, most preferably 350 to 2000.

[0322] X α41 It may be -C(O)OH. Examples of the compound (α41) include fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, or erucic acid (R α41 is a C1-C1 30 straight chain or branched chain alkyl), hydroxy caprylic acid, hydroxy capric acid, hydroxy lauric acid, hydroxy myristic acid, hydroxy palmitic acid, hydroxy stearic acid, hydroxy arachidic acid, hydroxy behenic acid, hydroxy lignoceric acid, hydroxy palmitoleic acid, hydroxy linoleic acid, hydroxy arachidonic acid, hydroxy oleic acid or hydroxy erucic acid (R α41 For hydroxyl functional C1~C 30 straight-chain or branched alkyl), and mercaptoalkanoic acid such as mercaptopropionic acid (R α41 Thiol functional groups C1 to C 30 Straight chain or branched chain alkyl), but not limited thereto.

[0323] X α41 It may be -SH. Examples of the compound (α41) include alkyl mercaptan (R) such as lauryl mercaptan and dodecyl mercaptan. α41 is a C1-C ... 30 Straight chain or branched chain alkyl), but not limited thereto.

[0324] X α41 It may be -NH(R'). Examples of the compound (α41) include alkylamines such as diisopropylamine, propylamine, hexylamine, and dodecylamine (R'). α41 is a C1-C ... 30 Straight-chain or branched alkyl), ethanolamine or propanolamine and other alkanolamines (R α41 For hydroxyl functional C1~C 30 Straight chain or branched alkyl), silicone prepolymer polyamine (R α41 is an amine-functional straight-chain or branched organosiloxane), an alkyl diamine (R α41 Amine functional C1~C 30 straight chain or branched alkyl), and aminoalkanesulfonic acid such as 2-aminoethanesulfonic acid (R α41for HO-S(O)2R α414 -), but is not limited to this.

[0325] ((α42) compound)

[0326] The compound (α42) is represented by the following formula.

[0327] R α421 -(OCH2CH(OR α422 )CH2) z -OR α423

[0328] [Wherein,

[0329] In R α421 , R α422 and R α423 At least one R α421 , R α422 or R α423 is -H, and each independently is -H, -R α424 、-C(O)R α424 , R α424 is independently a linear or branched alkyl group having 5 to 29 carbon atoms, optionally containing at least one unsaturated bond, and z is 1 to 15.]

[0330] Compound (α42) may be a compound generally referred to as polyglycerol. Other specific examples include, but are not limited to, triglyceryl monostearate, triglyceryl distearate, hexaglyceryl monostearate, hexaglyceryl distearate, decaglycerol mono(caprylate / caprate), decaglycerol di(caprylate / caprate), decaglycerol, polyglyceryl-3, and C18 diglycerol.

[0331] ((α43) Chain Extender)

[0332] The compound (α4) may be a chain extender (α43). The chain extender (α43) is a compound having two or more (eg, two) functional groups containing active hydrogen in the molecule. As the chain extender, a known chain extender can be used, and examples thereof include: aliphatic or aromatic diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, and cyclohexanedimethanol; aliphatic or aromatic diamines or polyamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, and diethyltoluenediamine; phenolic hydroxyl-containing compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbisphenol, and o,o'-diallyl-bisphenol A; and alcoholamines such as aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, and aminohexylpropanolamine.

[0333] 〔Raw material: isocyanate〕

[0334] The fluorine-containing compound has a moiety derived from the raw material isocyanate.

[0335] Examples of the raw material isocyanate include:

[0336] Aromatic polyisocyanate, which is selected from toluene diisocyanate (2,4- or 2,6-toluene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-phenylene diisocyanate, p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4' or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-tolidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylene diisocyanate (1,3- or 1,4-xylene diisocyanate or a mixture thereof) (XDI), tetramethylphenylene diisocyanate Methyl diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate;

[0337] a non-cyclic aliphatic polyisocyanate selected from trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyldecanoate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate;

[0338] Cyclic alicyclic polyisocyanate, selected from 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene bis (cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-methylene bis (cyclohexyl isocyanate or mixtures thereof ) (hydrogenated MDI), methyl cyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate methyl)cyclohexane (1,3- or 1,4-bis(isocyanate methyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, trans-cyclohexane 1,4-diisocyanate, hydrogenated toluene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI);

[0339] A bridged alicyclic polyisocyanate selected from norbornene diisocyanate, norbornene diisocyanate methyl ester, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl) tricyclodecane;

[0340] Selected from

[0341]

[0342] Compounds of

[0343] and the above-mentioned isocyanates, biuret-modified products, polymers of polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (e.g., allophanate derivatives obtained by reaction of the above-mentioned polyisocyanates with monohydric alcohols or dihydric alcohols, etc.), polyol derivatives (e.g., polyol derivatives (alcohol adducts, preferably trihydric alcohols) obtained by reaction of the above-mentioned polyisocyanates with trihydric alcohols (e.g., trimethylolpropane, etc.), methyl propane adducts) etc.), biuret derivatives (for example, biuret derivatives generated by the reaction of the above-mentioned polyisocyanates with water or amines, etc.), urea derivatives (for example, urea derivatives generated by the reaction of the above-mentioned polyisocyanates with diamines, etc.), oxadiazinetrione derivatives (for example, oxadiazinetrione generated by the reaction of the above-mentioned polyisocyanates with carbon dioxide, etc.), carbodiimide derivatives (carbodiimide derivatives generated by the decarboxylation condensation reaction of the above-mentioned polyisocyanates, etc.), uretdione derivatives, uretonimine derivatives, etc.

[0344] The average number of isocyanate groups of the raw material isocyanate is 2 or more, preferably 2.5, more preferably 2.9, and, for example, 3.8 or less. The raw material isocyanate may be a polyisocyanate having a plurality of isocyanate groups.

[0345] [Synthesis method of isocyanate derivatives]

[0346] Moreover, in order to obtain an isocyanate derivative, an active hydrogen compound and a raw material isocyanate are reacted. The reaction can be completed in one step or carried out in sequence in multiple steps. For example, when there are unreacted active hydrogen groups or active hydrogen reactive groups in the product, the synthesis can be carried out in sequence. Sequential reactions are particularly useful for the use of substituted sugar alcohols with a high OH number. Reaction conditions such as reaction concentration and reaction temperature are not particularly limited and can be determined by those skilled in the art. Specifically, the active hydrogen compound and the raw material isocyanate can be coordinated in a manner such that the equivalent ratio of the active hydrogen reactive group (isocyanate group) to the active hydrogen group (active hydrogen reactive group / active hydrogen group) reaches, for example, 1.2 or more, preferably 1.5 or more, and reaches, for example, 2.0 or less.

[0347] [Composition of fluorine-containing compounds]

[0348] The amount of the portion derived from the compound (α) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more relative to the isocyanate derivative.

[0349] The amount of the portion derived from the monomer (α) may be 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, or 15 wt % or less relative to the isocyanate derivative.

[0350] The amount of the portion derived from the hydrocarbon alcohol (α1) relative to the portion derived from the active hydrogen compound may be 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, or 70 wt % or more.

[0351] The amount of the portion derived from the hydrocarbon alcohol (α1) relative to the portion derived from the active hydrogen compound may be 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, or 15 wt % or less.

[0352] The amount of the portion derived from the sugar alcohol / hydroxy acid modified body (α2) relative to the portion derived from the active hydrogen compound may be 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, or 70 wt % or more.

[0353] The amount of the portion derived from the sugar alcohol / hydroxy acid modification relative to the portion derived from the active hydrogen compound may be 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, or 15 wt % or less.

[0354] The amount of the portion derived from the cationic active hydrogen compound (α3) relative to the portion derived from the active hydrogen compound may be 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, or 70 wt % or more.

[0355] The amount of the portion derived from the cationic active hydrogen compound (α3) relative to the portion derived from the active hydrogen compound may be 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, or 15 wt % or less.

[0356] The amount of the portion derived from other active hydrogen-containing compounds (α4) relative to the portion derived from other active hydrogen-containing compounds (α4) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more.

[0357] The amount of the portion derived from other active hydrogen-containing compound (α4) relative to the portion derived from the active hydrogen compound may be 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, or 15 wt % or less.

[0358] The amount of the portion derived from the raw material isocyanate relative to the isocyanate derivative may be 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, 60 wt % or more, or 70 wt % or more.

[0359] The amount of the portion derived from the raw material isocyanate relative to the isocyanate derivative may be 75 wt % or less, 65 wt % or less, 55 wt % or less, 45 wt % or less, 35 wt % or less, 25 wt % or less, or 15 wt % or less.

[0360] <Water repellent>

[0361] The water repellent in the present invention is used to impart water repellency to a substrate (eg, a fiber substrate). The water repellent in the present invention can impart good water repellency and / or permeation resistance to the substrate, for example, can impart good water repellency and permeation resistance to the substrate.

[0362] The water repellent of the present invention comprises the above-mentioned water repellent compound. As an example of the water repellent, the following water repellents can be cited:

[0363] A water repellent comprising a water repellent compound having a hydrocarbon group having 10 or more and 40 or less carbon atoms,

[0364] The hydrophobic compound comprises an acrylic polymer and an isocyanate derivative,

[0365] The isocyanate derivative has a water contact angle of 100° or more and has a portion derived from a cationic active hydrogen compound.

[0366] The weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20.

[0367] The water-repellent compound may be used as a water-repellent by itself or in combination with other components as described below.

[0368] The water repellent in the present invention may not contain any one selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The water repellent in the present invention can impart water repellency to the substrate even if it does not contain these fluorine compounds.

[0369] 〔Dispersant〕

[0370] The water repellent of the present invention may contain a dispersant.

[0371] The dispersant is selected from organic dispersants and inorganic dispersants. It can be at least one. The dispersant can be non-anionic, or at least one selected from nonionic dispersants, cationic dispersants, amphoteric dispersants and inorganic dispersants.

[0372] As the dispersant, an organic dispersant and an inorganic dispersant may be used separately or in combination.

[0373] As the dispersant, an organic dispersant may also be used. The organic dispersant may be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants, and the organic dispersant may refer to a surfactant.

[0374] The dispersant may also be a fluorine-free dispersant.

[0375] [Nonionic dispersant]

[0376] The dispersant may also include a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0377] The nonionic dispersant may be a low molecular weight type or a high molecular weight type. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0378] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0379] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0380] 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 1-50 carbon atoms (particularly 10-30 carbon atoms). Examples of fatty acids include saturated or unsaturated fatty acids having 2-50 carbon atoms, particularly 5-30 carbon atoms.

[0381] Examples of ester ethers are compounds obtained by adding alkylene oxide (especially ethylene oxide) to esters of alcohols and fatty acids. Examples of alcohols are 1-6-valent (especially 2-5-valent) alcohols (for example, aliphatic alcohols) having 1-50 carbon atoms (especially 3-30 carbon atoms). Examples of fatty acids are saturated or unsaturated fatty acids having 2-50 carbon atoms, especially 5-30 carbon atoms.

[0382] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolamides. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0383] The polyol may be a di- to 5-valent alcohol having 10 to 30 carbon atoms.

[0384] The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example, having 5 to 50 carbon atoms).

[0385] The nonionic dispersant is preferably a nonionic dispersant 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 dispersant is usually preferably 2 to 100.

[0386] The nonionic dispersant is selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0387] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, and the like. Among them, those having the structures of the alkylene oxide addition part and the polyalkylene glycol part being polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred.

[0388] In addition, the nonionic dispersant does not necessarily have to contain an aromatic group.

[0389] The nonionic dispersant may be a compound represented by the following formula.

[0390] R 1 O-(CH2CH2O) p -(R 2 O) q -R 3

[0391] [Where R 1 is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group,

[0392] R 2 are independently the same or different, and are alkylene groups having 3 or more (e.g., 3 to 10) carbon atoms,

[0393] 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.

[0394] q is a number greater than or equal to 0 or 1.]

[0395] R 1 The number of carbon atoms is preferably 8 to 20, particularly preferably 10 to 18. 1 Preferred specific examples include dodecyl, tridecyl and oleyl.

[0396] R 2 Examples of are propylene, butylene.

[0397] In the nonionic dispersant, 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 may also be formed.

[0398] The nonionic dispersant may be a polyoxyethylene alkylene ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include oxypropylene chains, oxybutylene chains, and styrene chains, among which oxypropylene chains are preferred.

[0399] Specific examples of nonionic dispersants 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, sorbitan fatty acid esters, glycerol fatty acid esters, polyglycerol fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc.

[0400] 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, relative to the molecular weight of the nonionic dispersant (copolymer).

[0401] The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example 500 to 3,000.

[0402] The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more.

[0403] [Cationic dispersant]

[0404] The dispersant may also include a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10000 or less), or a high molecular weight type (e.g., a molecular weight of 2000 or more). The cationic dispersant may also be a compound without an amide group.

[0405] The cationic dispersant may be a low molecular weight type or a high molecular weight type. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0406] The cationic dispersant may be an amine salt, a quaternary ammonium salt, or an ethylene oxide addition type ammonium salt. Specific examples of the cationic dispersant are not particularly limited, and include amine salt dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, benzethonium chloride, and other quaternary ammonium salt dispersants.

[0407] Preferred examples of the cationic dispersant are compounds represented by the following formula.

[0408] R 21 -N + (-R 22 )(-R23 )(-R 24 )X -

[0409] [Where R 21 , R 22 , R 23 and R 24 is a hydrocarbon group having 1 to 40 carbon atoms,

[0410] X is an anionic group.]

[0411] R 21 , R 22 , R 23 and -R 24 Specific examples of are alkyl groups (eg, methyl, butyl, stearyl, palmityl). Specific examples of X are halogens (eg, chlorine), acids (eg, hydrochloric acid, acetic acid).

[0412] The cationic dispersant is particularly preferably a monoalkyltrimethylammonium salt (the alkyl group has 4 to 40 carbon atoms).

[0413] The cationic dispersant is preferably an ammonium salt. The cationic dispersant may be an ammonium salt represented by the following formula.

[0414] R 1 p -N + R 2 q X -

[0415] [Where R 1 C12 or above (e.g. C 12 ~C 50 ) a straight-chain and / or branched aliphatic (saturated and / or unsaturated) group,

[0416] R 2 H or C1-4 alkyl, benzyl, polyoxyethylene (the number of oxyethylene groups is, for example, 1 (especially 2, more especially 3) to 50)

[0417] (CH3 and C2H5 are particularly preferred),

[0418] X is a halogen atom (for example), a C1-C4 fatty acid salt group,

[0419] p is 1 or 2, q is 2 or 3, p+q=4.]

[0420] R 1 The number of carbon atoms in may be 12-50, for example 12-30.

[0421] Specific examples of the cationic dispersant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydrogen polyoxyethylene)ammonium chloride, benzyldodecyldi(hydrogen polyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0422] [Anionic dispersant]

[0423] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0424] The anionic dispersant may be a low molecular weight type or a high molecular weight type. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0425] Examples of anionic dispersants 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-sulfo fatty acid salts, N-acylamino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinates.

[0426] [Amphoteric dispersants]

[0427] The dispersant may also include an amphoteric dispersant. The amphoteric dispersant may also be an amphoteric surfactant.

[0428] The amphoteric dispersant may be a low molecular weight type or a high molecular weight type. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 25000 or less, 750 or less, or 250 or less.

[0429] Examples of the amphoteric dispersant include alanine, imidazoline betaines, amide betaines, betaine acetate, and the like. Specifically, dodecyl betaine, octadecyl betaine, dodecylcarboxymethyl hydroxyethyl imidazoline betaine, dodecyldimethylaminoacetic acid betaine, and fatty acid amide propyl dimethylaminoacetic acid betaine, and the like.

[0430] [Inorganic dispersants]

[0431] The dispersant may also contain an inorganic dispersant.

[0432] The average primary particle size of the inorganic dispersant can be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more. The average primary particle size of the inorganic dispersant can be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured by observation using, for example, a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant can also be a hydrophilic particle.

[0433] Examples of inorganic dispersants include: polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0434] [Reactive emulsifier]

[0435] The dispersant may include a reactive emulsifier. When a hydrophobic compound (eg, a synthetic acrylic polymer) is prepared in the presence of a reactive emulsifier, the hydrophobic compound may form a polymer including a structural unit derived from the reactive emulsifier.

[0436] As long as the water-repellent compound is a polymer containing a structural unit derived from a reactive emulsifier, the product stability of the aqueous dispersion (water-repellent composition) can be improved without reducing the water repellency.

[0437] The reactive emulsifier is an emulsifying dispersant having free radical reactivity, that is, an emulsifier having one or more polymerizable unsaturated groups in the molecule, and is an emulsifier copolymerizable with the above-mentioned monomer component.

[0438] As the reactive emulsifier, for example, the reactive emulsifier of JP-A-2017-25440 can be mentioned. By using a reactive emulsifier, the product stability of the aqueous dispersion (water repellent) can be improved without reducing the water repellency.

[0439] [Amount of dispersant]

[0440] The amount of the dispersant 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, 75 parts by weight or more, or 100 parts by weight or more relative to 100 parts by weight of the hydrophobic compound. The amount of the dispersant may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less relative to 100 parts by weight of the hydrophobic compound.

[0441] 〔Liquid medium〕

[0442] The water repellent in 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. The water repellent may be a dispersion or a solution. The water repellent in the present invention may be a water-dispersible type and may contain at least water.

[0443] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may also include a compound having at least one hydroxyl group (e.g., polyols such as alcohols and glycol solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination of two or more.

[0444] [Amount of liquid medium]

[0445] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more relative to 1 part by weight of the hydrophobic compound. The amount of the liquid medium may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less relative to 1 part by weight of the hydrophobic compound.

[0446] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more relative to 1 part by weight of the hydrophobic compound. The amount of water may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less relative to 1 part by weight of the hydrophobic compound.

[0447] 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, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more relative to 1 part by weight of the hydrophobic compound. The amount of the organic solvent may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less relative to 1 part by weight of the hydrophobic compound.

[0448] 〔Organic Silicone〕

[0449] The water repellent in the present invention may also contain organosilicon (polyorganosiloxane). By containing organosilicon, in addition to good water repellency, good feel and durability can also be achieved. The preparation of the water repellent compound can be carried out in the presence of organosilicon (for example, polymerization of monomers), or organosilicon can be added to the water repellent compound.

[0450] As the organosilicon, known organosilicon can be used, and examples of organosilicon include: polydimethylsiloxane, modified organosilicon (amino-modified, epoxy-modified organosilicon, carboxyl-modified organosilicon, methyl hydrogen-containing organosilicon, etc.). The organosilicon may also be a waxy organosilicon wax. These may be used alone or in combination of two or more.

[0451] The weight average molecular weight of the organosilicon may be 1000 or more, 10000 or more, or 50000 or more. The weight average molecular weight of the organosilicon may be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

[0452] [Amount of silicone]

[0453] The amount of the organosilicon may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more relative to 100 parts by weight of the hydrophobic compound. The amount of the organosilicon may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less relative to 100 parts by weight of the hydrophobic compound.

[0454] 〔wax〕

[0455] The water repellent in the present invention may contain wax. By containing wax, water repellency can be imparted to the substrate well.

[0456] 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 are n-alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontan, triundecane, dotacosane, tritacosane, tetratacosane, pentacontan, hexatacosane), n-olefins (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosene, triacontan, triundecane, dotacosane, tritacosane, tetratacosane, pentacontan, hexatacosene). The number of carbon atoms in the compounds constituting waxes 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.

[0457] The melting point of the wax may be 40° C. or higher, 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 is measured in accordance with JIS K 2235-1991.

[0458] [Amount of wax]

[0459] 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, 75 parts by weight or more, or 100 parts by weight or more relative to 100 parts by weight of the hydrophobic 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, 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 hydrophobic compound.

[0460] 〔Organic acid〕

[0461] The water repellent of the present invention may also contain an organic acid. As the organic acid, a known substance can be used. As the organic acid, preferably carboxylic acid, sulfonic acid, sulfinic acid, etc. can be mentioned, 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. can be mentioned, and formic acid or acetic acid is particularly preferred. In the present invention, the organic acid can be used alone or in combination of two or more. For example, formic acid and acetic acid can also be used in combination.

[0462] [Amount of organic acid]

[0463] 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, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the water-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, 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 water-repellent compound. The amount of the organic acid may also be adjusted so that the pH of the water-repellent agent is 3 to 10, for example, 5 to 9, and particularly 6 to 8. The water-repellent agent may also be acidic (pH 7 or less, for example, 6 or less).

[0464] 〔Curing agent〕

[0465] The water repellent of the present invention may contain a curing agent (active hydrogen reactive compound or active hydrogen-containing compound).

[0466] The curing agent (crosslinking agent) in the water repellent can cure the water repellent compound well. The curing agent can be an active hydrogen reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen reactive group possessed by the water repellent compound. Examples of active hydrogen reactive compounds are isocyanate compounds, epoxy compounds, chloromethyl-containing compounds, carboxyl-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds are hydroxyl-containing compounds, amino-containing compounds, carboxyl-containing compounds, keto-containing compounds, hydrazide compounds, and melamine compounds.

[0467] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound is used 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 in which the isocyanate group of the isocyanate compound is shielded with a blocking agent to inhibit the reaction.

[0468] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates of methyl 2,6-diisocyanatohexanoate, and lysine ester triisocyanates, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, and the like. These may be used alone or in combination of two or more.

[0469] 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.

[0470] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0471] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-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.

[0472] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biuret, allophanate, carbodiimide, uretdione, uretonimine, isocyanurate, and iminooxadiazinedione. These may be used alone or in combination of two or more.

[0473] The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is shielded by a blocking agent and the reaction is inhibited. Among them, the isocyanate compound can include, for example, the above-mentioned polyisocyanate compound, as an example, can include: 4,4'-diisocyanatophenylmethane, toluene diisocyanate, hexamethylene diisocyanate, trimer of diisocyanate and trimethylolpropane adduct, etc. The blocking agent can be a known blocking agent, and can include, for example: alcohols (for example, secondary or tertiary alcohols), active methylene compounds, phenols, oximes, substituted pyrazoles, amine compounds, phenol compounds, lactams, etc. The blocked isocyanate compound can be obtained by reacting the isocyanate compound with the blocking agent using a known method. After the reaction, a surfactant can be used to emulsify and disperse it by a known method. For example, after blocking 70 to 95% of all isocyanate groups of the isocyanate compound, an emulsifier (e.g., polyalkylene glycol, particularly polyethylene glycol) is allowed to react with the remaining isocyanate groups, thereby improving the self-dispersibility of the blocked isocyanate compound. By using the blocked isocyanate compound, the washing durability of the water repellent can be improved, the product stability can be improved, and the like.

[0474] These polyisocyanates can be used alone or in combination of two or more.

[0475] As the polyisocyanate compound, it is preferred to use 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). The blocked polyisocyanate compound is also relatively stable in solution and can be used in the same solution as the water repellent. For these reasons, it is preferred to use a blocked polyisocyanate compound.

[0476] The blocking agent is used to block the free isocyanate group. The blocked polyisocyanate compound can regenerate the isocyanate group by heating to 100° C. or higher, for example, 130° C. or higher, and then easily react with the hydroxyl group. Examples of the blocking agent are phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compound can be used alone or in combination of two or more.

[0477] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound are epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether.

[0478] 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.

[0479] 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.

[0480] Specific examples of the ketone group-containing compound include (poly) diacetone acrylamide, diacetone alcohol, and the like.

[0481] Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic dihydrazide and the like.

[0482] Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0483] [Amount of curing agent]

[0484] 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, 75 parts by weight or more, or 100 parts by weight or more relative to 100 parts by weight of the hydrophobic 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, 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 hydrophobic compound.

[0485] 〔Other ingredients〕

[0486] The water repellent may contain other ingredients in addition to the above ingredients. Examples of other ingredients include: adhesive resin, anti-slip agent, sizing agent, paper strength enhancer, PVA, penetrant, organic acid, pigment, filler, antistatic agent, preservative, ultraviolet absorber, antibacterial agent, deodorant, fragrance, polysaccharide, paper enhancer, coagulant, yield enhancer, coagulant, etc. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components may be added: other water-repellent and / or oil-repellent agents (for example, dendrimer-based water-repellents (ECO PLUS (manufactured by Rudolph)), dispersants, texture regulators, softeners, flame retardants, paint fixatives, anti-wrinkle agents, drying speed regulators, crosslinking agents, film-forming aids, solubilizers, antifreeze agents, viscosity regulators, ultraviolet absorbers, antioxidants, pH regulators, insect repellents, defoamers, anti-shrinkage agents, clothing anti-wrinkle agents, shape retaining agents, drape retaining agents, ironing property improvers, whitening agents, bleaching agents, fabric softening clay, dye transfer inhibitors such as polyvinyl pyrrolidone, polymer dispersants, stain removers, scum dispersants, 4,4-bis(2-sulfostyryl)biphenyl disodium (TINOPAL manufactured by CIBA SPECIALTY CHEMICALS) CBS-X), dye fixing agent, anti-fading agent such as 1,4-bis(3-aminopropyl)piperazine, detergent, cellulase, amylase, protease, lipase, keratinase and other enzymes as fiber surface modifiers, defoamer, silk protein powder that can give silk feel and functions such as moisture absorption and release, their surface modified products or emulsified dispersions (such as K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (upper hair), SILKGEN G Soluble S (ICHIMARU PHARCOS)), antifouling agent (such as non-ionic polymer compound composed of alkylene terephthalate and / or alkylene isophthalate unit and polyoxyalkylene unit (such as FR627 manufactured by Huying Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan Co., Ltd., etc.). These can be used alone or in combination of two or more.

[0487] [Antistatic Agent]

[0488] Examples of antistatic agents include: quaternary ammonium salts, pyridinium salts, cationic antistatic agents with cationic functional groups such as primary amino groups, secondary amino groups, and tertiary amino groups; anionic antistatic agents with anionic functional groups such as sulfonates and sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and their derivatives, nonionic antistatic agents such as amino alcohols and their derivatives, glycerol and their derivatives, polyethylene glycol and their derivatives, etc. It can be an ion conductive polymer obtained by polymerization or copolymerization of monomers having these cationic, anionic, and zwitterionic ion conductive groups. These can be used alone, and two or more can also be used in combination.

[0489] [preservative]

[0490] Preservatives are mainly used to enhance the antiseptic and bactericidal properties and to 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.

[0491] [Ultraviolet light absorber]

[0492] The ultraviolet absorber is a drug having an ultraviolet protection effect, and is a component that absorbs ultraviolet rays and converts them into infrared rays or visible light, etc. Examples of the ultraviolet absorber include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-tert-butyl-4'-methoxybenzoylmethane.

[0493] [Antibacterial agent]

[0494] The antimicrobial agent is a component that has the effect of inhibiting the proliferation of bacteria on the fiber, thereby inhibiting the generation of unpleasant odors caused by microbial degradation products. Examples of the antimicrobial agent include cationic fungicides such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanide hydrochloride, 8-oxoquinoline, polylysine, and the like.

[0495] [Deodorant]

[0496] Examples of the deodorant include clustered dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyl dimethylamine oxide, and aminocarboxylic acid metal complexes (zinc complex of trisodium methylglycine diacetate described in International Publication No. 2012 / 090580).

[0497] [Amount of other ingredients]

[0498] The amount of each or the total amount of other components relative to 100 parts by weight of the hydrophobic compound may be 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, 75 parts by weight or more, or 100 parts by weight or more. The amount of each or the total amount of other components relative to 100 parts by weight of the hydrophobic compound may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0499] <Fiber structure and method for producing the same>

[0500] The fiber structure in the present invention is a treated fiber product obtained by treating a fiber substrate with a water repellent. The method for manufacturing the fiber structure includes a treatment step, that is, treating the substrate with the above-mentioned water repellent so that the water repellent compound as an active ingredient of the water repellent is attached to the fiber substrate. "Treatment" means applying the water repellent to the substrate by impregnation, spraying, coating, etc. The water repellent compound as an active ingredient of the water repellent is attached to the inside and / or surface of the substrate by treatment. Here, attachment can be physical attachment or chemical attachment. For example, the water repellent compound can also be modified on the hydroxyl group possessed by the substrate (fiber, etc.) by physical or (reaction) chemical means.

[0501] The water repellency of the fiber structure obtained by the spray test method specified in JIS L1092:2009 may be 3 or higher, 4 or higher, or 5 or higher, preferably 4 or higher, and more preferably 5 or higher. The penetration rate of the fiber structure obtained by the DIN53924 test method may be 25 mm / 2h or lower, 20 mm / 2h or lower, 15 mm / 2h or lower, 10 mm / 2h or lower, or 5 mm / 2h or lower, preferably 15 mm / 2h or lower, and more preferably 10 mm / 2h or lower.

[0502] [Base material]

[0503] The substrate treated with the water repellent in the present invention is not limited, but is preferably a fiber product or a paper product, particularly a fiber product.

[0504] Examples of the base material of fiber products include natural fibers of plants and animals 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 (e.g., water-repellent clothing, such as raincoats), and blankets, but fibers, yarns, and intermediate fiber products (e.g., slivers or rovings, etc.) in a state before being made into cloth may also be processed.

[0505] The air permeability of the fiber substrate can be greater than 20cc / cm 2 / sec, greater than 25cc / cm 2 / sec, greater than 35cc / cm 2 / sec, greater than 45cc / cm 2 / sec, greater than 55cc / cm 2 / sec, greater than 65cc / cm 2 / sec or greater than 75cc / cm 2 / sec. The air permeability of the fiber substrate can be less than 200cc / cm 2 / sec, less than 180cc / cm 2 / sec, less than 160cc / cm 2 / sec, less than 140cc / cm 2 / sec、120cc / cm 2 / sec, less than 100cc / cm 2 / sec, less than 80cc / cm 2 / sec, less than 60cc / cm 2 / sec or less than 40cc / cm 2 / sec. It should be noted that even after the fiber substrate is treated with a water repellent (after the water repellent compound is attached), the air permeability generally does not change much, and the air permeability of the fiber substrate can also be understood as the air permeability of the fiber structure. The fiber structure of the present invention can also show suitable water repellency and / or permeability resistance even when the air permeability of the fiber substrate is high.

[0506] The fabric density of the fiber substrate can be greater than 100g / m 2 , greater than 125g / m 2 , greater than 150g / m 2 , greater than 175g / m 2 , greater than 200g / m 2 , greater than 225g / m 2 Or more than 250g / m 2The fabric density of the fiber substrate can be less than 500g / m 2 , less than 450g / m 2 , less than 400g / m 2 , less than 350g / m 2 , less than 300g / m 2 , less than 250g / m 2 , less than 200g / m 2 , less than 150g / m 2 Or less than 125g / m 2 It should be noted that after the fiber substrate is treated with a water-repellent agent (after the water-repellent compound is attached), the fabric density usually does not change much, and the fabric density of the fiber substrate can be understood as the fabric density of the fiber structure. The fiber structure of the present invention can also show suitable water repellency and / or permeability resistance even when the fabric density of the fiber substrate is high.

[0507] In particular, the fiber structure of the present invention is suitable for fabrics for applications requiring high air permeability and high fabric density (for example, fabrics for shoes).

[0508] Examples of substrates for paper products include: paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as groundwood pulp, mechanical pulp or thermomechanical pulp, waste paper pulps such as waste newspapers, waste magazine paper, waste cardboard or deinked waste paper, containers made of paper, molded bodies made of paper, etc. Specific examples of paper products include: food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general-purpose lining paper and core, neutral pure white roll paper, neutral lining paper, rust-proof lining paper and metal composite 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., and as suitable examples, food packaging materials and food containers can be listed.

[0509] The substrate treated with the water repellent of the present invention is not limited to fiber products or paper products, and can also include stone, filters (e.g., electrostatic filters), dust covers, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, coated surfaces, and gypsum.

[0510] In the case where the substrate is glass, the manufactured glass product can be an optical component. A certain layer (or film) such as a hard coating and an anti-reflection layer may also be formed on the surface (outermost layer) of the glass substrate. The anti-reflection layer may also use any one of a single-layer anti-reflection layer and a multi-layer anti-reflection layer. Examples of inorganic substances that can be used for the anti-reflection layer include: SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic substances can be used alone or in combination of two or more thereof (for example, as a mixture). In the case of a multi-layer anti-reflection layer, it is preferred that SiO2 and / or SiO be used in its outermost layer. In the case where the article to be manufactured is an optical glass component for a touch panel, a transparent electrode may also be provided on a portion of the surface of the substrate (glass), using a thin film such as indium tin oxide (ITO) or indium zinc oxide. In addition, the substrate may also have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating layer, a polarizing film, a phase difference film, and a liquid crystal display module, etc., depending on its specific specifications.

[0511] [Handling method]

[0512] The water repellent of the present invention can be applied to a substrate as a treatment agent (especially a surface treatment agent) by a known method. As a method of treatment, the following method can be used: after the water repellent in the present invention is dispersed in an organic solvent or water and diluted as needed, it is attached to the interior and / or surface of the substrate and dried by known methods such as dip coating, spraying, foam coating, etc. After drying, a product with solid components in the water repellent is obtained. In addition, as needed, it can also be cured after being applied together with an appropriate cross-linking agent. In the water repellent of the present invention, as needed, various additives such as water repellent and / or oil repellent, anti-slip agent, antistatic agent, texture regulator, softener, antibacterial agent, flame retardant, paint fixative, anti-wrinkle agent, drying speed regulator, cross-linking agent, film-forming aid, solubilizer, antifreeze agent, viscosity regulator, ultraviolet absorber, antioxidant, pH regulator, insect repellent, defoamer, etc. can be further used. As an example of various additives, it can be the same as described in the "other ingredients" in the above description. The concentration of the water repellent in the treatment agent in contact with the substrate can be appropriately changed depending on the application, and may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0513] The water repellent can be applied to the substrate by any method known for treating the substrate by liquid. The substrate can be immersed in a solution of the water repellent, or the solution of the water repellent can be attached to or sprayed on the substrate. For the treated substrate, in order to make it show liquid repellency, it is preferably dried and cured by heating. The heating temperature can be, for example, 100°C to 200°C, 100°C to 170°C or 100°C to 120°C. In the present invention, good performance can be obtained even if it is heated at a low temperature (for example, 100°C to 140°C). In the present invention, the heating time can be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the substrate is paper, it can be applied to the paper, or the solution can be attached to or sprayed on the paper, or it can be mixed with the pulp slurry before papermaking and then treated. The treatment can be an external addition treatment or an internal addition treatment. Alternatively, the water repellent can be used for fiber products by a cleaning method, or it can be used for fiber products by, for example, washing applications or dry cleaning methods.

[0514] [Pretreatment of fiber products]

[0515] The fiber product may be pretreated before being treated with the water repellent of the present invention. By pretreating the fiber product, excellent fastness can be imparted to the fiber product after being treated with the water repellent.

[0516] Examples of pretreatment of fiber products include: cationization treatment by reaction with reactive quaternary ammonium salts, anionization treatment such as sulfonation, carboxylation, phosphorylation, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, polymer coating treatment, etc.

[0517] The method for pretreating the fiber products is not limited, and the fiber products can be pretreated by existing known methods. It can also be the following method: as needed, the pretreatment liquid is dispersed in an organic solvent or water for dilution, and it is attached to the inside and / or surface of the fiber products by known methods such as dipping, spraying, foam coating, etc. and then dried. The pH and temperature of the pretreatment liquid can be adjusted according to the required degree of treatment. As an example of the pretreatment method of the fiber products, the method of pretreating the fiber products by the above-mentioned treatment agent will be described in detail.

[0518] The method for pretreating a fiber product may also include the following step: imparting to the fiber a compound selected from -SO3M 1 (Where M 1 represents a monovalent cation) represents a monovalent group, -COOM 2 (Where M 2 represents a monovalent cation), and -OP(O)(OX 1 )(OX 2 )(where X1 and X 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) and one or more functional groups (hereinafter sometimes referred to as "specific functional groups") in a monovalent group represented by.

[0519] As M 1 , H, K, Na or an ammonium ion which may have a substituent. 2 , which may include H, K, Na or an ammonium ion which may have a substituent. 1 or X 2 In the case of an alkyl group, an alkyl group having 1 to 22 carbon atoms is preferred, and an alkyl group having 4 to 12 carbon atoms is more preferred.

[0520] The fiber containing the above-mentioned specific functional group (hereinafter, sometimes referred to as "functional group-containing fiber") can be prepared by, for example, the following method.

[0521] (i) The compound having the above-mentioned specific functional group is attached to the fiber material. It should be noted that the compound may be attached in a state where a part of the compound is chemically bonded to a part of the fiber within a range where a sufficient amount of the above-mentioned specific functional group remains.

[0522] (ii) A fiber in which the above-mentioned specific functional group is directly introduced into a material constituting the fiber is prepared.

[0523] In the case of (i), for example, the functional group-containing fiber is obtained by a functional group introduction step in which the fiber material is treated with a pretreatment solution containing one or more compounds having the above-mentioned specific functional group.

[0524] 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 also be in any form such as fibers (tows, slivers, etc.), threads, knitted fabrics (including mixed knitting), woven fabrics (including mixed weaving), and nonwoven fabrics.

[0525] In this embodiment, from the viewpoint of improving the water repellency of the obtained fiber product, it is preferred to use a fiber material containing polyamide and polyester as raw materials, and in particular, it is preferred to use nylon 6, nylon 6,6 and other nylons, polyethylene terephthalate (PET), polyethylene trimethylene terephthalate, polyesters such as polylactic acid, and mixed fibers containing these.

[0526] As having the above-SO3M 1As the compound, a phenolic polymer can be used. As such a phenolic polymer, for example, a substance containing at least one compound represented by the following general formula can be cited.

[0527]

[0528] [Wherein, X 2 Represents-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.]

[0529]

[0530] [Wherein, M 4 represents a monovalent cation.]

[0531] As the above M 3 , examples include H, K, Na, and an ammonium ion which may have a substituent.

[0532] As the above M 4 , examples include H, K, Na, and an ammonium ion which may have a substituent.

[0533] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0534] As with the above-COOM 2 The compound includes polycarboxylic acid polymers.

[0535] As the polycarboxylic acid polymer, for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer, or a commercially available product can be used.

[0536] As a method for producing a polycarboxylic acid polymer, for example, the following method can be cited: a free radical polymerization initiator is added to an aqueous solution of the above-mentioned monomer and / or its salt, and the reaction is heated at 30 to 150° C. for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, isopropanol or an aqueous solvent such as acetone can also be added to the aqueous solution of the above-mentioned monomer and / or its salt. As a free radical polymerization initiator, for example, a redox polymerization initiator formed by a combination of persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, a 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 in combination of two or more. In addition, during free radical polymerization, a chain transfer agent (for example, octyl thioglycolate) can also be added to adjust the degree of polymerization.

[0537] In the case of free radical polymerization, in addition to the above-mentioned monomers, copolymerizable monomers may also be used. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, methacrylates, and the like. Acrylates and methacrylates are preferably substances having a hydrocarbon group having 1 to 3 carbon atoms which may optionally 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, propyl methacrylate, and the like. These copolymerizable monomers may be used alone or in combination of two or more.

[0538] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized with alkali metals and amine compounds, etc. Examples of the alkali metals include sodium, potassium, and lithium, and examples of the amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0539] 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.

[0540] As the polycarboxylic acid-based polymer, commercially available products such as “NEOCRYSTAL 770” (trade name, manufactured by Nikka Chemical Co., Ltd.) and “CELLOPOL PC-300” (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0541] As the above-OP(O)(OX 1 )(OX 2 ) can be exemplified by the phosphate ester compounds represented by the following general formula.

[0542]

[0543] [Wherein, X 1 or X 2 Same meaning as above, X 3 represents an alkyl group having 1 to 22 carbon atoms.]

[0544] 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.

[0545] From the viewpoint of improving the water repellency of the obtained fiber product, it is preferable to use dodecyl phosphate or decyl phosphate.

[0546] As the phosphate 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.

[0547] The pretreatment liquid containing one or more compounds having the above-mentioned specific functional groups can be, for example, an aqueous solution of the above-mentioned compounds. In addition, the pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, and the like.

[0548] As a method for treating the fiber material with the above-mentioned pretreatment liquid, for example, a pressure dyeing treatment, an immersion treatment, a spray treatment, and a coating treatment can be cited. As a pressure dyeing treatment, for example, a method using a pressure dyeing device described in the Dictionary of Fiber Dyeing Processing (1963 (Showa 38), published by Nikkan Kogyo Shimbun) pages 396-397 and Color Dyeing Chemistry III (1975, published by Jikyo Publishing Co., Ltd.) pages 256-260 can be cited. As a coating treatment, for example, a method using a coating machine described in the Overview of Dyeing and Finishing Machines (1981 (Showa 56)), pages 473-477 can be cited. As an immersion treatment, for example, a method using an intermittent dyeing machine described in the Overview of Dyeing and Finishing Machines (1981, published by Textile Company) pages 196-247 can be used, and a liquid flow dyeing machine, an air flow dyeing machine, a drum dyeing machine, a capstan rope dyeing machine, a washing dyeing machine, a bobbin dyeing machine, etc. can be used. As spray treatment, for example, there can be cited the method of using an air sprayer that sprays the treatment liquid after it is made into mist by compressed air, and an air sprayer with a hydraulic atomization method. The concentration of the treatment liquid at this time and the treatment conditions such as the heat treatment after the treatment can be appropriately adjusted after considering various conditions such as its purpose and performance. In addition, when the pretreatment liquid contains water, it is preferably dried to remove the water after it is attached to the fiber material. There is no particular restriction on the drying method, and it can also be any method of dry heat method and wet heat method. There is no particular restriction on the drying temperature, for example, drying at room temperature to 200°C for 10 seconds to several days. It can also be heated at a temperature of 100 to 180°C for about 10 seconds to 5 minutes after drying as needed.

[0549] It should be noted that, when the fiber material is the material to be dyed, the treatment with the pretreatment liquid can be carried out before dyeing or in the same bath as dyeing. However, in the case of reduction soaping, since the compounds with the above-mentioned specific functional groups (for example, phenolic polymer compounds, etc.) adsorbed during the process may fall off, it is preferred to carry out the pretreatment after the reduction soaping after dyeing.

[0550] The treatment temperature during the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0551] In the functional group introduction step using the pretreatment liquid, it is preferred to treat the fiber material so that the amount of the compound having the specific functional group attached is 1.0 to 7.0 parts by weight relative to 100 parts by weight of the fiber material. Within this range, both durable water repellency and texture can be achieved at a high level.

[0552] The pH of the pretreatment liquid may be adjusted to less than 7, for example, 3 to 5. A pH adjuster such as acetic acid or malic acid can be used for pH adjustment.

[0553] In the pretreatment solution, a salt may be used in combination in order to effectively adsorb the compound having the above-mentioned specific functional group to the fiber material by the salting-out effect. Examples of the salt that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0554] In the functional group introduction step using the pretreatment liquid, it is preferred to remove the excess compound having the above-mentioned specific functional group after treatment. As a removal method, a method using water washing can be cited. By sufficiently removing it, it is possible to prevent the display of water repellency from being hindered in the water repellent processing in the later stage, and the texture of the obtained fiber product will also become good. In addition, the obtained functional group-containing fiber is preferably fully dried in advance before contacting with the above-mentioned treatment agent.

[0555] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fibers include cationic dyeable polyester (CD-PET).

[0556] From the viewpoint of improving the water repellency of the obtained fiber product, the surface zeta potential of the functional group-containing fiber is preferably -100 to -0.1 mV, more preferably -50 to -1 mV. The surface zeta potential of the fiber can be measured by, for example, a zeta potential-particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0557] It should be understood that although the above embodiments have been described, various changes in form and details may be made without departing from the spirit and scope of the scope of the claims.

[0558] Example

[0559] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

[0560] <Production Examples 1 to 6: Synthesis of Hydrophobic Compounds as Acrylic Polymers>

[0561] [Production Example 1]

[0562] Into a 500 ml container, 30 g of a water-soluble glycol solvent as a liquid medium, 120 g of pure water, 40 g of octadecyl acrylate, 2 g of a sorbitan fatty acid ester as a surfactant, 2 g of a cationic emulsifier as an emulsifier, and 6 g of a polyoxyethylene alkyl ether were placed, heated to 80° C., stirred at 2000 rpm for 1 minute using a homomixer, and then dispersed by ultrasonic emulsification for 15 minutes.

[0563] Next, the mixture was transferred to a 500 ml autoclave, purged with nitrogen, and charged with 0.2 g of dodecyl mercaptan and 20 g of vinyl chloride as a chain transfer agent. 1 g of azo group-containing water-soluble initiator was added as a polymerization initiator, and the mixture was heated to 60°C and reacted for 4 hours to obtain a polymer dispersion. The dispersion was further diluted with pure water to prepare an aqueous dispersion with a solid content concentration of 30%.

[0564] [Production Examples 2 to 4, 6]

[0565] An aqueous dispersion was prepared in the same manner as in Production Example 1 except that the formulation was changed according to Table 1.

[0566] [Production Example 5]

[0567] (Preparation of Silicone Polymer)

[0568] Into a 200mL four-necked flask with a stirring rod, a thermometer, and a reflux tube, 12g of methyl hydrogen silicone oil (SiH:SiCH3 molar ratio = 50:50 measured by 1HNMR) and 0.02g of platinum catalyst were placed. Next, 36g of 1-hexadecene was placed in a dropping funnel, maintained at 70°C, and 1-hexadecene was added dropwise from the dropping funnel. After the addition was completed, the reaction was further carried out at 70°C for 3 hours. After confirming the disappearance of the SiH peak by infrared spectroscopy (IR), 47g of solid organosilicon polymer was obtained.

[0569] Next, 28 g of the organosilicon polymer, 5.6 g of a water-soluble glycol solvent, 60 g of pure water, 1.7 g of a sorbitan fatty acid ester, 0.7 g of a polyoxyethylene alkyl ether, and 0.6 g of a cationic emulsifier were placed in a 250 ml glass container, heated to 75° C., stirred at 2000 rpm for 1 minute using a homomixer, and then dispersed by ultrasonic emulsification for 10 minutes to obtain a dispersion of the organosilicon polymer. Then, pure water was added to obtain an aqueous dispersion of the organosilicon polymer having a solid content concentration of 30% by mass.

[0570] (Preparation of Acrylic Polymer in the Presence of Silicone Polymer)

[0571] In a 500 ml container, 25.5 g of a water-soluble glycol solvent, 17 g of octadecyl acrylate, 17 g of an octadecyl-containing amide acrylate, 153 g of pure water, 1.7 g of a sorbitan fatty acid ester, 1.7 g of a cationic emulsifier, 5.1 g of a polyoxyethylene alkyl ether, and 11 g of the above-synthesized silicone polymer were placed, heated to 80°C, stirred at 2000 rpm for 1 minute by a homomixer, and then dispersed by ultrasonic emulsification for 15 minutes. The emulsified dispersion was transferred to a 500 ml autoclave, purged with nitrogen, and then 0.17 g of dodecyl mercaptan and 17 g of vinyl chloride were placed. 0.85 g of an azo-containing water-soluble initiator was added, the temperature was raised to 60°C, and the reaction was performed for 4 hours to obtain an aqueous dispersion of the polymer. The dispersion was then diluted with pure water to prepare an aqueous dispersion with a solid content concentration of 30%.

[0572] In addition, the octadecyl group-containing amide acrylate represents stearylamide ethyl acrylate, and the polyoxyethylene alkylphenol represents Ramtel PD-420 manufactured by Kao Corporation.

[0573] <Production Examples 7 to 11: Production of Hydrophobic Compounds as Isocyanate Derivatives>

[0574] [Production Example 7]

[0575] (Synthesis of Isocyanurate Derivatives)

[0576] In a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube and a cooling tube, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, trade name: TAKENATE 700), 0.25 parts by mass of 2,6-di-tert-butyl-4-methylphenol (also known as dibutylhydroxytoluene, BHT, hindered phenol antioxidant), and 0.25 parts by mass of tetraphenyl-dipropylene glycol-diphosphite (organic phosphite, co-catalyst) were mixed under a nitrogen atmosphere, and 10.7 parts by mass of 1,3-butanediol was added to the mixed solution, and nitrogen was introduced into the liquid phase for 1 hour. Then, the mixed solution was heated to 80°C and reacted for 3 hours, and then cooled to 60°C. Then, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium-2-ethylhexanoate was added as an isocyanurate catalyst and reacted for 1.5 hours. Then, 0.04 parts by mass of o-toluenesulfonamide was added to 100 parts by mass of HDI. Then, the reaction mixture was passed into a thin film distillation apparatus (temperature 150° C., vacuum degree 93.3 Pa) and distilled to reduce the amount of residual HDI monomer to 0.5% or less, thereby obtaining an aliphatic polyisocyanate derivative (isocyanurate derivative of hexamethylene diisocyanate). The isocyanate group content of the obtained isocyanurate derivative was 20.9%, and the average number of isocyanate functional groups was 3.0.

[0577] (Manufacture of hydrocarbon-based polyurethane)

[0578] In a reactor equipped with a stirrer, a thermometer, a cooler and a nitrogen inlet pipe, 100.20 g of the isocyanurate derivative obtained above, 67.60 g of KALCOL 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound and 22.30 g of oleyl alcohol were mixed and reacted under a nitrogen atmosphere at 110° C. for 4 hours until the concentration of the isocyanate group reached 3.67%.

[0579] Next, the reaction liquid was cooled to 80° C., 9.90 g of N-methyldiethanolamine was added as a cationic active hydrogen compound, and the mixture was reacted at 80° C. for 1 hour.

[0580] Next, 50.00 g of methyl ethyl ketone was added as a solvent, and the reaction was carried out at 80° C. until the disappearance of the isocyanate group was confirmed by infrared absorption spectrum.

[0581] Next, 57.69 g of methyl ethyl ketone was added to the reaction liquid, the temperature was raised to 80°C, and the mixture was mixed until the reaction liquid was completely dissolved, and then the mixture was cooled to 75°C.

[0582] Then, 18.96 g of acetic acid was added as an acid compound to neutralize it.

[0583] Next, while the reaction liquid was maintained at 75° C., 800.0 g of ion-exchanged water heated to 70° C. was slowly added thereto for emulsification (internal emulsification).

[0584] Next, the solvent was removed in an evaporator at a water bath temperature of 60° C. under reduced pressure until the solid content concentration reached 20% by weight or more.

[0585] Next, the solid content concentration excluding the acid compound (acetic acid) was adjusted to 20% by weight using ion-exchanged water to obtain an aqueous dispersion containing polyurethane.

[0586] [Production Example 8]

[0587] In a 500 mL four-necked flask equipped with a stirring rod, a thermometer, and a reflux tube, 116 g of sorbitan tristearate and 150 g of 4-methyl-2-pentanone (MIBK) were placed. Next, in order to remove excess water vapor in the mixed solution, the temperature of the mixed solution was maintained at 70°C while the mixed solution was stirred, and the mixed solution was refluxed for 1 hour, and then allowed to cool to 50°C. Next, while maintaining stirring, 30 g of Desmodur N-100 (a biuret derivative of hexamethylene diisocyanate, Covestro) was added dropwise to the mixed solution using a dropping funnel. After the addition was completed, a drop of dibutyltin dilaurate was added as a catalyst, and the mixture was reacted at 80°C for 1 hour. Next, 25 g of sorbitan monostearate was added, and the mixture was reacted at 80°C for another 4 hours.

[0588] Next, after cooling to 60°C, the reaction solution was recovered and slowly mixed with 60°C water containing an arbitrary amount of a cationic emulsifier and a polyoxyethylene alkyl ether. The mixed solution was stirred at 6000 rpm using a homomixer and then dispersed by ultrasonic emulsification for 15 minutes. Then, the solvent (MIBK) was removed by decompression, and pure water was added to adjust the concentration to obtain an aqueous dispersion containing polyurethane having a solid content concentration of 20%.

[0589] [Production Example 9]

[0590] 150 g of methyl ethyl ketone (MEK) and 51 g of stearyl alcohol were placed in a 500 mL four-necked flask equipped with a stirring rod, a thermometer, and a reflux tube. Next, in order to remove excess water vapor from the mixed solution, the temperature of the mixed solution was maintained at 70° C., while the mixed solution was stirred, and the mixed solution was refluxed for 1 hour, and then allowed to cool to 50° C. Next, 30 g of Desmodur N3200A (a biuret derivative of hexamethylene diisocyanate, manufactured by Covestro) was added to the mixed solution, and the mixture was reacted at 80° C. for another 4 hours.

[0591] Next, after cooling to 60° C., the reaction solution was recovered and slowly mixed with water containing an arbitrary amount of polyoxyethylene alkyl ether at 60° C. The mixture was stirred at 6000 rpm by a homomixer and then dispersed by ultrasonic emulsification for 15 minutes.

[0592] Next, the solvent (MEK) was removed by a reduced pressure operation, and then pure water was added to adjust the concentration to obtain an aqueous dispersion containing polyurethane having a solid content concentration of 20%.

[0593] [Production Example 10]

[0594] 190.6 g of trimethylolpropane, 808.2 g of stearic acid and 1.2 g of p-toluenesulfonic acid were added to a 1000 mL flask, and a dehydration reaction was carried out at 140-210°C for 3 hours under a nitrogen flow to obtain a product. The acid value and hydroxyl value of the obtained product were measured, and the results showed that the acid value was 1.8 mgKOH / g and the hydroxyl value was 89 mgKOH / g. 715.5 g of the above product, 180.2 g of hexamethylene diisocyanate and 1.3 g of a bismuth-based catalyst (Nitto Kasei Co., Ltd., Neostan U-600) were added to another container, and the reaction was carried out at 80°C for 5 hours. The reaction was carried out until the NCO% reached 5.0. After the reaction, the temperature was lowered to 40°C, and then 103.0 g of 3,5-dimethylpyrazole was added, and the reaction was carried out at 40°C for 1 hour to obtain an isocyanate derivative. It should be noted that, in the isocyanate derivative, two hydroxyl groups in trimethylolpropane form ester groups with stearic acid, and one hydroxyl group forms a urethane bond with hexamethylene diisocyanate whose one end is protected by 3,5-dimethylpyrazole.

[0595] 40 g of the isocyanate derivative obtained above, 50 g of methyl ethyl ketone, 10 g of polyglycerol fatty acid ester, and 5 g of a cationic emulsifier were added to a 500 mL stainless steel container and heated to 50° C. to dissolve. Then, 295 g of hot water at 80° C. was added and emulsified for 20 minutes while maintaining 80° C. using an ultrasonic emulsifier. The mixture was then cooled to obtain a 10% dispersion of the isocyanate derivative.

[0596] <Examples and Comparative Examples>

[0597] The dispersion obtained in the above-mentioned Production Example was diluted with tap water to have the composition shown in Table 2, and 1000 g of a test solution having a solid content concentration of 1.0 mass % was prepared.

[0598] Next, the test cloth shown in Table 2 was impregnated with the test liquid and passed through a cloth mangle to pass the test cloth at 160° C. for 1 minute and dried and cured. Then, the following [Water Repellency Test] and [Permeation Resistance Test] were performed.

[0599] As the dendrimer-based water repellent, ECOPLUS (manufactured by Rudolph) was used.

[0600] As a curing agent, a 40 mass % aqueous dispersion of a dimethylpyrazole block product of an HDI (hexamethylene diisocyanate) trimer was used.

[0601] The test procedure is as follows. The results are shown in Table 2.

[0602] [Water repellency test]

[0603] The evaluation is performed by the spray test method specified in JIS L1092:2009 (AATCC-22) "Test method for water resistance of textile products" and the grade is determined.

[0604] Water repellency: Status

[0605] 5: No moisture attached to the surface;

[0606] 4: The surface shows a little adhesion and moisture;

[0607] 3: The surface part appears wet;

[0608] 2: The surface appears wet;

[0609] 1: The surface appears wet as a whole;

[0610] 0: Both sides appear completely wet.

[0611] [Permeation resistance test]

[0612] The permeation resistance test was evaluated by the method specified in the DIN53924 test method. Specifically, the test was performed by the following method. Prepare a fiber structure cut into a size of 3 cm wide and 8 cm long, and mark a water level 1 cm from the bottom. Next, suspend the fiber structure so that its bottom is immersed in water to the water level and let it stand for 2 hours. After 2 hours, measure the length (mm) of the portion wetted by the capillary phenomenon (length from the water level).

[0613] [Water contact angle test]

[0614] The water contact angle of the hydrophobic compound is obtained by spin-coating a chloroform solution of the hydrophobic compound having a solid content concentration of 1.0% on a silicon wafer substrate, dropping 2 μL of water on the coating film, and measuring the contact angle 1 second after the dropping.

[0615] [Air permeability test]

[0616] The measurement was performed by the "Frazir method" in accordance with JIS L1096:2010 8.26.1A.

[0617] [Fabric density determination]

[0618] Cut 10 pieces of fabric according to the size of 10cm×10cm, measure the weight, and calculate the average weight. Calculate the fabric density g / m based on the above average weight. 2 .

[0619] [Table 1]

[0620]

[0621] [Table 2]

[0622]

[0623] The air permeability of polyester 1 is from 80cc / cm 2 / sec increased to 88cc / cm after water repellent treatment 2 / sec, fabric density from 230g / m 2 Increased to 232g / m after water repellent treatment 2 .

[0624] The air permeability of nylon 1 is 70cc / cm 2 / sec increased to 77cc / cm after water repellent treatment 2 / sec, fabric density from 200g / m 2 Increased to 201g / m after water repellent treatment 2 .

[0625] The air permeability of polyester 2 is from 80cc / cm 2 / sec increased to 86cc / cm after water repellent treatment 2 / sec, fabric density from 40g / m 2 No changes.

[0626] It should be noted that there is no significant difference between the embodiments and the comparative examples.

Claims

1. A fiber structure, characterized in that: A hydrophobic compound having a hydrocarbon group having 6 to 40 carbon atoms is attached to a fiber base material. The fiber structure has an air permeability greater than 20cc / cm 2 / sec, and the fabric density is greater than 100g / m 2 .

2. The fiber structure according to claim 1, characterized in that: The hydrophobic compound is at least one selected from acrylic polymers and isocyanate derivatives.

3. The fiber structure according to claim 2, characterized in that: The hydrophobic compound comprises the acrylic polymer, The acrylic polymer has a repeating unit derived from a polycarbonyl monomer, wherein the repeating unit has one ethylenically unsaturated double bond and has two or more carbonyl groups.

4. The fiber structure according to claim 2 or 3, characterized in that: The hydrophobic compound comprises the isocyanate derivative, The isocyanate derivative has a moiety derived from a cationic active hydrogen compound.

5. The fiber structure according to claim 2 or 3, characterized in that: The hydrophobic compound includes the acrylic polymer and the isocyanate derivative.

6. The fiber structure according to claim 2 or 3, characterized in that: The hydrophobic compound includes the acrylic polymer and the isocyanate derivative having a water contact angle of 100° or more and having a moiety derived from a cationic active hydrogen compound.

7. The fiber structure according to claim 2 or 3, characterized in that: The weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20.

8. The fiber structure according to claim 1 or 2, characterized in that: The water repellency obtained by the spray test method specified in JIS L1092:2009 is above level 4, and the penetration rate obtained by the DIN53924 test method is less than 10mm / 2h.

9. A water repellent, characterized in that: A hydrophobic compound comprising a hydrocarbon group having 6 to 40 carbon atoms, The hydrophobic compound comprises an acrylic polymer and an isocyanate derivative, The isocyanate derivative has a water contact angle of 100° or more and has a portion derived from a cationic active hydrogen compound, The weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20.

10. The water repellent according to claim 9, characterized in that: The hydrophobic compound comprises the acrylic polymer, The acrylic polymer has a repeating unit derived from a polycarbonyl monomer, wherein the repeating unit has one ethylenically unsaturated double bond and has two or more carbonyl groups.

11. A method for producing a fiber structure, characterized in that: The process includes the following steps: The air permeability is greater than 20cc / cm 2 / sec and the fabric density is greater than 100g / m 2 The fiber base material is treated with a water-repellent agent containing a water-repellent compound having a hydrocarbon group having 6 to 40 carbon atoms.

12. A method for producing a fiber structure, characterized in that: include: The air permeability is greater than 20cc / cm 2 / sec fiber base material is treated with a water repellent agent, The water repellent comprises a water repellent compound having a hydrocarbon group having 6 or more and 40 or less carbon atoms, The hydrophobic compound comprises an acrylic polymer and an isocyanate derivative, The isocyanate derivative has a moiety having a water contact angle of 100° or more and derived from a cationic active hydrogen compound.

13. The method for manufacturing a fiber structure according to claim 12, characterized in that: The weight ratio of the acrylic polymer to the isocyanate derivative is 50 / 50 to 80 / 20.

14. The method for producing a fiber structure according to claim 12 or 13, characterized in that: The hydrophobic compound comprises the acrylic polymer, The acrylic polymer has a repeating unit derived from a polycarbonyl monomer, wherein the repeating unit has one ethylenically unsaturated double bond and has two or more carbonyl groups.

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