Repellent

Abstract

Provided is a novel repellent which contains a compound including an aromatic hydrocarbon ring as a base skeleton and can impart liquid-repellent properties to textile products and / or paper products. The repellent contains a compound α represented by formula A(-X-Rn)m [wherein A is an m-valent group formed by removing m hydrogen atoms from an optionally substituted, aromatic hydrocarbon ring, X, independently on each appearance, is a direct bond or a (1+n)-valent group, R, independently on each appearance, is an optionally substituted, C6-C40 aliphatic hydrocarbon group, n, independently on each appearance, is an integer of 1-3, and m is an integer of 1-6].

Description

repellent

[0001] The present disclosure relates to repellents and products (especially textile or paper products) treated with the repellents.

[0002] In recent years, development of non-fluorine-based repellents capable of imparting liquid repellency (water repellency and / or oil repellency) to various substrates has been progressing.

[0003] Patent Document 1 discloses the use of a compound having a heterocyclic ring as a base skeleton to which an aliphatic group having 14 to 100 carbon atoms, an aromatic group having 14 to 100 carbon atoms, or a heterocyclic group having 14 to 100 carbon atoms is bonded via a divalent linking group as a component of a metal surface treatment agent.

[0004] Japanese Patent Application Laid-Open No. 2001-247981

[0005] The compounds in the metal surface treatment agents described in Patent Document 1 contain heterocycles as essential components, and do not describe or suggest the use of hydrocarbon aromatic rings. Furthermore, Patent Document 1 is a metal surface treatment agent, and is not intended to treat textile products or paper products.

[0006] An object of the present disclosure is to provide a novel repellent agent that contains a compound having a hydrocarbon aromatic ring as a main skeleton and that can impart liquid repellency to textile products and / or paper products.

[0007] The present disclosure includes the following aspects: [Item 1] A compound represented by the following formula: A(-X-R ｎ ) ｍ [wherein A is an m-valent group obtained by removing m hydrogen atoms from an optionally substituted hydrocarbon aromatic ring, X is, independently in each occurrence, a direct bond or a 1+n-valent group, R is, independently in each occurrence, an aliphatic hydrocarbon group having from 6 to 40 carbon atoms which may be substituted, n is, independently in each occurrence, an integer of from 1 to 3, and m is an integer of from 1 to 6.] [Item 2] The repellent according to Item 1, wherein R has 12 or more carbon atoms. [Item 3] The repellent according to Item 1 or 2, wherein the compound α has two or more R. [Item 4] X is, independently in each occurrence, a direct bond, —O—, —C(═O)—, —S(═O)—, or —S(═O)—. ２-, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent) １ and X is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. ２ The repellent according to any one of items 1 to 3, wherein X is a 1+n-valent group consisting of one or more selected from the group consisting of: １ - or -X １ -X ２ -X １ - [wherein, X １ is independently in each occurrence a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, —SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ (wherein, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent), and X ２ [Item 6] The repellent according to any one of items 1 to 4, wherein X is a group represented by the formula: -O-C(=O)-NR'-, -C(=O)-NR'-, -SO ２ NH-, -C(OR')R'-, or -C(OR')(-) ２[wherein R' represents a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.] [Item 7] The repellent according to any one of Items 1 to 6, wherein the compound α is an alkyl group which may have a hydroxy group. [Item 8] The repellent according to any one of Items 1 to 7, which comprises water, an organic solvent, or a mixture of water and an organic solvent, and is in the form of a dispersion or a solution. [Item 9] The repellent according to any one of Items 1 to 8, which comprises one or more selected from the group consisting of polysaccharides, paper strength agents, flocculants, fixing agents, retention aids, coagulants, silicone waxes, and blocked isocyanates. [Item 10] The repellent according to any one of Items 1 to 9, which is used for textile products. [Item 11] The repellent according to any one of Items 1 to 9, which is used for paper products. [Item 12] The repellent according to any one of Items 1 to 11, which does not have a fluorine atom. [Item 13] A textile product treated with the repellent according to any one of Items 1 to 12. [Item 14] A paper product treated with the repellent according to any one of Items 1 to 12.

[0008] The repellent agents of the present disclosure can impart liquid repellency to textiles and / or paper products.

[0009] <Definition of Terms> As used herein, an "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. Furthermore, an "n-valent organic group" refers to an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain.

[0010] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C １－２０Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

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

[0012] <Repellent Agent> The repellent agent in the present disclosure imparts liquid repellency to a substrate (e.g., a fiber substrate, a paper substrate), and can function as at least one selected from the group consisting of a water repellent agent, an oil repellent agent, an oil-resistant agent, and a water-resistant agent.

[0013] The repellent according to the present disclosure includes compound α. The repellent according to the present disclosure may contain only compound α. The repellent according to the present disclosure may contain other components such as a liquid medium in addition to compound α.

[0014] The repellent agent in the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

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

[0016] The water contact angle of compound α may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, preferably 40° or more, for example, 60° or more. The water contact angle of compound α may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When compound α has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. As shown in the examples, the water contact angle is the static contact angle of compound α with a spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0017] The HD (hexadecane) contact angle of compound α may be 10° or more, 15° or more, 25° or more, 35° or more, 55° or more, 60° or more, or 65° or more. The HD contact angle of compound α may be 100° or less, 90° or less, or 75° or less. When compound α has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly oil repellency) to the substrate. The HD contact angle is the static contact angle of compound α with a spin-coated film, as shown in the examples, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0018] Compound α in the present disclosure may not have any group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if compound α does not contain these fluorine-containing groups, it can impart liquid repellency to a substrate.

[0019] The compound α in the present disclosure may not have an active hydrogen-containing group. Examples of the active hydrogen-containing group include an amino group, a hydroxyl group, and a carboxyl group. In particular, the compound α in the present disclosure may not have a hydroxyl group from the viewpoint of improving liquid repellency.

[0020] Compound α in the present disclosure is represented by the following formula: A(-X-R ｎ ) ｍ[wherein A is an m-valent group obtained by removing m hydrogen atoms from an optionally substituted hydrocarbon aromatic ring, X is, independently in each occurrence, a direct bond or a 1+n-valent group, R is, independently in each occurrence, an optionally substituted aliphatic hydrocarbon group having from 6 to 40 carbon atoms, n is, independently in each occurrence, an integer of from 1 to 3, and m is an integer of from 1 to 6.]

[0021] [A] A is an m-valent group obtained by removing m hydrogen atoms from an aromatic hydrocarbon ring which may have a substituent. m may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and is preferably 2 or more (e.g., 3 or more). m may be 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less, and is preferably 4 or less.

[0022] Examples of the hydrocarbon aromatic ring include benzene, naphthalene, anthracene, phenanthrene, tetracene, pentacene, pyrene, and coronene.

[0023] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent on the hydrocarbon aromatic ring include, but are not limited to, —OR′, —N(R′) ２ , —COOR′ (wherein R′ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a halogen atom, optionally substituted with one or more halogen atoms, C １－６ Alkyl group, C ２－６ Alkenyl group, C ２－６ Alkynyl group, C ３－１０ Cycloalkyl group, C ３－１０ Unsaturated cycloalkyl groups, 5- to 10-membered heterocyclyl groups, 5- to 10-membered unsaturated heterocyclyl groups, C ６－１０ Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.

[0024] The number of carbon atoms in the hydrocarbon aromatic ring may be 6 or more, 8 or more, or 10 or more. The number of carbon atoms in the hydrocarbon aromatic ring may be 30 or less, 20 or less, 16 or less, 12 or more, or 8 or less.

[0025] The hydrocarbon aromatic ring may be a condensed polycyclic ring containing a plurality of aromatic ring carbons and / or non-aromatic hydrocarbons (for example, 2 to 5, preferably 2 to 3).

[0026] [X] X is a direct bond or a 1+n-valent group, where n can be 1 to 3, 2 to 3, 1 to 2, 1, 2, or 3.

[0027] The molecular weight of X may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. The molecular weight of X may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more.

[0028] X is a direct bond, —O—, —C(═O)—, or —S(═O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms (e.g., 1 to 20, 1 to 12, 1 to 8, or 1 to 4) which may have a substituent.) １ and X is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. ２ and may be a (1+n) valent group consisting of one or more selected from the group consisting of: In this specification, the right side of the group described as X is bonded to R.

[0029] [X １ ] X １ is a non-hydrocarbon linker.

[0030] X １ is a direct bond or a divalent or higher valent group. １ The valence of X may be 2 to 4, 2 to 3, or 2. １ is preferably not only a direct bond.

[0031] X １ The molecular weight of X may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. １ may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0032] X １ is -O-, -C(=O)-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms (e.g., 1 to 20, 1 to 12, 1 to 8, or 1 to 4) which may have a substituent.)

[0033] The hydrocarbon group having 1 to 40 carbon atoms which may have a substituent in R' may be a hydrocarbon group having a substituent, or may be an unsubstituted hydrocarbon group. Examples of the substituent include -OR', -N(R') ２ , —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the total amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the substituted hydrocarbon group, the amount of carbon atoms relative to the total amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, a group having 6 to 40 carbon atoms may have 1 to 3 (for example, 1) -OR' (particularly -OH) as a substituent (for example, other than at a terminal position).

[0034] X １ Examples of include a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, —SO ２ -, -SO ２ NR'-, -C(OR')R'-, -C(OR')(-)２ and the like (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms (e.g., 1 to 20, 1 to 12, 1 to 8, or 1 to 4) which may have a substituent).

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

[0036] X ２ The hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, may be a hydrocarbon group having a substituent, or may be an unsubstituted hydrocarbon group. Examples of the substituent include -OR', -N(R') ２ , —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the total amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the substituted hydrocarbon group, the amount of carbon atoms relative to the total amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, a group having 6 to 40 carbon atoms may have 1 to 3 (for example, 1) -OR' (particularly -OH) as a substituent (for example, other than at a terminal position).

[0037] X ２ is a divalent or higher valent group. ２ The valency of may be, for example, 2-4, 2-3, or 2.

[0038] X ２ The number of carbon atoms in X may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more. ２may have 40 or fewer, 35 or fewer, 30 or fewer, 25 or fewer, 20 or fewer, 15 or fewer, 10 or fewer, or 5 or fewer carbon atoms.

[0039] X ２ X may have a substituent and may be a cyclic, branched, or straight-chain hydrocarbon group. ２ may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, for example, an aliphatic hydrocarbon group (e.g., a saturated aliphatic hydrocarbon group).

[0040] X ２ Examples of -(CH ２ ) ｐ -(p is 1 to 40, for example, 1 to 10), a linear hydrocarbon group having an unsaturated bond of 1 to 40 carbon atoms, for example, 1 to 10 carbon atoms, a hydrocarbon group having a branched structure of 1 to 40 carbon atoms, for example, 1 to 10 carbon atoms, -(CH ２ ) ｑ -C ６ H ４ -(CH ２ ) ｒ -(q and r are each independently 0 to 40, for example, 1 to 10; -C ６ H ４ - is a phenylene group).

[0041] [Examples of X] Examples of X are described below. In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms (e.g., 1 to 20, 1 to 12, 1 to 8, or 1 to 4) which may have a substituent.

[0042] Preferred examples of X include -X １ -or-X １ -X ２ -X １ -. X is -X １ - or -X １ -X ２ -X １ - [wherein, X １is independently in each occurrence a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, —SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ (wherein, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms (e.g., 1 to 20, 1 to 12, 1 to 8, or 1 to 4) which may have a substituent), and X ２ is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.] This makes it possible to impart good liquid repellency to the substrate.

[0043] X may have an amide group, a urea group, or a urethane group. Examples of such X include groups containing: -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-NR'-, etc. The NR' group in the amide group, urea group, or urethane group does not have to be adjacent to an aromatic ring.

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

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

[0046] Examples of X include, when X is tetravalent, -X １ -X ２ (-X １ -) ３ , -X ２ (-X １ -) ３ , -X ２ (-X １ -C(=O)-) ３ , -X ２ (-C(=O)-X １ -) ３ , -X ２ (-X １ -C(=O)-X １ -) ３ , -X ２ (-X １ -X ２ -) ３ , -X ２ (-X １ -X ２ -X １ -) ３ , -X ２ (-X １ -X ２ -X １ -C(=O)-) ３ , -X ２ (-X １ -X ２ -C(=O)-X １ -) ３ , -X ２ (-X １ -X ２ -X １ -C(=O)-X １ -) ３ , -X ２ (-X １ -X ２ -X １ -X ２ -) ３ etc.

[0047] Specific examples of X when X is divalent include -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR'-, and -O-X ２ -S(=O) ２ —NR′—, —O—X ２ —NR′—, —O—X ２ -NR'-S(=O) ２ -, -O-X２ -NR'-C(=O)-、-O-X ２ -NR'-C(=O)-O-、-O-X ２ -NR'-C(=O)-NR'-、-O-^ ２ -NR'-X ２ -、-O-X ２ -O-、-O-X ２ -O-C(=O)-、-O-X ２ -O-C(=O)-NR'-、-O-X ２ -C(=O)-O-、-O-X ２ -C(=O)-NR'-、-O-X ２ -O-X ２ -、-O-X ２ -、-NR'-、-NR'-C(=O)O-、-NR'-C(=O)-NR'-、-NR'-E ２ -S(=O) ２ -NR'-、-NR'-X ２ -NR'-、-NR'-X ２ -NR'-S(=O) ２ -、-NR'-X ２ -NR'-C(=O)-、-NR'-X ２ -NR'-C(=O)-O-、-NR'-X ２ -NR'-C(=O)-NR'-、-NR'-X ２ -NR'-X ２ -、-NR'-X ２ -O-、-NR'-X ２ -O-C(=O)-、-NR'-X ２ -O-C(=O)-NR'-、-NR'-X ２ -O-X ２ -、-NR'-X ２ -C(=O)-O-、-NR'-X ２ -C(=O)-NR'-、-NR'-X ２ -、-C(=O)-、-C(=O)-O-、-C(=O)-NR’-、-C(=O)---、-SO ２ -、-S ２ NR'-、-C(OR')(R')(-) 、 etc. can be mentioned.

[0048] As an example of ----- ２ (-O-)２ -、-X ２ (-O-C(=O)-) ２ -、-X ２ (-O-C(=O)-O-) ２ -、-X ２ (-O-C(=O)-NR’-) ２ -、-X ２ (-O-X ２ -S(=O) ２ -NR’-) ２ -、-X ２ (-O-X ２ -NR’-) ２ -、-X ２ (-O-X ２ -NR’-S(=O) ２ -) ２ -、-X ２ (-O-X ２ -NR’-C(=O)-) ２ -、-X ２ (-O-X ２ -NR’-C(=O)-O-) ２ -、-X ２ (-O-X ２ -NR’-C(=O)-NR’-) ２ -、-X ２ (-O-X ２ -NR’-X ２ -) ２ -、-X ２ (-O-X ２ -O-) ２ -、-X ２ (-O-X ２ -O-C(=O)-) ２ -、-X ２ (-O-X ２ -O-C(=O)-NR’-) ２ -、-X ２ (-O-X ２ -C(=O)-O-) ２ -、-X ２ (-O-X ２ -C(=O)-NR’-) ２ -、-X ２ (-O-X ２ -O-X ２ -) ２ -、-X ２ (-O-X ２ -) ２-、-X ２ (-NR’-) ２ -、-X ２ (-NR’-C(=O)-) ２ -、-X ２ (-NR’-C(=O)-O-) ２ -、-X ２ (-NR’-C(=O)-NR’-) ２ -、-X ２ (-NR’-X ２ -S(=O) ２ -NR’-) ２ -、-X ２ (-NR’-X ２ -NR’-) ２ -、-X ２ (-NR’-X ２ -NR’-S(=O) ２ -) ２ -、-X ２ (-NR’-X ２ -NR’-C(=O)-) ２ -、-X ２ (-NR’-X ２ -NR’-C(=O)-O-) ２ -、-X ２ (-NR’-X ２ -NR’-C(=O)-NR’-) ２ -、-X ２ (-NR’-X ２ -NR’-X ２ -) ２ -、-X ２ (-NR’-X ２ -O-) ２ -、-X ２ (-NR’-X ２ -O-C(=O)-) ２ -、-X ２ (-NR’-X ２ -O-C(=O)-NR’-) ２ -、-X ２ (-NR’-X ２ -O-X ２ -) ２ -、-X ２ (-NR’-X ２ -C(=O)-O-) ２ -、-X ２ (-NR’-X ２ -C(=O)-NR’-)２ -, -X ２ (-NR'-X ２ -) ２ -, -X ２ (-C(=O)-) ２ -, -X ２ (-C(=O)-O-) ２ -, -X ２ (-C(=O)-NR'-) ２ -, -X ２ (-C(=O)-S-) ２ -, -X ２ (-SO ２ -) ２ -, -X ２ (-SO ２ NR'-) ２ -, -X ２ (-C(OR')(R')(-)) ２ -, -C(OR')(-) ２、 etc.

[0049] Specific examples of X include, when X is tetravalent, -X ２ (-O-) ３ -, -X ２ (-O-C(=O)-) ３ -, -X ２ (-OC(=O)-O-) ３ -, -X ２ (-OC(=O)-NR'-) ３ -, -X ２ (-O-X ２ -S(=O) ２ -NR'-) ３ -, -X ２ (-O-X ２ -NR'-) ３ -, -X ２ (-O-X ２ -NR'-S(=O) ２ -) ３ -, -X ２ (-O-X ２ -NR'-C(=O)-) ３ -, -X ２ (-O-X ２ -NR'-C(=O)-O-) ３ -, -X ２ (-O-X ２ -NR'-C(=O)-NR'-) ３-、-X ２ (-O-X ２ -NR’-X ２ -) ３ -、-X ２ (-O-X ２ -O-) ３ -、-X ２ (-O-X ２ -O-C(=O)-) ３ -、-X ２ (-O-X ２ -O-C(=O)-NR’-) ３ -、-X ２ (-O-X ２ -C(=O)-O-) ３ -、-X ２ (-O-X ２ -C(=O)-NR’-) ３ -、-X ２ (-O-X ２ -O-X ２ -) ３ -、-X ２ (-O-X ２ -) ３ -、-X ２ (-NR’-) ３ -、-X ２ (-NR’-C(=O)-) ３ -、-X ２ (-NR’-C(=O)-O-) ３ -、-X ２ (-NR’-C(=O)-NR’-) ３ -、-X ２ (-NR’-X ２ -S(=O) ２ -NR’-) ３ -、-X ２ (-NR’-X ２ -NR’-) ３ -、-X ２ (-NR’-X ２ -NR’-S(=O) ２ -) ３ -、-X ２ (-NR’-X ２ -NR’-C(=O)-) ３ -、-X ２ (-NR’-X ２ -NR’-C(=O)-O-) ３ -、-X ２(-NR'-X ２ -NR'-C(=O)-NR'-) ３ -、-X ２ (-NR'-X ２ -NR'-X ２ -) ３ -、-X ２ (-NR'-X ２ -O-) ３ -、-X ２ (-NR'-X ２ -O-C(=O)-) ３ -、-X ２ (-NR'-X ２ -O-C(=O)-NR'-) ３ -、-X ２ (-NR'-X ２ -O-X ２ -) ３ -、-X ２ (-NR'-X ２ -C(=O)-O-) ３ -、-X ２ (-NR'-X ２ -C(=O)-NR'-) ３ -、-X ２ (-NR'-X ２ -) ３ -、-X ２ (-C(=O)-) ３ -、-X ２ (-C(=O)-O-) ３ -、-X ２ (-C(=O)-NR'-) ３ -、-X ２ (-C(=O)-S-) ３ -、-X ２ (-S) ２ -) ３ -、-X ２ (-S) ２ NR'-) ３ -、-X ２ (-C(OR')(R')(-)) ３ -、etc can be mentioned。

[0050] [R] R is a monovalent aliphatic hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent. R may be cyclic, branched, or linear, preferably branched or linear, more preferably linear. R is preferably a saturated aliphatic hydrocarbon group (alkyl group), which may have a substituent.

[0051] The number of carbon atoms in R may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more. The number of carbon atoms in R may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

[0052] Here, the monovalent aliphatic hydrocarbon group having 6 to 40 carbon atoms and optionally having a substituent, R, may be a hydrocarbon group having a substituent, or may be an unsubstituted hydrocarbon group. Examples of the substituent include -OR', -N(R') ２ , —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the total amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the substituted hydrocarbon group, the amount of carbon atoms relative to the total amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, a group having 6 to 40 carbon atoms may have 1 to 3 (for example, 1) -OR' (particularly -OH) as a substituent (for example, other than at a terminal position).

[0053] [Method for producing compound α] The method for modifying the hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent on the hydrocarbon aromatic ring, is not particularly limited. For example, methods such as a urethane bond formation reaction, a urea bond formation reaction, an ester bond formation reaction, an amide bond formation reaction, and an ether bond formation reaction can be used. In the bond formation reaction, an acylating agent, a condensing agent, a catalyst, etc. are appropriately used.

[0054] The hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent on the hydrocarbon aromatic ring, may be modified by reacting it with a hydrocarbon group-containing reactant. The hydrocarbon group-containing reactant is a compound having a hydrocarbon group and a group capable of reacting with a functional group possessed by the hydrocarbon aromatic ring.

[0055] Examples of hydrocarbon group-containing reactants are: ２ N-R HO-R HO(O=)C-R G(O=)C-R RC(=O)OC(=O)R O=C=N-R S=C=N-R (CH ２ OCH)CH ２ OR G-R, wherein R is an aliphatic hydrocarbon group having an integer of 6 to 40, as defined above, and G is a halogen atom (particularly F, Cl, Br, or I).

[0056] (Urethane Bond Formation) The hydrocarbon aromatic ring and the hydrocarbon group may be bonded via a urethane bond. The urethane bond may be formed, for example, by reacting a hydroxyl group-containing hydrocarbon aromatic ring with an aliphatic hydrocarbon-containing isocyanate. A tin catalyst or an amine can be used as a catalyst during the reaction. For example, by reacting a hydroxyl group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing isocyanate in an organic solvent for a certain period of time, the hydroxyl group reacts with the isocyanate group, thereby obtaining a compound α in which the hydrocarbon aromatic ring and the hydrocarbon group are bonded via a urethane bond.

[0057] (Urea Bond Formation) The hydrocarbon aromatic ring and the hydrocarbon group may be bonded via a urea bond. The urea bond may be formed, for example, by reacting an amino group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing isocyanate group (or by reacting an isocyanate group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing amine). A catalyst may be used as appropriate during the reaction. For example, by reacting an amino group-containing hydrocarbon aromatic ring with an aliphatic hydrocarbon-containing isocyanate in an organic solvent for a certain period of time, the amino group reacts with the isocyanate group, thereby obtaining a compound α in which the hydrocarbon aromatic ring and the hydrocarbon group are bonded via a urea bond.

[0058] (Ester bond formation) The hydrocarbon aromatic ring and the hydrocarbon group may be bonded via an ester bond. The ester bond may be formed, for example, by reacting a hydroxyl group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing hydrocarbon aromatic ring with a hydrocarbon group-containing alcohol). An acylation catalyst, a condensing agent, or the like may be used during the reaction. For example, by reacting a hydroxyl group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing carboxylic acid in an organic solvent for a certain period of time, the hydroxyl group reacts with the carboxylic acid, thereby obtaining a compound α in which the hydrocarbon aromatic ring and the hydrocarbon group are bonded via an ester bond.

[0059] (Amide bond formation) The hydrocarbon aromatic ring and the hydrocarbon group may be bonded via an amide bond. The amide bond may be formed, for example, by reacting an amino group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing hydrocarbon aromatic ring with a hydrocarbon group-containing amine). An acylation catalyst, a condensing agent, or the like may be used during the reaction. For example, by reacting an amino group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing carboxylic acid in an organic solvent for a certain period of time, the amino group reacts with the carboxylic acid, thereby obtaining a compound α in which the hydrocarbon aromatic ring and the hydrocarbon group are bonded via an amide bond.

[0060] (Ether bond formation) The hydrocarbon aromatic ring and the hydrocarbon group may be bonded via an ether bond. The ether bond may be formed, for example, by reacting a halogen-containing hydrocarbon aromatic ring with a hydrocarbon group-containing alcohol (or by reacting a hydroxyl group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing halide). An acid catalyst, a base catalyst, or the like may be used during the reaction. For example, by heating and reacting a halogen-containing hydrocarbon aromatic ring with a hydrocarbon group-containing alcohol in an organic solvent in the presence of a catalyst, the hydrocarbon group-containing alcohol acts as a nucleophile, and a compound α in which the hydrocarbon aromatic ring and the hydrocarbon group are bonded via an ether bond is obtained.

[0061] [Amount of Compound α] The amount of compound α in the repellent may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more. The amount of compound α in the repellent may be 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less.

[0062] [Liquid Medium] The repellent agent of the present disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent agent may be a dispersion or a solution.

[0063] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., polyhydric alcohols such as alcohols and glycol-based solvents, ethers of polyhydric alcohols (e.g., monoethers), etc.). These may be used alone or in combination.

[0064] [Amount of Liquid Medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight) of compound α. The amount of the liquid medium may be 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight).

[0065] 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, or 50 parts by weight or more relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight) of compound α. The amount of organic solvent may be 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight).

[0066] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight) of compound α. The amount of the organic solvent may be 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less relative to 1 part by weight (or 10 parts by weight, or 100 parts by weight).

[0067] [Surfactant] The repellent may contain a surfactant. The surfactant may include one or more surfactants selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.

[0068] [Nonionic Surfactant] Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.

[0069] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0070] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0071] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to hexa-hydric (particularly di- to penta-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0072] Examples of alkanolamides are those formed from fatty acids and alkanolamines. The alkanolamides may be monoalkanolamides or dialkanolamines. Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0073] The polyhydric alcohol may be a dihydric to pentahydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0074] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100. The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

[0075] The nonionic surfactant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct moiety and the polyalkylene glycol moiety is polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, due to environmental concerns (biodegradability, endocrine disrupters, etc.), it is preferable that the nonionic surfactant have a structure that does not contain an aromatic group.

[0076] The nonionic surfactant has the formula: 1 O-(CH ２ CH ２ O) p -(R 2 O) q -R 3 [In the formula, R 1 is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, 2 are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), 3is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.

[0077] R 1 R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. 1 Preferred specific examples of R include a lauryl group, a tridecyl group, and an oleyl group. 2 Examples of the nonionic surfactant are a propylene group and a butylene group. In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among these, an oxypropylene chain is preferred.

[0078] Specific examples of nonionic surfactants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C １２ -C １６ ) thiol, sorbitan mono fatty acid (C ７ -C １９ ) or alkyl (C １２ -C １８ ) condensation products with amines, etc.

[0079] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example 500 to 3,000. The nonionic surfactant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. An example of a compound having an HLB of less than 15 is a sorbitan fatty acid ester. An example of a compound having an HLB of 15 or more is a polyoxyethylene alkyl ether. The weight ratio of the compound having an HLB of less than 15 to the compound having an HLB of 15 or more may be 90:10 to 20:80, for example 85:15 to 55:45. The nonionic surfactant may be a single type or a mixture of two or more types.

[0080] [Cationic Surfactant] The cationic surfactant is preferably a compound having no amide group.

[0081] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene adduct ammonium salt.Specific examples of the cationic surfactant include, but are not limited to, amine salt surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, and quaternary ammonium salt surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride.

[0082] Preferred examples of cationic surfactants include: ２１ -N ＋ (-R ２２ ) (-R ２３ ) (-R ２４ ) X － [In the formula, R ２１ , R ２２ , R ２３ and R ２４ is a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group.２１ , R ２２ , R ２３ and -R ２４ Specific examples of X are alkyl groups (e.g., methyl, butyl, stearyl, and palmityl). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).

[0083] The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula: １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g. C １２ ~C ５０ ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R ２ is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH ３ , C ２ H ５ is particularly preferred), X is a halogen atom (for example), C １ ~C ４ where p is 1 or 2, q is 2 or 3, and p+q=4. １ may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0084] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0085] [Anionic Surfactants] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid surfactants, phosphate mono- or diester surfactants, and sulfosuccinate esters.

[0086] [Amphoteric Surfactant] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0087] The surfactant may be a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant, each of which may be one type or a combination of two or more types.

[0088] [Amount of Surfactant] The amount of surfactant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, relative to 100 parts by weight of compound α. The amount of surfactant may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of compound α.

[0089] [Silicone] The repellent agent according to the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

[0090] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0091] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more. The weight average molecular weight of the silicone may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[0092] [Amount of Silicone] The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, relative to 100 parts by weight of compound α. The amount of silicone may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of compound α.

[0093] [Wax] The repellent agent according to the present disclosure may contain wax. By including wax, it is possible to impart good liquid repellency to the substrate.

[0094] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, mineral wax, etc. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane), and normal alkenes (e.g., 1-eicosane, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane). The number of carbon atoms in the compounds constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be from 200 to 2000, for example, from 250 to 1500, or from 300 to 1000. These may be used alone or in combination of two or more.

[0095] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0096] [Amount of Wax] The amount of wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, relative to 100 parts by weight of compound α. The amount of wax may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of compound α.

[0097] [Organic Acid] The repellent may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one type of organic acid may be used, or two or more types may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0098] [Amount of Organic Acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, relative to 100 parts by weight of compound α. The amount of organic acid may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of compound α. The amount of organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0099] [Hardening Agent] The repellent agent may contain a hardening agent (active hydrogen reactive compound or active hydrogen containing compound).

[0100] The curing agent (crosslinking agent) in the repellent agent can effectively cure compound α. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of compound α. Examples of active hydrogen-reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0101] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

[0102] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate, Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0103] 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.

[0104] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0105] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0106] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0107] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as the repellent.

[0108] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination of two or more.

[0109] An epoxy compound is a compound having an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound having a chloromethyl group. An example of a chloromethyl group-containing compound is chloromethyl polystyrene. A carboxyl group-containing compound is a compound having a carboxyl group. Examples of a carboxyl group-containing compound are (poly)acrylic acid, (poly)methacrylic acid, etc.

[0110] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resins and methyl etherified melamine resins.

[0111] [Amount of Curing Agent] The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, relative to 100 parts by weight of compound α. The amount of curing agent may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of compound α.

[0112] [Other Components] The repellent may contain other components in addition to the above components. Examples of other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, anti-slip agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above components, other components include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, antifoaming agents, shrinkage inhibitors, anti-wrinkle agents after washing, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, and anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine. The following may be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers; foam inhibitors; silk protein powder, surface-modified products thereof, or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)); stain inhibitors (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.) that can impart silk texture and functionality such as moisture absorption and release. These may be used alone or in combination of two or more.

[0113] [Polysaccharides] Examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, pullulan, etc. The polysaccharide may be a substituted modified polysaccharide, in particular a modified polysaccharide into which a hydroxyl group or a cationic group has been introduced.

[0114] [Paper Strength Agents, Flocculants, Retention Aids, or Coagulants] Examples of paper strength agents, flocculants, retention aids, or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formalin condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0115] [Sizing Agents] Examples of sizing agents include cellulose-reactive sizing agents, e.g., rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, e.g., emulsions / dispersions of acid anhydrides such as alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, e.g., copolymers of styrene and acrylate.

[0116] [Antistatic Agent] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, and nonionic antistatic agents such as aminoalcohols and its derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. Ion-conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ionic conductive groups may also be used. These may be used alone or in combination of two or more.

[0117] [Preservatives] Preservatives can be used mainly to enhance antiseptic and bactericidal properties and maintain antiseptic properties during long-term storage. Examples of preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol.

[0118] [Ultraviolet Absorber] An ultraviolet absorber is a chemical agent that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0119] [Antibacterial Agent] An antibacterial agent is a component that has the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors resulting from microbial decomposition products. Examples of the antibacterial agent include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylenebiguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0120] [Deodorant] Examples of deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (e.g., zinc complex of trisodium methylglycine diacetate described in WO 2012 / 090580).

[0121] [Amount of Other Components] The amount of each of the other components or the total amount thereof may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more, relative to 100 parts by weight of compound α. The amount of each of the other components or the total amount thereof may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of compound α.

[0122] <Method for Producing Treated Textile or Paper Products> The method for producing a repellent-treated product according to the present disclosure includes treating a substrate with the repellent described above.

[0123] The term "treatment" means that the repellent is applied to a substrate by immersion, spraying, painting, etc. By the treatment, compound α, which is the active ingredient of the repellent, penetrates into the interior of the substrate and / or adheres to the surface of the substrate.

[0124] [Substrate] The substrate to be treated with the repellent agent of the present disclosure is not limited, but is preferably a textile product or a paper product.

[0125] Examples of substrates for textile products include natural fibers of animal or plant origin such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as clothing fabrics and carpets, and the treatment may be applied to fibers, yarns, and intermediate textile products (for example, slivers or rovings) in a state prior to being made into fabric.

[0126] Examples of substrates for paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating media, neutral white roll paper, neutral liner, anti-corrosion liner and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc.

[0127] Substrates that can be treated with the repellent of the present disclosure are not limited to textiles or paper products, but also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0128] [Treatment Method] The repellent agent of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may involve dispersing and diluting the repellent agent in an organic solvent or water, as needed, and applying it to the surface of the substrate by a known method such as dip coating, spray coating, or foam coating, followed by drying. After drying, a textile product is obtained with the solid components of the repellent attached. If necessary, the repellent agent may be applied together with an appropriate crosslinking agent and cured. The repellent agent of the present disclosure may also be used in combination with various additives, such as water and / or oil repellents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and antifoaming agents, as needed. Examples of the various additives may be the same as those described in the "Other Components" section of the water repellent composition above. The concentration of the repellent in the treatment agent to be brought into contact with the substrate may be varied as appropriate depending on the application, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.

[0129] The repellent agent can be applied to the substrate by any of the known methods for treating a substrate with a liquid. The substrate may be immersed in the repellent agent, or a solution may be applied or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the textile product is paper, the repellent agent may be coated on the paper, or the solution may be applied or sprayed onto the paper, or the repellent agent may be mixed with the pulp slurry before papermaking. The treatment may be an external or internal addition treatment. Alternatively, the repellent agent may be applied to the textile product by a cleaning method, such as a laundry application or a dry cleaning method.

[0130] [Paper Treatment] Examples of paper substrates include paper, paper containers, paper molded articles (e.g., pulp molds), etc. Methods for treating paper substrates include external addition treatment or internal addition treatment.

[0131] The paper can be produced by a conventional papermaking method, such as an internal treatment method in which the repellent is added to the pulp slurry before papermaking, or an external treatment method in which the repellent is applied to the paper after papermaking.

[0132] The internal treatment method may refer to a treatment method in which a repellent is added to a pulp slurry before papermaking. The internal treatment method may include, but is not limited to, one or more of the following steps: adding a repellent to a pulp slurry and stirring and mixing it; suction-dewatering the pulp composition prepared in the above step through a mesh of a predetermined shape to deposit the pulp composition and form a pulp molded intermediate; and molding and drying the pulp molded intermediate in a heated mold to obtain paper, a paper container, or a molded paper product. The treated paper may be subjected to a heat treatment after simple drying at room temperature or an elevated temperature, depending on the paper's properties. The heat treatment temperature may be 150°C or higher, 180°C or higher, or 210°C or higher, and 300°C or lower, 250°C or lower, or 200°C or lower, and particularly 80°C to 180°C. Heat treatment within this temperature range can exhibit excellent oil resistance, water resistance, etc.

[0133] Size presses using external additive treatment methods can also be divided into the following categories based on the application method. One application method is the so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to the nip formed by passing paper between two rubber rolls, creating a pool of coating liquid called a pond, and the paper is passed through this pool of coating liquid to apply the size liquid to both sides of the paper. Other application methods include the gate roll type, in which the size liquid is applied using a surface transfer method, and the rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates into the paper, while in the surface transfer type, the size liquid components tend to remain on the paper surface. In the surface transfer type, the coating layer tends to remain on the paper surface compared to the pond-type two-roll size press, and a larger coating layer is formed on the surface than in the pond-type two-roll size press. In the present disclosure, performance can be imparted to paper even when the former pond-type two-roll size press is used. Papers treated in this way may exhibit excellent oil and water resistance etc., after simple drying at room temperature or at elevated temperatures, optionally followed by a heat treatment which may range in temperature up to 300°C, for example up to 200°C, especially between 80°C and 180°C, depending on the properties of the paper.

[0134] The present disclosure can be used in gypsum board base paper, coated base paper, medium paper, general liners and mediums, neutral pure white roll paper, neutral liners, anti-rust liners and metal interleaving paper, kraft paper, etc. It can also be used in 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.

[0135] Pulp raw materials that can be used include 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, and recycled paper pulp such as recycled newspapers, recycled magazines, recycled corrugated cardboard, and deinked recycled paper. Mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.

[0136] A sizing agent can be added to improve the water resistance of paper. Examples of sizing agents include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents and neutral rosin-based sizing agents). The amount of sizing agent may be 0.01 to 5% by weight of the pulp.

[0137] If necessary, the paper can contain additives used in paper production, such as paper strength agents such as starch, modified starch, carboxymethyl cellulose, and polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, retention aids, dyes, fluorescent dyes, slime control agents, and antifoaming agents, to the extent that they are commonly used. Starch and modified starch are preferably used. If necessary, repellents can be applied to the paper using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc., using a size press, gate roll coater, bill blade coater, calendar, etc.

[0138] In the case of external addition, the amount of the liquid repellent compound contained in the coating layer is 0.01 to 2.0 g / m ２ , particularly 0.1 to 1.0 g / m ２ The coating layer is preferably formed from a repellent and starch and / or modified starch. The solid content of the paper repellent in the coating layer is preferably 2 g / m. ２ In the internal addition, the repellent is preferably mixed with the pulp so that the amount of the repellent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, particularly 0.2 to 5.0 parts by weight, per 100 parts by weight of the pulp forming the paper.

[0139] In the external addition, oil resistance can also be imparted to paper by using a so-called pond-type two-roll size press treatment, in which a treatment solution is accumulated between rolls and the base paper is passed through the treatment solution between the rolls at any roll speed and nip pressure.

[0140] In the external additive treatment, the paper substrate may contain additives such as sizing agents, strength agents, flocculants, retention agents, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives may be -10,000 to 10,000 μeq / g, preferably -4,000 to 8,000 μeq / g, and more preferably -1,000 to 7,000 μeq / g. Additives such as sizing agents, strength agents, flocculants, retention agents, or coagulants (solids or active ingredients) are generally used in amounts of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) based on the pulp. In the case of paper substrates containing cationic additives (e.g., sizing agents, strength agents, flocculants, retention agents, or coagulants), the repellent is preferably anionic.

[0141] In the internal addition treatment, it is preferable to make paper from a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (e.g., 2.5 to 4.0% by weight).Additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, or coagulants) and liquid-repellent compounds can be added to the pulp slurry. Examples of additives (for example, sizing agents, paper strength agents, flocculants, retention agents, or coagulants) include alkylketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formalin condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0142] [Pretreatment of Textile Products] The textile product may be pretreated before being treated with the repellent of the present disclosure. Pretreatment of the textile product can impart excellent durability to the textile product after treatment with the repellent.

[0143] Examples of pretreatments for textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphate, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0144] The method for pretreating a textile product is not limited, and the textile product can be pretreated by a conventionally known method. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the surface of the textile product by a known method such as dip coating, spray coating, foam coating, etc., followed by drying. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of a method for pretreating a textile product, a method for pretreating a textile product with a hydrocarbon-based water repellent will be described in detail.

[0145] The pretreatment method for textile products is to add -SO ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and —O—P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as a "specific functional group").

[0146] M １ Examples of M include H, K, Na, and ammonium ions which may have a substituent. ２ Examples of X include H, K, Na, and ammonium ions which may have a substituent. １ or X ２ When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0147] Fibers containing the specific functional groups (hereinafter sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following methods: (i) A compound having the specific functional groups is attached to a fiber material. The attachment of the compound may be in a state where a portion of the compound is chemically bonded to a portion of the fiber, to the extent that a sufficient amount of the specific functional groups remains. (ii) Fibers are prepared in which the specific functional groups are directly introduced into the material that constitutes the fiber.

[0148] In the case of (i), for example, functional group-containing fibers can be obtained by a functional group introduction step in which a fiber material is treated with a pretreatment liquid containing one or more compounds having the above-mentioned specific functional groups.

[0149] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any form such as fiber (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, etc.

[0150] In this embodiment, from the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use a textile material containing polyamide and polyester as raw materials, and it is particularly preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate and polylactic acid, and mixed fibers containing these.

[0151] Above -SO ３ M １ A phenolic polymer can be used as the compound having the formula:

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

[0152] [In the formula, X ２ Ha-SO ３ M ３ (In the formula, M ３represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0153] [In the formula, M ４ represents a monovalent cation.

[0154] The above M ３ Examples of the cation include H, K, Na, and ammonium ions which may have a substituent.

[0155] The above M ４ Examples of the cation include H, K, Na, and ammonium ions which may have a substituent.

[0156] 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.

[0157] Above - COOM ２ Examples of compounds having the formula include polycarboxylic acid polymers.

[0158] 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.

[0159] Examples of methods for producing polycarboxylic acid polymers include adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt and heating the mixture at 30 to 150°C for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, or isopropyl alcohol, or an aqueous solvent such as acetone, may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite; hydrogen peroxide; and water-soluble azo-based polymerization initiators. These radical polymerization initiators may be used alone or in combination. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0160] In addition to the above-mentioned monomers, copolymerizable monomers can be used for radical polymerization. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Preferred acrylates and methacrylates have a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used alone or in combination of two or more.

[0161] The carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, etc. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0162] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0163] As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (trade name, manufactured by Nicca Chemical Co., Ltd.) and "Ceropol PC-300" (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0164] The above -O-P(O)(OX １ ) (OX ２ ) may be exemplified by phosphate ester compounds represented by the following general formula: [In the formula, X １ or X ２ is as defined above, and X ３ represents an alkyl group having 1 to 22 carbon atoms.

[0165] As the phosphate ester compound, phosphate monoesters, diesters and triesters, in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.

[0166] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0167] As the phosphate ester compound, for example, commercially available products such as "Phosphanol ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0168] The pretreatment liquid containing one or more compounds having the specific functional group may be, for example, an aqueous solution of the compounds described above. The pretreatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc.

[0169] Methods for treating textile materials with the pretreatment liquid include, for example, padding, immersion, spraying, and coating. Examples of padding include methods using padding devices described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating include methods using coating machines described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion include methods using batch dyeing machines described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). These machines include jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatment include air spraying, in which the treatment liquid is atomized using compressed air, and methods using a hydraulic atomization air spray. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, can be adjusted appropriately, taking into account various conditions, such as the purpose and performance. Furthermore, when the pretreatment liquid contains water, it is preferable to dry the pretreatment liquid after application to remove the water. The drying method is not particularly limited, and may be either a dry heat method or a wet heat method. The drying temperature is also not particularly limited, and may be, for example, drying at room temperature to 200°C for 10 seconds to several days. If necessary, heat treatment at a temperature of 100 to 180°C for 10 seconds to 5 minutes may be performed after drying.

[0170] When the textile material is to be dyed, the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as the dyeing. However, when reduction soaping is carried out, there is a risk that the compound having the specific functional group (e.g., a phenolic polymer compound) adsorbed during the treatment may fall off, so it is preferable to carry out the treatment after reduction soaping after dyeing.

[0171] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0172] In the functional group introduction step using a pretreatment liquid, the amount of the compound having the specific functional group attached is preferably 1.0 to 7.0 parts by weight per 100 parts by weight of the textile material. Within this range, durable water repellency and texture can both be achieved at high levels.

[0173] The pH of the pretreatment liquid is preferably adjusted to 3 to 5. The pH can be adjusted using a pH adjuster such as acetic acid or malic acid.

[0174] The pretreatment solution may contain a salt to effectively adsorb the compound having the specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0175] In the functional group introduction step using a pretreatment liquid, it is preferable to remove the compound having the specific functional group that has been treated in excess. An example of a removal method is washing with water. By performing sufficient removal, it is possible to prevent the development of water repellency in the subsequent water repellent treatment from being hindered, and in addition, the feel of the resulting textile product is improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fiber before contacting it with a hydrocarbon-based water repellent.

[0176] (ii) An example of a fiber in which the specific functional group is directly introduced into the material that constitutes the fiber is cationic dyeable polyester (CD-PET).

[0177] From the viewpoint of improving the water repellency of the resulting textile product, the functional group-containing fiber preferably has a surface zeta potential of −100 to −0.1 mV, more preferably −50 to −1 mV. The zeta potential of the fiber surface can be measured, for example, using a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0178] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0179] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0180] <Test Method> The test procedure is as follows.

[0181] [Water Contact Angle] A solution of a liquid-repellent compound with a solid content of 1.0% was spin-coated on a silicon wafer to obtain a smooth spin-coated film. 2 μL of water was dropped on the spin-coated film, and the contact angle 1 second after the drop was dropped was recorded as the water contact angle of the liquid-repellent compound.

[0182] [HD Contact Angle] A solution of a liquid-repellent compound with a solid content of 1.0% was spin-coated on a silicon wafer to obtain a smooth spin-coated film. 2 μL of HD was dropped onto the spin-coated film, and the contact angle 1 second after the drop was dropped was taken as the HD contact angle of the liquid-repellent compound.

[0183] [Preparation of treated fabric] The compound was dissolved in chloroform at a concentration of 22.5 mg / mL to prepare a treatment solution. A polyethylene terephthalate fabric (basis weight 88 g / m, 70 denier, gray) was immersed in this treatment solution, air-dried, and then dried at 150°C for 3 minutes.

[0184] [Water-repellent performance of fabric] A drop of water was applied to the treated fabric, and after 15 seconds, the state of water repellency and the degree of staining after wiping were visually judged. Water droplets were repelled, and no staining was observed after wiping: ◯ Water droplets were repelled, but staining was observed after wiping: △ Water droplets spread and stained: ×

[0185] [Preparation of Treated Paper] A pulp slurry was prepared using wood pulp in weight ratios of 60% by weight (LBKP) and 40% by weight (NBKP), with a pulp freeness of 400 ml (Canadian Standard Freeness). A wet strength agent and a sizing agent were added to the pulp slurry, and the resulting paper was spun on a Fourdrinier paper machine to produce a paper with a density of 0.58 g / cm and a basis weight of 45 g / m. This paper was used as base paper for external treatment (size press treatment). The oil resistance (KIT value) of this base paper was 0, and the water resistance (Cobb value) was 52 g / m. ２ It was.

[0186] A treatment solution prepared by dissolving the compound in chloroform at a ratio of 14.9 mg / mL was applied to this base paper using a Baker applicator with a gap set to 0 mil, followed by drying. This process was repeated three times, and then the paper was dried at 140°C for one minute to produce treated paper.

[0187] [KIT Test] Measurements were made using a 3M kit test (TAPPI T-559cm-02). In the 3M kit test, a test oil containing a blend of castor oil, toluene, and heptane was placed on the surface of treated paper, and after 15 seconds, the test oil was wiped off and the evaluation was based on whether or not oil stains were present on the treated paper. Tests were carried out using test oils with kit numbers 1 to 6, and the highest kit number that showed no stains was used to evaluate the oil resistance.

[0188] [Water-repellent performance of paper] A drop of water was applied to the treated paper, and after 15 seconds, the paper was wiped and the presence or absence of staining was visually judged. No stain after wiping: ◯ Stain after wiping: ×

[0189] <Synthesis of Compound 1> 4.44 g of stearylamine was dissolved in 15.0 mL of dehydrated tetrahydrofuran, and then 1.3 g of triethyl 1,3,5-benzenetricarboxylate was added and stirred overnight at an oil bath temperature of 52° C. The next day, the mixture was cooled to room temperature, filtered, and dried to obtain 3.18 g of Compound 1 shown below.

[0190] <Synthesis of Compound 2> 0.58 g of magnesium and 1 grain of iodine were dissolved in 40 mL of dehydrated tetrahydrofuran, and then 4 g of 1-bromooctadecane was added and stirred at room temperature. After 20 minutes, 4 g of 1-bromooctadecane was added, and the mixture was stirred for an additional 2 hours at room temperature. After 2 hours, the reaction solution was cooled in an ice bath, and then 1 g of dimethyl isophthalate was added in three portions and stirred overnight. The next day, the mixture was neutralized with 3N hydrochloric acid, filtered, and the resulting solid was washed with acetone and diethyl ether to obtain 3.19 g of Compound 2 shown below.

[0191] <Synthesis of Compound 3> 0.5 g of phloroglucinol was dissolved in 20.0 mL of dehydrated tetrahydrofuran, and then 3.75 g of octadecyl isocyanate, 1.71 mL of triethylamine, and 3 drops of dibutyltin dilaurate were added in that order. The mixture was heated and stirred overnight in an oil bath at 60°C. The next morning, the mixture was cooled and filtered. The resulting solid was washed with acetone, methanol, and dichloromethane to obtain 3.27 g of Compound 3 shown below.

[0192] <Synthesis of Compound 4> Compound 4 shown below, which is a known compound, was obtained with reference to Tetrahedron Letters (1999), 40(29), 5323-5326.

[0193] <Synthesis of Compound 5> Compound 5 shown below is a known compound and was obtained with reference to United States, US20220089508 A1 2022-03-24.

[0194] Example 1 Compound 1 was used to evaluate the contact angle, water repellency on fabric, KIT test, and water repellency on paper.

[0195] Example 2 Evaluation was carried out in the same manner as in Example 1, except that Compound 2 was used instead of Compound 1.

[0196] Example 3 Evaluation was carried out in the same manner as in Example 1, except that Compound 3 was used instead of Compound 1.

[0197] Comparative Example 1 The same performance evaluation as in Example 1 was carried out on a silicon wafer, a polyethylene terephthalate cloth, and a base paper that had not been treated with a compound.

[0198] Example 4 Using Compound 4, the contact angle and water repellency of fabric were evaluated.

[0199] Example 5 Evaluation was carried out in the same manner as in Example 4, except that Compound 5 was used instead of Compound 4.

[0200] The test results are summarized in the table below.

[0201] [Table 1: Contact angle test]

[0202] Table 2: Fabric Test

[0203] Table 3: Paper test

Claims

1. The following formula: A(-X-R ｎ ) ｍ [In the formula, A represents an m-valent group obtained by removing m hydrogen atoms from an optionally substituted hydrocarbon aromatic ring, X is independently in each occurrence a direct bond or a group having a valence of 1+n; R independently in each occurrence represents an optionally substituted aliphatic hydrocarbon group having from 6 to 40 carbon atoms; n is independently in each occurrence an integer from 1 to 3, m is an integer of 1 or more and 6 or less. A repellent comprising a compound α represented by the formula: the substituents which the hydrocarbon aromatic ring may have are one or more groups selected from -OR', -N(R') 2 , -COOR' (wherein R' is a hydrocarbon group having 1 to 4 carbon atoms), a halogen atom, a C 1-6 alkyl group optionally substituted by one or more halogen atoms, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C 3-10 unsaturated cycloalkyl group, a 5-10 membered heterocyclyl group, a 5-10 membered unsaturated heterocyclyl group, a C 6-10 aryl group and a 5-10 membered heteroaryl group; The following (1) and (2): (1) The compound α has two or more R (2) R has 10 or more carbon atoms. At least one of the following is satisfied: A repellent, wherein the compound α does not have a fluorine atom.

2. The repellent according to claim 1 , wherein R has 12 or more carbon atoms.

3. The repellent according to claim 1 or 2, wherein the compound α has two or more R.

4. X, Direct bond, -O-, -C(=O)-, -S(=O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein, R' is independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent in each occurrence.) １ and, X is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. ２ and, The repellent according to claim 1 or 2, wherein the repellent is a 1+n valent group consisting of one or more groups selected from the group consisting of:

5. X, -X １ -or- -X １ -X ２ -X １ - [In the formula, X １ but, independently for each occurrence, direct binding, -O-, -O-C(=O)-, -O-C(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO ２ -、 -SO ２ NR'-、 -C(OR')R'-, or -C(OR’)(-) ２ (In the formula, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. is a group represented by X ２ is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.] The repellent according to claim 1 or 2, wherein the R is a group represented by the formula:

6. X is -OC(=O)-NR'-, -C(=O)-NR'-, -SO ２ H -C(OR')R'-, or -C(OR’)(-) ２ [In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.] The repellent according to claim 1 or 2,

7. The repellent described in claim 1 or 2, wherein R is an alkyl group which may have a hydroxyl group.

8. 3. The repellent according to claim 1 or 2, which comprises water, an organic solvent, or a mixture of water and an organic solvent and is a dispersion or solution.

9. The repellent according to claim 1 or 2, comprising one or more selected from the group consisting of polysaccharides, paper strength agents, flocculants, fixing agents, retention aids, coagulants, silicone waxes, and blocked isocyanates.

10. The repellent according to claim 1 or 2, which is for use in textile products.

11. The repellent according to claim 1 or 2, which is for use in paper products.

12. The repellent according to claim 1 or 2, which does not contain fluorine atoms.

13. A textile product treated with the repellent according to claim 1 or 2.

14. A paper product treated with the repellent according to claim 1 or 2.