Repellent

Abstract

Provided is a new repellent capable of imparting liquid repellency to a base material (for example, fiber products and / or pulp products). The repellent comprises a liquid repellent compound that has: a structure in which a monovalent hydrocarbon group having 6-40 carbon atoms and optionally having a substituent is bonded to a carbon atom or a nitrogen atom of an amide group or a urea group; a moiety derived from a compound (a) that has one or more reactive groups; and a moiety derived from a compound (b) that has two or more reactive groups and that does not have a monovalent hydrocarbon group having 6-40 carbon atoms and optionally having a substituent.

Description

repellent

[0001] The present disclosure relates to repellents.

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

[0003] Special table 2016-524628 publication

[0004] The present inventors have conducted extensive research to determine whether there is still room for development of a repellent agent that can impart liquid repellency to a substrate, and as a result have found that there is still room for development of a novel liquid repellent compound that is different from conventional liquid repellent compounds and that can impart liquid repellency to a substrate.

[0005] The present disclosure aims to provide a novel repellent agent that can impart liquid repellency to a substrate (e.g., a textile product and / or a pulp product).

[0006] The present disclosure includes the following aspects: [Item 1] A liquid repellent agent comprising a moiety derived from compound (a) having a structure in which a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, is bonded to a carbon atom or nitrogen atom of an amide group or urea group, and having one or more reactive groups, and a moiety derived from compound (b) having no monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, and having two or more reactive groups. [Item 2] The moiety derived from compound (a) and the moiety derived from compound (b) are represented by the following formula: -X １ -CO-X ２ - [wherein, X １ and X ２ are each independently a group consisting of one or more selected from the group consisting of a direct bond, —O—, and —NH—. Item 3. The repellent according to Item 1, wherein X is bonded by a group represented by the following formula or a direct bond: １ and X ２ [Item 4] The compound (a) is a compound represented by the following formula: １ -CO-R ２ , —CO—NR １ -R ２ , -NH-CO-NR １ -R ２, and -NR １ —CO—NH—R ２ [In the formula, R １ are each independently a hydrogen atom or a monovalent hydrocarbon group having from 1 to 20 carbon atoms which may have a substituent, and R ２ and each independently represent a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent.]. [Item 5] The compound (a) is a polyamine modified product having one or more amino groups or derivatives thereof, obtained by modifying an amino group of a polyamine with a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent. [Item 6] The polyamine modified product is a polyamine modified product represented by the following formula: N(R ３ ) ｌ (-H) ｍ -L １ - [NR １ -L １ -] ｔ -N(-CO-R ２ ) ｐ (-H) ｑ [In the formula, L 1 are each independently a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, and R １ are each independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ２ are each independently a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, ３ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or —CO—R ２Item 7. The repellent according to any one of Items 1 to 4, wherein the compound (a) is a compound represented by the formula: [wherein t is an integer of 0 or more and 10 or less, p is an integer of 1 or more and 2 or less, q is an integer of 0 or more and 2 or less, p+q is 2, l is an integer of 0 or more and 2 or less, m is an integer of 0 or more and 2 or less, and l+m is 2. [Item 7] The repellent according to any one of Items 1 to 4, wherein the compound (a) is a polycarboxylic acid modified product having one or more carboxyl groups or derivatives thereof, obtained by modifying a carboxyl group of a polycarboxylic acid with a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent. [Item 8] The polycarboxylic acid modified product is a compound represented by the formula: A{-CONR ２ -R １} ｎ {-COOH} ｍ [wherein A is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent to tetravalent aromatic hydrocarbon group; R １ are each independently a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, ２ are each independently a hydrogen atom or a straight-chain or branched-chain aliphatic hydrocarbon group having from 1 to 20 carbon atoms, n is an integer of from 1 to 4, m is an integer of from 1 to 4, and n + m is an integer of from 2 to 4. [Item 9] The liquid repellent according to any one of Items 1 to 8, wherein the liquid repellent compound further comprises a moiety derived from compound (c), and compound (c) is a monocarboxylic acid or derivative thereof having a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, and / or a monoamine or derivative thereof having a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. [Item 10] The compound (a) is a modified polyamine obtained by modifying an amino group of a polyamine with a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent; the compound (b) is a polycarboxylic acid that does not have a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent; and the moiety derived from the compound (a) and the moiety derived from the compound (b) are represented by the following formula: -X １ -CO-X ２- [wherein, X １ and X ２ are each independently a group consisting of one or more selected from the group consisting of a direct bond, —O—, and —NH—.] The repellent according to item 1, wherein the liquid repellent compounds are bonded via a group represented by the formula: [Item 11] The repellent according to any one of items 1 to 10, wherein the compound (a) and the compound (b) are compounds other than sugar alcohols. [Item 12] The repellent according to any one of items 1 to 11, wherein the liquid repellent compound does not have a fluorine atom. [Item 13] The repellent according to any one of items 1 to 12, which is an organic solvent solution, an organic solvent dispersion, or an aqueous dispersion. [Item 14] A method for producing a textile product, which comprises applying the repellent according to any one of items 1 to 13 to a textile substrate. [Item 15] A textile product in which the liquid repellent compound of the repellent according to any one of items 1 to 13 is adhered to a textile substrate.

[0007] According to the present disclosure, a new repellent agent capable of imparting liquid repellency to a substrate can be provided.

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

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

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

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

[0012] <Repellent Agent> The repellent agent in the present disclosure adheres to a substrate (particularly a fiber substrate and / or a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and can also function as a water-resistant agent, oil-resistant agent, water repellent agent, oil repellent agent, and / or stain resistance agent. The repellent agent in the present disclosure is particularly suitable as an oil-resistant agent that imparts oil resistance to a substrate (particularly a fiber substrate and / or a pulp substrate).

[0013] The liquid repellent of the present disclosure includes a moiety derived from compound (a) having a structure in which a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, is bonded to a carbon atom or a nitrogen atom of an amide group or a urea group, and having one or more reactive groups, and a moiety derived from compound (b) having two or more reactive groups and not having a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent.

[0014] The repellent agent of the present disclosure can be attached to a substrate (particularly a textile product and / or a pulp product) and impart good liquid repellency to the substrate.

[0015] 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.

[0016] The volumetric abundance ratio of particles of 100 μm or larger in the repellent agent of the present disclosure, as measured by a laser diffraction scattering method, may be 0.1% or larger, 0.3% or larger, 0.5% or larger, 1% or larger, 1.5% or larger, 3% or larger, 4% or larger, 5% or larger, or 10% or larger, or may be 50% or smaller, 30% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or smaller, 3% or smaller, or 1.5% or smaller, preferably 20% or smaller, and more preferably 5% or smaller. The method for achieving the volumetric abundance ratio of such particles within the above range is not limited, and may involve, for example, micronizing the particles in the raw material and / or dispersion using a grinder, homogenizer, or the like.

[0017] The volumetric abundance ratio of particles of 10 μm or larger in the repellent agent of the present disclosure, as measured by a laser diffraction scattering method, may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, or may be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, preferably 30% or less, more preferably 15% or less. The method for achieving the volumetric abundance ratio of such particles within the above range is not limited, and may be, for example, by micronizing the particles in the raw material and / or dispersion using a grinder, homogenizer, or the like.

[0018] The volume median diameter of the repellent agent of the present disclosure, as measured by a laser diffraction scattering method, may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, or may be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less, and in one embodiment, 0.01 μm or more and 1 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in a volume-based particle size distribution measured by a laser diffraction scattering method.

[0019] [Liquid-repellent compound] The liquid-repellent compound of the present disclosure has a moiety derived from a compound (a) having a structure in which a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, is bonded to a carbon atom or a nitrogen atom of an amide group or a urea group, and having one or more reactive groups, and a moiety derived from a compound (b) having no monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, and having two or more reactive groups.

[0020] The liquid-repellent compound of the present disclosure is a compound obtained by reacting compound (a) with compound (b), and has a portion derived from compound (a) and a portion derived from compound (b).

[0021] Specifically, the reactive group of compound (a) reacts with the reactive group of compound (b) to form the liquid-repellent compound of the present disclosure having a portion derived from compound (a) and a portion derived from compound (b).

[0022] Between the portion derived from compound (a) and the portion derived from compound (b), an organic group is formed by the reaction between the reactive group of compound (a) and the reactive group of compound (b). Such an organic group may be at least one selected from the group consisting of an amide group, a urea group, an ester group, and a urethane group. These groups can improve the film-forming properties of the repellent on a substrate.

[0023] The moiety derived from compound (a) and the moiety derived from compound (b) are represented by the following formula: -X １ -CO-X ２ - [wherein, X １ and X ２ are each independently a group consisting of one or more selected from the group consisting of a direct bond, —O—, and —NH—.] or a direct bond.

[0024] [X １ ] X １ are each independently a group consisting of one or more selected from the group consisting of a direct bond, —O—, and —NH—.

[0025] [X ２ ] X ２ are each independently a group consisting of one or more selected from the group consisting of a direct bond, —O—, and —NH—.

[0026] [-X １ -CO-X ２ -Example] -X １ -CO-X ２ Examples of - include -CO-O-, -CO-NH-, -O-CO-, -O-CO-NH-, -NH-CO-, -NH-CO-O-, or -NH-CO-NH-.

[0027] In the present disclosure, —CO— can mean —C(═O)—.

[0028] X １ and X ２ One of the groups may be —NH—.

[0029] The repellent agent of the present disclosure includes a liquid repellent compound that adheres to a substrate (particularly a fiber substrate and / or a pulp substrate) and imparts liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, particularly oil resistance, to the substrate.

[0030] [Characteristics, etc.] The characteristics, etc. that the liquid repellent compound may have are listed below.

[0031] The HD (n-hexadecane) contact angle of the liquid-repellent compound may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may be 100° or less, 90° or less, or 75° or less. When the liquid-repellent compound has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly oil repellency) to the substrate. The HD contact angle is the static contact angle of the liquid-repellent compound with respect to a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film at room temperature (25° C.) and measuring the contact angle 1 second after the drop lands.

[0032] The water contact angle of the liquid-repellent compound may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the liquid-repellent compound has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the liquid-repellent compound with respect to a spin-coated film, and is obtained by dropping 2 μL of water onto the spin-coated film at room temperature (25° C.) and measuring the contact angle 1 second after the drop has landed.

[0033] The liquid-repellent compound is preferably a biobased compound containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased content means that the amount of fossil resource-based materials, such as petroleum, used is small. From this perspective, the higher the biobased content of the liquid-repellent compound, the better.

[0034] The biodegradability of the liquid-repellent compound after 180 days is preferably 5% or more. Since this reduces the environmental impact, a higher biodegradability is preferable. The biodegradability of the liquid-repellent compound after 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more. The biodegradability of the liquid-repellent compound after 60 days is preferably 5% or more. Since this reduces the environmental impact, a higher biodegradability is preferable. The biodegradability of the liquid-repellent compound after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, more preferably 30% or more. Such biodegradability may be biodegradability as defined in JIS K 6953-1 or ASTM D6400.

[0035] The liquid repellent compound may be a low molecular weight (for example, a weight average molecular weight of less than 1500, less than 1000, or 500 or less) and / or a high molecular weight. The weight average molecular weight of the liquid repellent compound may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0036] [Compound (a)] The liquid-repellent compound has a structure in which a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, is bonded to a carbon atom or a nitrogen atom of an amide group or a urea group, and has a moiety derived from compound (a) having one or more reactive groups.

[0037] [Structure, etc.]

[0038] The compound (a) may not have any one selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom.

[0039] Compound (a) may be a compound other than a sugar alcohol. For example, compound (a) may be a compound that does not have a sugar alcohol skeleton. A sugar alcohol is a polyhydric alcohol obtained by reducing the aldehyde group and ketone group of a sugar to an alcohol group. Examples of sugar alcohols include sorbitol, xylitol, maltitol, erythritol, and mannitol. The sugar alcohol skeleton refers to the molecular structure of a cyclic or acyclic sugar alcohol when one or more H atoms of the sugar alcohol are removed from the hydroxyl group -OH.

[0040] [Amide Group or Urea Group] The compound (a) has a structure in which a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, is bonded to a carbon atom or a nitrogen atom of an amide group or a urea group.

[0041] The carbon atom or nitrogen atom of the amide group or urea group in compound (a) may each independently have one, or two or more, monovalent hydrocarbon groups having 6 to 40 carbon atoms and which may have a substituent bonded thereto.

[0042] The monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, may be bonded to a nitrogen atom or a carbon atom of the amide group. The monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, may be bonded to a nitrogen atom of the amide group. The monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, may be bonded to a carbon atom of the amide group.

[0043] The monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, may be bonded to the nitrogen atom of the urea group.

[0044] Compound (a) may have one or more amide groups or urea groups bonded to a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, for example, two or more, three or more, or five or less, four or less, three or less, and typically one.

[0045] (Monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent) The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and particularly an aliphatic hydrocarbon group, such as a saturated or unsaturated aliphatic hydrocarbon group (such as an alkyl group or an alkenyl group). The hydrocarbon group may be branched, cyclic, or linear, and is more preferably linear.

[0046] The hydrocarbon group is typically monovalent and may be located at the end of the molecule, and the hydrocarbon group may have one or more methyl groups at the end. In this specification, a hydrocarbon compound (e.g., hydrocarbon wax) is understood to consist of only a monovalent hydrocarbon group and one hydrogen atom, and for example, an n-alkane having 20 carbon atoms (eicosane) is understood to consist of only an alkyl group having 20 carbon atoms and one hydrogen atom.

[0047] The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 6 or more, 10 or more, 12 or more, or 16 or more, and may be 75 or less, 65 or less, 60 or less, 50 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 40 or less, 30 or less, 25 or less, or 20 or less, and in one aspect, 6 or more and 60 or less, 6 or more and 40 or less, 12 or more and 30 or less, or 12 or more and 20 or less. The number of carbon atoms in the hydrocarbon group may typically be 6 or more and 40 or less.

[0048] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR' and -N(R'). ２, —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) —OR′ (particularly —OH) as a substituent (e.g., other than at the terminal).

[0049] Compound (a) is a compound represented by the following formula: １ -CO-R ２ , —CO—NR １ -R ２ , -NH-CO-NR １ -R ２ , and -NR １ —CO—NH—R ２ [In the formula, R １ are each independently a hydrogen atom or a monovalent hydrocarbon group having from 1 to 20 carbon atoms which may have a substituent, and R ２ are each independently a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.] ２ is a group bonded to a carbon atom or nitrogen atom of an amide or urea group.

[0050] In the above formula, -NR １ -CO-R ２ and -CO-NR １ -R ２ means a structure in which a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, is bonded to a nitrogen atom or a carbon atom of an amide group.

[0051] In the above formula, —NH—CO—NR １ -R ２ and -NR １ —CO—NH—R ２ means a structure in which a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, is bonded to the nitrogen atom of a urea group.

[0052] R １ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched.

[0053] The carbon number of the aliphatic hydrocarbons having 1 to 20 carbon atoms may be 1 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0054] The aliphatic hydrocarbon having 1 to 20 carbon atoms may have a substituent, but is preferably unsubstituted. 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 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) —OR′ (particularly —OH) as a substituent (e.g., other than at the terminal).

[0055] R ２R each independently has a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent. ２ The above description of (a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent) is used, but it is preferable that the hydrocarbon group does not have a substituent. Here, the hydrocarbon group is a monovalent group. The hydrocarbon group of compound (a) may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group is branched or linear, and more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and is preferably 30 or less, 25 or less, or 20 or less.

[0056] [Reactive Group] The compound (a) has one or more reactive groups. The reactive groups of the compound (a) are different from the reactive groups of the compound (b).

[0057] The reactive group possessed by the compound (a) may be a hydroxy group, an amino group, a carboxyl group, an isocyanate group, or a derivative thereof, but is typically an amino group or a carboxyl group.

[0058] The reactive group of compound (a) may be a reactive group that reacts with the reactive group of compound (b) to form an amide group, a urea group, an ester group, a urethane group, or the like, and is preferably a reactive group that forms an amide group or a urea group.

[0059] Compound (a) may have one or more reactive groups, or may have two or more, three or more, four or more, or five or more, or may have ten or fewer, eight or fewer, six or fewer, five or fewer, or three or fewer, and in one embodiment, one or more and five or fewer, or one or more and three or fewer reactive groups.

[0060] [Polyamine Modification] The compound (a) may be a polyamine modification. Specifically, the compound (a) is a compound obtained by modifying an amino group of a polyamine with a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, and may have one or more amino groups or derivatives thereof.

[0061] The modified polyamine may be a compound obtained by reacting a polyamine with a fatty acid having a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, and may have one or more amino groups.

[0062] The polyamine modification may be a polyamine modification having one or more amide structures, such as a polyamide in which an amine (a raw amine compound, such as a polyamine) is modified with one or more modifying groups via an amide structure. Here, the amide may be an amide structure contained in a urethane group, a urea group, an imide, or the like. The polyamine modification may have a structure in which a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, is bonded to a carbon atom of the amide group.

[0063] The modifying group may preferably be a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.

[0064] Compound (a) may be a compound obtained by modifying an amino group of a polyamine with a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. Here, the monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, is the same as the above description of (monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent).

[0065] Compound (a) may have one or more amino groups or derivatives thereof, where the one or more amino groups or derivatives thereof are reactive groups of the present disclosure.

[0066] The modified polyamine has an amine skeleton. The amine skeleton has one or more amino groups with a predetermined number of bonds (valence) obtained by removing a predetermined number of atoms or atomic groups (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton has one or more —NH ２, -NH-, and -N(-) ２ and includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide group, etc. The amine skeleton may be an aliphatic or aromatic group having one or more amino groups, and does not exclude the presence of heteroatoms other than nitrogen.

[0067] The weight-average molecular weight of the amine skeleton may be 30 or more, 50 or more, 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more, and may be 2800 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 600 or less, 450 or less, 300 or less, or 250 or less.

[0068] The number of carbon atoms in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and may be 100 or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less, preferably 50 or less, particularly 30 or less.

[0069] The amine skeleton has one or more amino groups. The amino group is a monovalent to trivalent amino group, and has the structure -NH ２ , -NH-, and -N(-) ２ The number of amino groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, preferably 2 or more, and may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0070] The molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, and may be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, and is preferably 6 or less or 4 or less.

[0071] When compound (a) is a modified polyamine, the moiety derived from compound (a) may have a structure in which at least one hydrogen atom bonded to a nitrogen atom of the modified polyamine has been removed, or a structure in which a nitrogen atom of the modified polyamine and at least one hydrogen atom bonded to the nitrogen atom have been removed.

[0072] (Example of Polyamine Modified Product) The polyamine modified product is a compound represented by the following formula: N(R ３ ) ｌ (-H) ｍ -L １ - [NR １ -L １ -] ｔ -N(-CO-R ２ ) ｐ (-H) ｑ [In the formula, L 1 are each independently a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, and R １ are each independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ２ are each independently a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, ３ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or —CO—R ２ wherein t is an integer of 0 or more and 10 or less, p is an integer of 1 or more and 2 or less, q is an integer of 0 or more and 2 or less, p+q is 2, l is an integer of 0 or more and 2 or less, m is an integer of 0 or more and 2 or less, and l+m is 2.

[0073] L 1 L are each independently a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms which may have a substituent. 1 may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon.

[0074] L １may each independently have 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms, or may have 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less carbon atoms.

[0075] The divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms may have a substituent. Examples of the substituent include -OR' and -N(R'). ２ , —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (for example, 1) -OR' (particularly -OH) as a substituent (for example, at the terminal).

[0076] R １ are each independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. １ may have 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms, and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0077] The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may have a substituent. Examples of the substituent include -OR' and -N(R'). ２, —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (for example, 1) -OR' (particularly -OH) as a substituent (for example, at the terminal).

[0078] R ２ are each independently a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. The monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, is described above in relation to the monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent.

[0079] t is an integer of 0 or more and 10 or less. t may be 0 or more, 1 or more, 2 or more, 4 or more, or 6 or more, and is preferably 0 or more or 2 or more, and t may be 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1 or less, for example, 0 or 1.

[0080] p, in each occurrence, is independently an integer of 1 to 2, and q, in each occurrence, is independently an integer of 0 to 2, and p+q is 2. Preferably, p, in each occurrence, may be independently 1 or greater, for example, 2.

[0081] R ３ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or —CO—R ２ Here, the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is １The contents of "monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent" in the above are incorporated by reference.

[0082] l, in each occurrence, is independently an integer from 0 to 2, inclusive; m, in each occurrence, is independently an integer from 0 to 2, inclusive; and l+m is 2.

[0083] (Specific Example) Specific examples of the modified polyamine include the compounds represented by the following formula: ２ each independently mean a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. The above explanation of (monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent) is used for the monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. The compounds shown below have a structure in which an amino group in a polyamine is modified with one or two monovalent hydrocarbon groups having from 6 to 40 carbon atoms, which may have a substituent, but the number of modifications is not limited to these. For example, in the modified polyamine shown below, other unmodified amino groups in the molecule may be further modified with monovalent hydrocarbon groups having from 6 to 40 carbon atoms, which may have a substituent. In this case, the molecule must have one or more amino groups. The compounds shown below have a structure in which an amino group of a polyamine is modified with one or two monovalent hydrocarbon groups having from 6 to 40 carbon atoms, which may have a substituent, via -C(=O)-; however, the monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, may also have a structure in which it is directly bonded to the nitrogen atom of the amino group without via -C(=O)-.

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100] (Production Method) The method for producing the modified polyamine is not limited, but examples thereof include a synthesis method in which various polyamines are reacted with a modifying agent. The modifying agent may be a carboxylic acid having a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, an acid halide of a carboxylic acid, an acid anhydride, an isocyanate, or the like. If necessary, the reaction may be carried out in the presence of a condensing agent. The condensing agent may be a known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, or Py-Bop.

[0101] The polyamine to be reacted with the modifying agent is a compound having two or more amino groups. A polyamine is a compound having two or more amino groups in the molecule. The polyamine to be used for producing the modified polyamine of the present disclosure may be the polyamine described in detail below.

[0102] Examples of modifying agents that react with polyamines are: Acid halides G(O=)C-R ２ Acid anhydride O(C(=O)-R ２ ) ２ Carboxylic acid HO(O=)C-R ２ Isocyanate O=C=N-R ２ [In the formula, R ２is as defined above, and G is a halogen atom (e.g., F, Cl, Br, or I).

[0103] The modified polyamine may be synthesized by reacting a polyamine with the above-mentioned modifying agent. For example, a modifying agent such as an acid halide compound, an acid anhydride, or a carboxylic acid may be reacted with the amino group of a polyamine to form an amide bond to synthesize the modified polyamine. Such a modified polyamine has a structure in which a monovalent hydrocarbon group having 6 to 40 carbon atoms and optionally having a substituent is modified via an amide bond. Alternatively, a modifying agent such as an isocyanate may be reacted with the amino group of a polyamine to form a urea bond to produce the modified polyamine. Such a modified polyamine has a structure in which a monovalent hydrocarbon group having 6 to 40 carbon atoms and optionally having a substituent is modified via a urea bond to the polyamine.

[0104] Those skilled in the art can appropriately design the reaction conditions between the polyamine and the modifying agent, such as by using a catalyst (for example, an acid catalyst or a base catalyst) or a condensing agent, depending on the desired product.

[0105] A method for producing a modified polyamine according to one embodiment of the present disclosure is described below. Diethylenetriamine and stearic acid were stirred overnight in a Dean-Stark apparatus under a nitrogen atmosphere at an oil bath temperature of 130°C to 180°C. After the reaction was completed, the mixture was cooled to room temperature, and liquid-liquid extraction was performed using chloroform and pure water to recover the chloroform phase. After concentration under reduced pressure, the chloroform solution was added dropwise to hexane and stirred for 1 hour. The hexane was filtered to obtain the modified polyamine.

[0106] [Polycarboxylic Acid Modified Product] The compound (a) may be a polycarboxylic acid modified product. Specifically, the compound (a) is a compound obtained by modifying a carboxyl group of a polycarboxylic acid with a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, and may have one or more carboxyl groups or derivatives thereof.

[0107] The modified polycarboxylic acid may be a compound obtained by reacting a polycarboxylic acid with an alkylamine having a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, and may have one or more amino groups.

[0108] The modified polycarboxylic acid may be a modified polycarboxylic acid having one or more amide structures, for example, a polycarboxylic acid in which a carboxylic acid (a raw carboxylic acid compound, such as a polycarboxylic acid) is modified with one or more modifying groups via an amide structure. Here, the amide may be an amide structure contained in a urethane group, a urea group, an imide, or the like. The modified polycarboxylic acid may have a structure in which a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, is bonded to the nitrogen atom of the amide group.

[0109] The modifying group may preferably be a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.

[0110] Compound (a) may be a compound obtained by modifying a carboxyl group of a polycarboxylic acid with a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. Here, the monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, is the same as the above description of (monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent).

[0111] Compound (a) may have one or more carboxyl groups or derivatives thereof. Here, the one or more carboxyl groups or derivatives thereof are reactive groups of the present disclosure. The number of carboxyl groups or derivatives thereof possessed by the polycarboxylic acid modification may each independently be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, or may be 10 or less, 9 or less, 8 or less, 7 or less, or 5 or less.

[0112] The average molecular weight of the polycarboxylic acid modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0113] When compound (a) is a modified polycarboxylic acid, the moiety derived from compound (a) may have a structure in which at least one hydroxyl group of the modified polycarboxylic acid has been removed, or a structure in which at least one carboxyl group of the modified polycarboxylic acid has been removed.

[0114] (Examples of Polycarboxylic Acid Modified Compounds) The polycarboxylic acid modified compounds are represented by the following formula: A{-CONR １ -R ２} ｎ {-COOH} ｍ [wherein A is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent to tetravalent aromatic hydrocarbon group; R １ are each independently a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, ２ are each independently a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, n is an integer of 1 to 4, m is an integer of 1 to 4, and n+m is an integer of 1 to 4.

[0115] A is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent to tetravalent aromatic hydrocarbon group.

[0116] The di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4 or less, 3 or less, or 2.

[0117] Examples of divalent to tetravalent aromatic hydrocarbon groups include groups in which 2 to 4 hydrogen atoms have been removed from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the aromatic hydrocarbon group is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4 or less, 3 or less, or 2.

[0118] R １ are each independently a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms. １ may be a hydrogen atom.

[0119] The linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms may be either linear or branched.

[0120] The carbon number of the aliphatic hydrocarbons having 1 to 20 carbon atoms may be 1 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.

[0121] R ２ are each independently a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. The monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, is described above in relation to the monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent.

[0122] n is bonded to A -CONR １ -R ２ n is an integer of 1 to 4, and may be 1 to 3, 1 to 2, or 1.

[0123] m is the number of —COOH groups bonded to A. It is an integer of 1 to 4, and may be 1 to 3, 1 to 2, or 1.

[0124] n+m is an integer between 2 and 4 inclusive.

[0125] (Specific Example) Specific examples of the modified polycarboxylic acid include compounds represented by the following formula: ２ each independently means a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. The above description of the monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, is incorporated herein by reference. In the compounds shown below, the carboxyl groups of the polycarboxylic acid are modified with one or two monovalent hydrocarbon groups having from 6 to 40 carbon atoms, which may have a substituent, although the number of modifications is not limited thereto. For example, in the modified polycarboxylic acid shown below, other unmodified carboxyl groups in the molecule may be further modified with monovalent hydrocarbon groups having from 6 to 40 carbon atoms, which may have a substituent. In this case, the molecule must have one or more carboxyl groups.

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133] (Production Method) The method for producing the modified polycarboxylic acid is not limited, but examples thereof include a synthesis method in which various polycarboxylic acids are reacted with a modifying agent. The modifying agent may be an amine, epoxy, alcohol, or the like having a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. If necessary, the reaction may be carried out in the presence of a condensing agent. The condensing agent may be a known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, or Py-Bop.

[0134] The polycarboxylic acid to be reacted with the modifying agent is a compound having two or more carboxyl groups. The polycarboxylic acid is a compound having two or more carboxyl groups in the molecule. The polycarboxylic acid to be used for producing the modified polycarboxylic acid of the present disclosure may be the polycarboxylic acid described in detail below.

[0135] Examples of modifiers that can be reacted with polycarboxylic acids are: Epoxy (CH ２ OCH)CH ２ O-R ２ Amine H ２ N-R ２ Hydroxy HO-R ２ [In the formula, R ２ is as described above.]

[0136] The polycarboxylic acid-modified product may be synthesized by reacting a polycarboxylic acid with the above-mentioned modifying agent. For example, a modifying agent such as an alcohol or an epoxy compound may be reacted with a carboxyl group of a polycarboxylic acid to form an ester bond to produce a polycarboxylic acid-modified product. Such a polycarboxylic acid-modified product has a structure in which a monovalent hydrocarbon group having 6 to 40 carbon atoms and optionally having a substituent is modified on the polycarboxylic acid via an ester bond. Alternatively, a modifying agent such as an amine may be reacted with a carboxyl group of a polycarboxylic acid to form an amide bond to produce a polycarboxylic acid-modified product. Such a polycarboxylic acid-modified product has a structure in which a monovalent hydrocarbon group having 6 to 40 carbon atoms and optionally having a substituent is modified on the polycarboxylic acid via an amide bond.

[0137] Those skilled in the art can appropriately design the reaction conditions between the polycarboxylic acid and the modifying agent, such as by using a catalyst (for example, an acid catalyst or a base catalyst) or a condensing agent, depending on the desired product.

[0138] A method for producing a modified polycarboxylic acid according to one embodiment of the present disclosure is described below. Trimesic acid and stearylamine were stirred overnight in a Dean-Stark apparatus under a nitrogen atmosphere at an oil bath temperature of 130°C to 180°C. After the reaction was completed, the mixture was cooled to room temperature, and liquid-liquid extraction was performed using chloroform and pure water to recover the chloroform phase. After concentration under reduced pressure, the chloroform solution was added dropwise to hexane and stirred for 1 hour. The hexane was filtered to obtain the modified polycarboxylic acid.

[0139] [Compound (b)] The liquid-repellent compound has a moiety derived from compound (b) that does not have a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, and has two or more reactive groups.

[0140] [Structure etc.] Compound (b) may not have any one selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom.

[0141] Compound (b) may be a compound other than a sugar alcohol. For example, compound (b) may be a compound that does not have a sugar alcohol skeleton. A sugar alcohol is a polyhydric alcohol obtained by reducing the aldehyde group and ketone group of a sugar to an alcohol group. Examples of sugar alcohols include sorbitol, xylitol, maltitol, erythritol, and mannitol. The sugar alcohol skeleton refers to the molecular structure of a cyclic or acyclic sugar alcohol when one or more H atoms of the sugar alcohol are removed from the hydroxyl group -OH.

[0142] Compound (b) does not have an optionally substituted monovalent hydrocarbon group having from 6 to 40 carbon atoms. With regard to the optionally substituted monovalent hydrocarbon group having from 6 to 40 carbon atoms, the contents of (Optionally substituted monovalent hydrocarbon group having from 6 to 40 carbon atoms) are incorporated by reference.

[0143] [Reactive Group] Compound (b) has two or more reactive groups. The reactive groups of compound (b) are different from the reactive groups of compound (a).

[0144] The reactive group possessed by the compound (b) may be a hydroxy group, an amino group, a carboxyl group, an isocyanate group, or a derivative thereof, but is typically an amino group or a carboxyl group.

[0145] The reactive group of compound (b) may be a reactive group that reacts with the reactive group of compound (a) to form an amide group, a urea group, an ester group, a urethane group, or the like, and is preferably a reactive group that forms an amide group or a urea group.

[0146] Compound (b) may have two or more reactive groups, or may have three or more, four or more, or five or more, or may have 10 or less, 8 or less, 6 or less, 5 or less, or 3 or less, and in one embodiment, 2 or more and 5 or less, or 2 or more and 3 or less.

[0147] Examples of the compound (b) include polyamines, polycarboxylic acids, polyols, and polyisocyanates.

[0148] [Polyamine] A polyamine is a compound having two or more amino groups. A polyamine is a compound having two or more amino groups in the molecule. The polyamine may be aliphatic or aromatic, but is preferably aliphatic.

[0149] The polyamine may have a low molecular weight (e.g., a weight average molecular weight of less than 1,000, or 500 or less) and / or a high molecular weight. The weight average molecular weight of the polyamine may be 100 or more, 300 or more, 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or 1,000,000 or less, 7,500,000 or less, 500,000 or less, 3,000,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0150] The number of amino groups in the polyamine may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0151] The amine equivalent weight of the polyamine may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The amine equivalent weight of the polyamine is the value obtained by dividing the weight average molecular weight of the polyamine by the number of amino groups.

[0152] Examples of polyamines include alkylene diamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl)ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminoprotoxy)ethyl]ether, spermine, and spermidine; monocyclic aromatic polyamines such as o-, m-, or p-phenylenediamine, o-, m-, or p-xylylenediamine, diaminotoluene, and 2,3-, 2,4-, or 2,5-tolylenediamine;Diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenyl phenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenylketone, bisaminoditrifluoromethylbenzylbenzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, aminophenoxyphenyl sulfide, bis[amino-α, [α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, 4,4'-bis(aminophenyl)amine, and other polycyclic aromatic polyamines; and hydroxyl group-containing polyamines such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. The polyamine may be a polymerized compound such as allylamine.

[0153] In one embodiment, the polyamine may be replaced by an alkylamine such as methylamine, ethylamine, propylamine, butylamine, dibutylamine, etc.

[0154] When compound (b) is a polyamine, the moiety derived from compound (b) may have a structure in which at least one hydrogen atom bonded to a nitrogen atom of the polyamine has been removed, or a structure in which a nitrogen atom of the polyamine and at least one hydrogen atom bonded to the nitrogen atom have been removed.

[0155] [Polycarboxylic Acid] Polycarboxylic acid is a compound having two or more carboxyl groups. Polycarboxylic acid is a compound having two or more carboxyl groups in the molecule. Polycarboxylic acid may be aliphatic or aromatic, but is preferably aliphatic.

[0156] The polycarboxylic acid may be low molecular weight (e.g., weight average molecular weight less than 1,000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polycarboxylic acid may be 100 or more, 300 or more, 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or 1,000,000 or less, 7,500,000 or less, 500,000 or less, 3,000,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0157] The number of carboxyl groups in the polycarboxylic acid may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0158] The carboxyl group equivalent of the polycarboxylic acid may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The carboxyl equivalent of the polycarboxylic acid is the value obtained by dividing the weight average molecular weight of the polycarboxylic acid by the number of hydroxyl groups.

[0159] The polycarboxylic acid may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The natural product also includes compounds converted from microorganisms.

[0160] The polycarboxylic acid may be at least one selected from the group consisting of dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, carboxyl group-containing compound polymers, and salts thereof.

[0161] Dicarboxylic acids are compounds having two carboxyl groups, and examples thereof include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldaric acid, and salts thereof.

[0162] Tricarboxylic acids are compounds having three carboxyl groups, and examples thereof include citric acid, tricarballylic acid, t-aconitic acid, trimesic acid, trimellitic acid, tricarboxybenzene, and salts thereof.

[0163] The tetracarboxylic acid is a compound having four carboxyl groups, and examples thereof include pyromellitic acid and its salts.

[0164] The carboxyl group-containing compound polymer is a compound having five or more carboxyl groups, and examples thereof include alginic acid, tragacanth gum, gum arabic, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyglutamic acid, hyaluronic acid, heparin, xanthan gum, gellan gum, carboxymethylcellulose alginate, galacturonic acid, mannuronic acid, and salts thereof.

[0165] When compound (b) is a polycarboxylic acid, the moiety derived from compound (b) may have a structure in which at least one hydroxyl group of the polycarboxylic acid has been removed, or a structure in which at least one carboxyl group of the polycarboxylic acid has been removed.

[0166] [Polyol] A polyol is a compound having two or more hydroxy groups in the molecule. The polyol may be aliphatic or aromatic, but is preferably aliphatic.

[0167] The polyol may have an ether bond. Preferably, the polyol may have two or more ether bonds. Specifically, the polyol is preferably a compound having two or more hydroxy groups and two or more ether bonds. In other words, the polyol is preferably a polyether having two or more hydroxy groups.

[0168] When the polyol is a polymer, the repeating structure of the monomer unit may contain a hydroxy group and an ether bond.

[0169] The polyol may be low molecular weight (e.g., weight average molecular weight less than 1,000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol may be 50 or more, 100 or more, 300 or more, 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0170] The number of hydroxy groups in the polyol may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0171] The hydroxy group equivalent weight of the polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The hydroxy group equivalent weight of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxyl groups.

[0172] Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymers, hydroxypropyl (meth)acrylate polymers, and hydroxybutyl (meth)acrylate polymers.

[0173] When compound (b) is a polyol, the portion derived from compound (b) may have a structure in which at least one hydroxyl group or one hydrogen atom bonded to an oxygen atom of a hydroxyl group in the polyol has been removed.

[0174] [Polyisocyanate] Examples of polyisocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4', or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or aromatic polyisocyanates selected from 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI), ω,ω'-diisocyanato-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4-, or 1,8-naphthalene diisocyanate or mixtures thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate;acyclic aliphatic polyisocyanates selected from trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaprate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate; 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate or a mixture thereof) (hydrogenated MDI), methylcyclohexyl Cycloalicyclic polyisocyanates selected from among methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); bridged cycloaliphatic polyisocyanates selected from among norbornene diisocyanate, norbornane diisocyanatomethyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, and di(diisocyanatomethyl)tricyclodecane; and biuret-modified products of the above-mentioned isocyanates, polymers of polyisocyanates (for example, dimers, trimers (for example, isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (for example, allophanate derivatives produced by the reaction of the above-mentioned polyisocyanates with monohydric alcohols or dihydric alcohols), polyol derivatives (for example, polyol derivatives (alcohol adducts, preferably trimethylolpropane) produced by the reaction of the above-mentioned polyisocyanates with trihydric alcohols (for example, trimethylolpropane, etc.) Examples of the derivatives include biuret derivatives (e.g., biuret derivatives formed by the reaction of the above-mentioned polyisocyanates with water or amines), urea derivatives (e.g., urea derivatives formed by the reaction of the above-mentioned polyisocyanates with diamines), oxadiazinetrione derivatives (e.g., oxadiazinetrione formed by the reaction of the above-mentioned polyisocyanates with carbon dioxide), carbodiimide derivatives (e.g., carbodiimide derivatives formed by the decarboxylation condensation reaction of the above-mentioned polyisocyanates), uretdione derivatives, and uretonimine derivatives.

[0175] The average number of isocyanate groups in the polyisocyanate is 2 or more, preferably 2.5, more preferably 2.9, and for example, 3.8 or less. The polyisocyanate may be a polyisocyanate having a plurality of isocyanate groups.

[0176] When compound (b) is a polyisocyanate, the portion derived from compound (b) may have a structure in which one hydrogen atom is bonded to the nitrogen atom of an isocyanate group contained in the polyisocyanate, or a structure in which at least one isocyanate group contained in the polyisocyanate has been removed.

[0177] [Compound (c)] The liquid repellent compound of the present disclosure may further have a moiety derived from compound (c), which may be a monocarboxylic acid having a monovalent hydrocarbon group of 6 to 40 carbon atoms, which may have a substituent, or a derivative thereof, and / or a monoamine having a monovalent hydrocarbon group of 6 to 40 carbon atoms, which may have a substituent, or a derivative thereof.

[0178] [Monocarboxylic acid] Monocarboxylic acid and derivatives thereof have a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. Here, the monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, is the same as the above description of (monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent).

[0179] The derivative of the monocarboxylic acid may be a halide of the monocarboxylic acid, preferably a monocarboxylic acid chloride.

[0180] A monocarboxylic acid is a compound having one carboxyl group in the molecule. The monocarboxylic acid may be aliphatic or aromatic, but is preferably aliphatic.

[0181] The monocarboxylic acid may be, for example, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid, etc.

[0182] [Monoamine] Monoamine and derivatives thereof have a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. Here, the monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, is the same as the above description of (monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent).

[0183] The derivative of the monoamine may be a salt of the monoamine, preferably a hydrochloride or phosphate of the monoamine.

[0184] A monoamine is a compound having one amino group in the molecule. The monoamine may be aliphatic or aromatic, but is preferably aliphatic.

[0185] The monoamine may be dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, and the like.

[0186] The repellent of the present disclosure may further comprise the following ingredients:

[0187] [Wax] The repellent of the present disclosure may contain wax, particularly hydrocarbon wax. The wax may be an organic substance that is solid at room temperature and becomes liquid when heated, and may be, for example, a hydrocarbon compound or a compound having a hydrocarbon group (e.g., an alkyl group) having 6 to 40 carbon atoms.

[0188] The waxes of the present disclosure can be adhered to a substrate (particularly a pulp substrate) to impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance to the substrate.

[0189] [Characteristics of Wax, etc.] The characteristics of wax, etc. are shown below.

[0190] The wax may be in a particulate (powder) form. The average particle size of the wax may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, and may be 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, preferably 1 μm or less. The above particle size is the primary particle size. A particle size within the above range can provide excellent particle stability and good liquid repellency. The average particle size can be measured using a microscope (scanning electron microscope). Specifically, a wax particle sample is observed under a microscope at an arbitrary magnification. Next, if the particle shape is spherical, the diameter is considered to be the particle size, and if the particle shape is non-spherical, the average value of the longest and shortest diameters is considered to be the particle size. By measuring the particle size of all particles present within the field of view, and then moving the field of view and measuring the particle size again, particle sizes are measured at 100 or more points, and the average value is considered to be the average particle size.

[0191] The HD (n-hexadecane) contact angle of the wax may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may be 100° or less, 90° or less, or 75° or less. When the wax has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly oil repellency) to the substrate. The HD contact angle is the static contact angle of the wax with respect to a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle one second after the drop lands.

[0192] The water contact angle of the wax may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the wax has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the wax with respect to a spin-coated film, and is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle 1 second after the drop lands.

[0193] The wax may be a low molecular weight (e.g., a molecular weight of 1000 or less, or 500 or less) or a polymer. When the wax is a polymer, its weight average molecular weight may be 1000 or more, 3000 or more, 5000 or more, 7500 or more, 10000 or more, 30000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, or 10,000,000 or less, 7,500,000 or less, 5,000,000 or less, 3,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 3 ...,000 or less, 75000 or less, 50000 or less, or 3,000 or less.

[0194] The melting point of the wax may be 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, particularly preferably 55°C or higher, and may be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower, preferably 120°C or lower. The melting point of the wax may be measured in accordance with JIS K 2235-1991. The melting point usually corresponds to the peak top temperature of the endothermic peak with the maximum temperature before melting observed in DSC (differential scanning calorimetry).

[0195] [Types of Wax, etc.] Examples of waxes include mineral waxes (petroleum waxes) such as paraffin wax, microcrystalline wax, montan wax, ozokerite wax, ceresin wax, and petrolatum wax; and synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and polypropylene wax, and are preferably paraffin wax or microcrystalline wax. The wax in the present disclosure may be a hydrocarbon wax, preferably a chain aliphatic hydrocarbon, for example, a linear or branched hydrocarbon, and particularly a linear hydrocarbon.

[0196] [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, or 20 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound, and may be 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.

[0197] [Dispersant] The repellent of the present disclosure may contain a dispersant. The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be at least one selected from an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant. In particular, the repellent of the present disclosure may contain a nonionic dispersant.

[0198] As the dispersant, an organic dispersant and an inorganic dispersant may be used individually, or a combination of an organic dispersant and an inorganic dispersant may be used.

[0199] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may refer to a surfactant.

[0200] The dispersant may not have a fluorine atom.

[0201] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant, which may be a nonionic surfactant.

[0202] The nonionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the nonionic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0203] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0204] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0205] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0206] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0207] 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.

[0208] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0209] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0210] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0211] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, those in which the alkylene oxide adduct moiety and the polyalkylene glycol moiety have a structure of polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not have to contain an aromatic group.

[0212] The nonionic dispersant has the formula: １ O-(CH ２ CH ２ O)ｐ - (R ２ O) ｑ -R ３ [In the formula, R １ is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, ２ are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), ３ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.

[0213] R １ R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. １ Preferred specific examples of R include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. ２ Examples of the nonionic dispersant are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R ２ O) ｑ - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, with the oxypropylene chain being preferred.

[0214] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C １２ -C １６ ) thiol, sorbitan mono fatty acid (C ７ -C １９ ) or alkyl (C １２ -C １８) condensation products with amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0215] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may 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. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylenes having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0216] [Cationic Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0217] The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0218] The cationic dispersant may be aliphatic or aromatic, and examples thereof include ammonium salts (e.g., quaternary ammonium salts). The cationic dispersant may be an oxyethylene adduct ammonium salt. Specific examples include amine salt-type dispersants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymer-type cationic dispersants such as Polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0219] The low molecular weight cationic dispersant is R ２１ -N ＋ (-R ２２ ) (-R ２３ ) (-R ２４ ) X － [In the formula, R ２１ , R ２２ , R ２３ and R ２４ is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group. ２１ , R ２２ , R ２３ and -R ２４Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups) and aromatic groups (e.g., benzyl and phenyl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms) and benzalkonium chloride.

[0220] Specifically, the low molecular weight cationic dispersant is represented by the formula: １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g. C １２ ~C ５０ ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group of the formula R ２ is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH ３ , C ２ H ５ is particularly preferred), and X is a halogen atom (e.g., chlorine), or C １ ~C ４ or a fatty acid salt of C １ ~C ４ where p is 1 or 2, q is 2 or 3, and p+q=4. １ may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0221] Examples of low molecular weight cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0222] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to -47) having a cationic group (e.g., ammonium group, quaternary ammonium group). Examples of the polymeric cationic dispersant include cationic natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0223] [Anionic Dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0224] The anionic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the anionic dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0225] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid type dispersants, phosphate mono- or diester type dispersants, and sulfosuccinate esters. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0226] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant, which may be an amphoteric surfactant.

[0227] The amphoteric dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10,000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the amphoteric dispersant may be 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0228] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0229] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0230] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0231] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0232] [Amount of Dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0233] [Liquid Medium] The repellent agent of the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent agent may be a dispersion or a solution. The repellent agent of the present disclosure is preferably an aqueous dispersion or an aqueous dispersion.

[0234] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., alcohol, polyols such as glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination.

[0235] The repellent in the present disclosure may be an organic solvent solution or an organic solvent dispersion. An organic solvent solution refers to a liquid in which a solute is dissolved in a solvent to form a uniform phase. An organic solvent dispersion refers to a liquid in which a solute is suspended or floated in the form of particles in a solvent, and which can be separated into a solute (dispersoid) and a solvent (dispersoid) by centrifugation or the like.

[0236] [Amount of Liquid Medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

[0237] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

[0238] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

[0239] [Organic Acid] The repellent of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one 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.

[0240] [Amount of Organic Acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the 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).

[0241] [Inorganic Acid] The repellent of the present disclosure may contain an inorganic acid. Known inorganic acids can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present disclosure, one type of inorganic acid may be used, or two or more types may be used in combination. Adding an inorganic acid can improve the stability of the aqueous dispersion.

[0242] [Amount of Inorganic Acid] The amount of inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of inorganic acid may be adjusted so that the pH of the 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).

[0243] [Hardening Agent] The repellent of the present disclosure may contain a hardening agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). When the repellent is for paper (e.g., an oil-proofing agent for paper), it does not need to contain a hardening agent.

[0244] The curing agent (crosslinking agent) in the repellent agent can cure the agent well. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with active hydrogen or an active hydrogen-reactive group. Examples of 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, melamine compounds, and urea-based compounds.

[0245] 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.

[0246] 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.

[0247] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3,5-triisocyanatocyclohexane, 4,4'methylenebis(cyclohexyl isocyanate), and 1,3-bis(isocyanatomethyl)cyclohexane. These may be used alone or in combination of two or more.

[0248] 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.

[0249] 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.

[0250] 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.

[0251] 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.

[0252] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, and pyrazole compounds. The polyisocyanate compounds can be used alone or in combination of two or more.

[0253] 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.

[0254] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resin and methyl etherified melamine resin. Specific examples of urea compounds include dimethylol dihydroxyethylene urea (DMDHEU) and dimethyl dihydroxyethylene urea.

[0255] [Amount of Curing Agent] The amount of the curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0256] [Other Components] The repellent may contain components other than those described above. Other components may be added after the production of the hydrocarbon-based water-repellent resin. Examples of other components include water and / or oil repellents, antislip agents, antistatic agents, preservatives, antibacterial agents, deodorizers, and penetrating agents. These may be used alone or in combination of two or more. In addition to the above-described components, other components include texture adjusters, softeners, antibacterial agents, flame retardants, wrinkle inhibitors, crosslinking agents, film-forming aids, compatibilizers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrink inhibitors, anti-wrinkle agents, shape-retaining agents, drape-retaining agents, ironing improvers, polymer dispersants, scum dispersants, fluorescent brighteners, dye fixatives, and foam inhibitors. These may be used alone or in combination of two or more.

[0257] (Antistatic Agent) Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, and nonionic antistatic agents such as aminoalcohols and its derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. Ionic conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ionic conductive groups may also be used. These may be used alone or in combination of two or more.

[0258] (Preservatives) Preservatives can be used primarily to enhance preservative and bactericidal properties and maintain preservative properties during long-term storage. Examples of preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The content of the preservative is preferably 0.0001 to 1 wt % relative to the total weight of the repellent. When the content of the preservative is equal to or greater than the lower limit of the above range, the effect of adding the preservative is sufficiently obtained, and when it is equal to or less than the upper limit, the storage stability of the repellent is good.

[0259] (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.

[0260] (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).

[0261] (Anti-slip Agent) A component that has the effect of suppressing slippage of fibers and sewn parts during sewing or wearing. Examples of anti-slip agents include polysiloxane compounds, colloidal silicas, silicone resin derivatives, colloidal organic silicones, and amino-modified silicones.

[0262] (Softener) Softener is a component that has the effect of imparting a soft and smooth texture to fabrics. Examples of softener components include cationic surfactants such as quaternary ammonium salts and amine salts, anionic surfactants such as soap, sulfated oil, higher alcohol sulfate ester salts and sulfonate salts, nonionic surfactants such as polyhydric alcohols and polyethylene glycols, amphoteric surfactants such as betaines and amino acids, and siloxane resins.

[0263] [Amount of Other Components] The amount of each or the total amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0264] <Uses of Repellent Agent> Examples of uses of the repellent agent in the present disclosure include external treatment agents (surface treatment agents) or internal treatment agents, repellents (water repellents, oil repellents, or water and oil repellents, etc., particularly water repellents), antifouling agents, stain release agents, stripping agents, and release agents (external release agents or internal release agents).

[0265] <Method of Manufacturing Treated Product> A method of manufacturing a treated product in the present disclosure includes a step of treating a substrate with a repellent agent.

[0266] [Treated Products] Substrates that can be treated with the repellent of the present disclosure include fibrous substrates, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Various examples of fibrous substrates can be mentioned. Examples include natural fibers of animal and plant origin, such as cotton, linen, wool, and silk; synthetic fibers, such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers, such as rayon and acetate; inorganic fibers, such as glass fiber, carbon fiber, and asbestos fiber; and mixtures of these fibers. As an example of a substrate that can be treated with the repellent, a woven or knitted fabric will be described in detail.

[0267] (Woven and knitted fabrics) - Manufacturing method of knitted and woven fabrics Woven and knitted fabrics can be obtained by weaving and knitting long and short fiber yarns made of the above-mentioned fibers to obtain a greige fabric, which is then post-processed and subjected to a water-repellent treatment. The weaving and knitting can be performed using known looms and knitting machines, and known equipment can also be used for the preparation process prior to the weaving and knitting.

[0268] The woven or knitted fabric can be post-processed using known scouring and dyeing methods and equipment suited to the fiber material of the woven or knitted fabric.

[0269] After the post-processing, the woven or knitted fabric may be subjected to a water-repellent treatment. In the water-repellent treatment, first, an aqueous solution containing a water-repellent agent (which may be the repellent agent of the present disclosure) is prepared. Next, the aqueous solution is applied to the woven or knitted fabric after the post-processing using a padding method, a spray method, a kiss roll coater method, a slit coater method, or the like, and then dried and subjected to a dry heat treatment. The aqueous solution may also contain a crosslinking agent, a softener, an antistatic agent, or the like, as necessary. After the water-repellent treatment, the woven or knitted fabric may be calendered.

[0270] The woven and knitted fabrics are suitable for use in clothing applications requiring water repellency, particularly sportswear applications for outdoor activities, skiing, snowboarding, golf, etc., and uniform applications.

[0271] The woven / knitted fabric of the present disclosure may be provided as a laminated fabric having a moisture-permeable waterproof layer on one side thereof. The moisture-permeable waterproof layer may be laminated directly onto the woven / knitted fabric, or may be laminated onto the woven / knitted fabric via an adhesive layer. When the laminated fabric of the present disclosure is used for clothing or the like, the woven / knitted fabric side is arranged to repel rainwater and the like.

[0272] - Moisture-permeable waterproof layer The moisture-permeable waterproof layer is a layer that covers one side of a woven or knitted fabric, and is a layer formed of a waterproof and moisture-permeable resin or structural film.

[0273] The moisture-permeable waterproof layer may be formed by applying a resin (the resin that constitutes the moisture-permeable waterproof layer) directly to the woven or knitted fabric, or may be laminated to one side of the woven or knitted fabric via an adhesive layer described below.

[0274] The resin that constitutes the moisture-permeable waterproof layer is not particularly limited, but non-porous and porous resins are used. For non-porous ones, polyurethane resins and polyester elastomer resins that contain hydrophilic components are used to provide moisture permeability. For porous ones, polyurethane resins that form wet-process porous membranes and polyurethane resins that are made porous by electrospinning are used, as well as porous PTFE membranes and porous membranes made of PE or PP.

[0275] As the polyurethane resin, a conventionally known resin obtained by reacting a polyisocyanate component with a polyol component can be used.

[0276] A moisture-permeable waterproof membrane having a microporous structure can be obtained by wet coagulation of a DMF solution of a polyurethane resin containing an inorganic fine powder. Examples of inorganic fine powder include fine powders made of silicon dioxide, aluminum dioxide, or titanium dioxide. The average primary particle size of the inorganic fine powder is preferably about 7 to 40 nm. The content of the inorganic fine powder is preferably 3 to 50 wt %, and more preferably 5 to 50 wt %, of the total weight of the moisture-permeable waterproof layer.

[0277] The thickness of the moisture-permeable waterproof layer is preferably 5 μm or more, and more preferably 10 to 30 μm. A thickness within this range provides an excellent balance between waterproofness and moisture permeability, and is also advantageous in terms of texture.

[0278] Adhesive layer: The laminated fabric preferably includes an adhesive layer. That is, the woven or knitted fabric and the moisture-permeable waterproof layer are preferably laminated via an adhesive layer. In terms of moisture permeability, it is also preferable that the adhesive layer be a discontinuous layer such as a dot or grid pattern.

[0279] The type of adhesive that constitutes the adhesive layer is not particularly limited, but it is preferable that it has excellent adhesion to the moisture-permeable waterproof layer. For example, if a resin containing polyurethane resin as the main component is selected as the resin that constitutes the moisture-permeable waterproof layer, it is preferable to use an adhesive layer made of a polyurethane-based adhesive. The polyurethane-based adhesive may be of any structure, such as an ether-based, ester-based, or polycarbonate-based adhesive.

[0280] The adhesive layer may be formed over the entire surface of one side of the woven or knitted fabric, or may be formed in a pattern from the viewpoint of moisture permeability, texture, etc. The pattern shape is not particularly limited, but examples include dots, lines, a grid, a checkerboard pattern, a tortoiseshell pattern, etc., and it is preferable that any of these patterns be uniformly arranged over the entire surface.

[0281] The thickness of the adhesive layer is preferably about 10 to 100 μm, and more preferably 20 to 80 μm.

[0282] In the laminated fabric of the present disclosure, a lining fiber fabric may be laminated on the moisture-permeable waterproof layer (on the side of the moisture-permeable waterproof layer opposite to the side on which the woven or knitted fabric of the present disclosure is laminated). The lining fiber fabric can protect the moisture-permeable waterproof layer and can provide even better waterproofness (water pressure resistance) and strength.

[0283] Examples of the fiber fabric for the lining include various woven fabrics, knitted fabrics, etc. Among them, knitted fabrics are preferred because, compared with woven fabrics, the constituent yarns are more likely to protrude from the surface, resulting in an uneven surface, and the knitted fabric exhibits a stronger anchoring effect, making it less likely to peel off from the moisture-permeable waterproof layer.

[0284] Furthermore, tricot knitted fabrics are also preferred in that they can be produced as long grey fabrics during knitting, have few seams, and can be evenly layered on the moisture-permeable waterproof layer.

[0285] The material of the fibers constituting the lining fiber fabric is not particularly limited and can be selected as appropriate, but nylon fiber is preferred. This is because acid dyes are generally used in nylon fibers, which makes it less likely for the disperse dye to migrate and sublimate into the moisture-permeable waterproof layer, a problem that occurs with polyester fibers, etc., which use disperse dyes. The form (long fiber, short fiber, or spun yarn) or fineness of the fibers constituting the lining fiber fabric is not particularly limited and can be selected as appropriate as long as the effects of the present disclosure are not impaired.

[0286] Characteristics of the Laminated Fabric The laminated fabric has excellent waterproofness. A suitable example of the waterproofness of the laminated fabric of the present disclosure is a water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) of, for example, 10,000 mm or more, preferably 15,000 mm or more, more preferably 16,000 mm or more, and particularly preferably 20,000 mm or more.

[0287] The laminated fabric has excellent moisture permeability. A preferred example of the moisture permeability of the laminated fabric of the present disclosure is a moisture permeability of, for example, 10,000 g / m2, as measured in accordance with JIS L 1099:2021 B-1 method (potassium acetate method). 2 24 hours or more, preferably 15,000 g / m 2 24 hours or more, more preferably 20,000 g / m2 The upper limit of the moisture permeability is not particularly limited, but is, for example, 40,000 g / m 2 24h or 35,000g / m 2 24h mm. In addition, the moisture permeability measured in accordance with JIS L 1099:2021 A-1 method (calcium chloride method) is, for example, 4000 g / m 2 24 hours or more, preferably 8000 g / m 2 24 hours or more, more preferably 10,000 g / m 2 24 hours or more. The upper limit of the moisture permeability is 13,000 to 15,000 g / m2, which is the limit of the measurement method. 2 ・It will take about 24 hours.

[0288] In the laminated fabric of the present disclosure, the peel strength between the woven or knitted fabric and the breathable waterproof layer, as measured in accordance with the method of JIS K 6404-2, is preferably 2.55 N / 2.54 cm or more for clothing applications, and may be preferably 5 N / 2.54 cm or more for use in applications.

[0289] - Manufacturing method of laminated fabric There are no particular limitations on the manufacturing method of the laminated fabric, and examples include the first manufacturing method and the second manufacturing method shown below. First manufacturing method: Includes a step of forming the moisture-permeable waterproof layer by applying a resin that constitutes the moisture-permeable waterproof layer to the surface of a woven or knitted fabric. Second manufacturing method: Includes a step of forming an adhesive layer on the woven or knitted fabric or the moisture-permeable waterproof layer, and a step of bonding the woven or knitted fabric and the moisture-permeable waterproof layer together via the adhesive layer.

[0290] In the first manufacturing method, the resin that constitutes the moisture-permeable waterproof layer can be applied to the surface of the woven or knitted fabric by, for example, a coating method. A knife coater or a comma coater can be used in the coating method. From the viewpoint of providing excellent moisture permeability, it is preferable to obtain the moisture-permeable waterproof layer by a wet method.

[0291] In the second manufacturing method, examples of techniques for forming an adhesive layer on a woven or knitted fabric or a moisture-permeable waterproof layer include lamination. In the lamination method, a resin solution or a hot-melt method can be used to form the adhesive layer. First, a moisture-permeable waterproof layer-forming resin composition (e.g., a resin composition containing a resin and an organic solvent) is applied to the surface of a release material (such as release paper, release cloth, or release film) with a clearance, and a moisture-permeable waterproof layer is formed while adjusting the thickness. The film is then dried and heat-treated to obtain a film. The release material can be removed as appropriate after lamination or aging. Furthermore, when laminating using a hot-melt method, the release material can be peeled off and the film can be laminated alone. Furthermore, the moisture-permeable waterproof membrane can be formed by laminating a membrane produced by a solventless extrusion method such as the T-die method or inflation method, a porous membrane produced by electrospinning, or a porous membrane made of PTFE, PE, PP, or the like.

[0292] An adhesive layer is then formed on the woven or knitted fabric or the moisture-permeable waterproof layer. For example, in the case of a method using a resin solution, a two-component curing polyurethane resin solution adjusted to a viscosity in the range of 500 to 5,000 mPa·s may be applied to the entire surface or in a pattern. The resulting solution is then dried to form an adhesive layer, and the woven or knitted fabric and the moisture-permeable waterproof layer are bonded together via the adhesive layer, and the two are then pressure-bonded or thermocompression-bonded, thereby completing the second manufacturing method.

[0293] On the other hand, in the case of hot melt, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practical use, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, the hot melt resin is first melted while taking into consideration the melting point of the resin and its viscosity when melted. The second manufacturing method can then be carried out by applying the molten resin to the woven or knitted fabric or the moisture-permeable waterproof layer to form an adhesive layer, and bonding the woven or knitted fabric and the moisture-permeable waterproof layer together under pressure. Alternatively, if texture is important, the resin can be applied in a pattern to the moisture-permeable waterproof membrane and then bonded to the woven or knitted fabric.

[0294] Thereafter, a lining fiber fabric can be laminated on the moisture-permeable waterproof layer using any known appropriate method.

[0295] - Uses of laminated fabrics The laminated fabrics have excellent water repellency and breathable waterproof properties, and the breathable waterproof layer does not peel off even in harsh environments, making them suitable for use in fields such as uniforms, sportswear, and outdoor products used outdoors.

[0296] [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 repellent agent of the present disclosure may be dispersed and diluted in an organic solvent or water, if necessary, and applied to the surface of the substrate by a known method such as dip coating, spray coating, foam coating, or the like, followed by drying. After drying, a fibrous substrate with the solid components of the repellent adhered thereto is obtained. If necessary, the repellent agent may be applied together with an appropriate crosslinking agent and cured. Furthermore, the repellent agent of the present disclosure may be used in combination with various additives such as water and / or oil repellents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, and antifoaming agents. Examples of the various additives may be the same as those described above under "Other Components" for the repellent agent. The concentration of the hydrocarbon-based water-repellent resin 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.

[0297] [Fiber Substrate] Various examples of the fiber substrate as the substrate include cloth products and paper products.

[0298] Examples of textile products include natural fibers of animal or plant origin such as cotton, linen, wool, silk, etc., synthetic fibers such as polyamide, polyester (particularly polyethylene terephthalate is preferred), polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., semi-synthetic fibers such as rayon, acetate, etc., inorganic fibers such as glass fiber, carbon fiber, asbestos fiber, etc., or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, nonwoven fabrics, clothing fabrics, and carpets, but the treatment may also be applied to fibers, yarns, and intermediate textile products (for example, slivers or rovings) in a state prior to being made into textiles.

[0299] Examples of paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating mediums, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc.

[0300] The repellent agent can be applied to a fibrous substrate (e.g., fabric) by any of the known methods for treating the fibrous substrate with a liquid. The fibrous substrate may be immersed in the repellent agent, or the solution may be applied or sprayed onto the fibrous substrate. The treated fibrous substrate is preferably dried and cured by heating to develop water and oil repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0301] Alternatively, the liquid repellent compound may be applied to the textile substrate by a cleaning method, such as in a laundry application or a dry cleaning method.

[0302] The treated fibrous substrate may be a fabric, including woven fabrics, knitted fabrics, and nonwoven fabrics, clothing fabrics, carpets, etc., but may also be a fiber or yarn or intermediate fiber product (e.g., sliver or roving, etc.) The repellent agents of the present disclosure are particularly effective in making fibrous substrates (e.g., synthetic fibers) water repellent.

[0303] The fibers constituting the fibrous substrate may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, or inorganic fibers. The fibers may be used alone or in combination of two or more types.

[0304] Examples of natural fibers include cellulosic fibers such as cotton, flax, and pulp, chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as ground wood pulp (GP), pressure-raised ground wood pulp (PGW), and thermomechanical pulp (TMP), chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N wood), bleached softwood kraft pulp (NBKP; N wood, NB wood), unbleached hardwood kraft pulp (LUKP; L wood), and bleached hardwood kraft pulp (LBKP, L wood), recycled paper pulps such as deinking pulp (DIP) and waste pulp (WP), and semi-chemical pulp (CP).

[0305] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymer polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupra, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0306] Alternatively, the fibrous substrate may be leather. The liquid-repellent compound may be applied to the leather from an aqueous solution or emulsion at various stages of leather processing, for example, during the wet processing of the leather or during the finishing of the leather, to render the leather hydrophobic and oleophobic. Alternatively, the fibrous substrate may be paper. The liquid-repellent compound may be applied to preformed paper or may be applied at various stages of papermaking, for example, during the drying of the paper.

[0307] The term "treatment" means that the repellent agent is applied to a substrate by immersion, spraying, painting, etc. By the treatment, the liquid-repellent compound, which is the active ingredient of the repellent agent, penetrates into the interior of the substrate and / or adheres to the surface of the substrate.

[0308] [Pretreatment of Fiber Substrate] The fiber substrate may be pretreated before being treated with the repellent of the present disclosure. Pretreatment of the fiber substrate can impart excellent fastness to the fiber substrate after treatment with the repellent.

[0309] Examples of pretreatments of fiber substrates 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.

[0310] The method for pretreating the fibrous substrate is not limited, and the fibrous substrate 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 fibrous substrate 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 fibrous substrate, a method for pretreating a fibrous substrate with a hydrocarbon-based water repellent will be described in detail.

[0311] The pretreatment method for the fiber substrate 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").

[0312] 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 X２ 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.

[0313] 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.

[0314] 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.

[0315] The raw material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any of fibers (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, paper, etc.

[0316] In this embodiment, from the viewpoint of improving the water repellency of the resulting fiber substrate, it is preferable to use a fiber material containing polyamide and polyester as raw materials, and in particular, it is 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.

[0317] 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:

[0318] [In formula (2), X２ Ha-SO ３ M ３ (In the formula, M ３ represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0319] [In the formula, M ４ represents a monovalent cation.

[0320] The above M ３ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0321] The above M ４ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0322] 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.

[0323] Above - COOM ２ Examples of compounds having the formula include polycarboxylic acid polymers.

[0324] 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.

[0325] 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.

[0326] 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.

[0327] 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.

[0328] 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 fiber substrate.

[0329] 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.

[0330] 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.

[0331] 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.

[0332] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0333] 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.

[0334] 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.

[0335] 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.

[0336] 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.

[0337] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0338] 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.

[0339] 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.

[0340] 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.

[0341] 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.

[0342] (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).

[0343] 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.).

[0344] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0345] <Test Method> The test procedure is as follows.

[0346] [Water Contact Angle] A solution (or dispersion) of 1.0% solids content of the repellent agent was spin-coated onto a silicon wafer at 2000 rpm for 30 seconds to obtain a spin-coated film. This was then heated at 150°C for 5 minutes to produce a repellent-treated silicon wafer. Chloroform was used as the solvent or dispersion medium. 2 μL of water was dropped onto the repellent-treated silicon wafer, and the contact angle 1 second after the drop landed was recorded as the water contact angle.

[0347] [HD Contact Angle] A solution (or dispersion) of 1.0% solids of repellent was spin-coated onto a silicon wafer at 2000 rpm for 30 seconds to obtain a spin-coated film. This was then heated at 150°C for 5 minutes to produce a repellent-treated silicon wafer. Chloroform was used as the solvent or dispersion medium. 2 μL of hexadecane was dropped onto the repellent-treated silicon wafer, and the contact angle measured 1 second after the drop landed was taken as the water contact angle.

[0348] In a Dean-Stark apparatus under a nitrogen atmosphere, 18.1 g of diethylenetriamine and 10.0 g of stearic acid were stirred overnight at an oil bath temperature of 155°C. After completion of the reaction, the mixture was cooled to room temperature and subjected to liquid-liquid extraction with chloroform and pure water, and the chloroform phase was recovered. After concentration under reduced pressure, the chloroform solution was added dropwise to 500 mL of hexane and stirred for 1 hour. The hexane was filtered to obtain 9.49 g of polyamine-modified product. 1.56 g of this polyamine-modified product was weighed into a 30 mL side-arm reaction tube and placed under a nitrogen atmosphere. 2.67 g of triethylamine and 7 mL of dehydrated chloroform were added, and the mixture was heated and stirred (80°C, 700 rpm) until dissolved. 0.70 g of trimesoyl chloride was dissolved in 7 mL of dehydrated chloroform and added dropwise to the polyamine-modified product solution. The mixture was heated and stirred (80°C, 700 rpm) overnight. After cooling to room temperature, 30 mL of pure water was added to the reaction solution and stirred for 1 hour. The chloroform phase was added dropwise to 300 mL of methanol and stirred for 1 hour. The methanol was filtered to obtain 1.55 g of polymer. The water contact angle and HD contact angle of this polymer were evaluated. The results are shown in Table 1.

[0349] 1.45 g of the solid obtained in Example 1 was weighed into a 30 mL side-arm reaction tube and placed under a nitrogen atmosphere. 3.14 g of triethylamine and 7 mL of dehydrated chloroform were added, and the mixture was heated and stirred (90°C, 700 rpm) to dissolve. 0.94 g of stearic acid chloride was dissolved in 7 mL of dehydrated chloroform and added dropwise to the repellent solution. The mixture was heated and stirred overnight (90°C, 700 rpm). After cooling to room temperature, 30 mL of pure water was added to the reaction solution and stirred for 1 hour. The chloroform phase was added dropwise to 300 mL of methanol and stirred for 1 hour. The methanol was filtered to obtain 1.30 g of polymer. The water contact angle and HD contact angle of this polymer were evaluated. The results are shown in Table 1.

[0350] In a Dean-Stark apparatus under a nitrogen atmosphere, 5.0 g of triethylenetetramine and 17.5 g of stearic acid were stirred overnight at an oil bath temperature of 155°C. After completion of the reaction, the mixture was cooled to room temperature and subjected to liquid-liquid extraction with chloroform and pure water, and the chloroform phase was recovered. After concentration under reduced pressure, the chloroform solution was added dropwise to 500 mL of hexane and stirred for 1 hour. The hexane was filtered to obtain 10.5 g of polyamine-modified product. 1.94 g of this polyamine-modified product was weighed into a 30 mL side-arm reaction tube and placed under a nitrogen atmosphere. 1.93 g of triethylamine and 7 mL of dehydrated chloroform were added, and the mixture was heated and stirred (80°C, 700 rpm) until dissolved. 0.51 g of trimesoyl chloride was dissolved in 7 mL of dehydrated chloroform and added dropwise to the polyamine-modified product solution. The mixture was heated and stirred (80°C, 700 rpm) overnight. After cooling to room temperature, 30 mL of pure water was added to the reaction solution and stirred for 1 hour. The chloroform phase was added dropwise to 300 mL of methanol and stirred for 1 hour. The methanol was filtered to obtain 1.87 g of polymer. The water contact angle and HD contact angle of this polymer were evaluated. The results are shown in Table 1.

[0351] 0.34 g of the polyamine modified product from Example 3 was weighed into an 18 mL side-arm reaction tube and placed under a nitrogen atmosphere. 0.50 g of triethylamine and 2 mL of dehydrated chloroform were added, and the mixture was heated and stirred (90°C, 700 rpm) to dissolve. 0.10 g of terephthaloyl chloride was dissolved in 2 mL of dehydrated chloroform and added dropwise to the polyamine modified product solution. The mixture was heated and stirred (90°C, 700 rpm) overnight. After cooling to room temperature, 10 mL of pure water was added to the reaction solution and stirred for 1 hour. The chloroform phase was added dropwise to 200 mL of methanol and stirred for 1 hour. The methanol was filtered to obtain 0.18 g of polymer. The water contact angle and HD contact angle of this polymer were evaluated. The results are shown in Table 1. Comparative Example 1

[0352] An untreated silicon wafer was rinsed with ethanol and acetone and dried by heating at 150°C for 5 minutes to obtain an untreated silicon wafer. This substrate was used to evaluate water contact and HD contact angle. The results are shown in Table 1.

[0353]

Claims

1. A liquid repellent agent comprising a portion derived from a compound (a) having a structure in which a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent, is bonded to the carbon atom or nitrogen atom of an amide group or urea group, and having one or more reactive groups, and a portion derived from a compound (b) having two or more reactive groups and not having a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent.

2. The moiety derived from the compound (a) and the moiety derived from the compound (b) are represented by the following formula: -X １ -CO-X ２ - [wherein, X １ and X ２ are each independently a group consisting of one or more selected from the group consisting of a direct bond, —O—, and —NH—.

3. X １ and X ２ The repellent according to claim 2, wherein one of the groups is —NH—.

4. The compound (a) is represented by the following formula: —NR １ -CO-R ２ , —CO—NR １ -R ２ , -NH-CO-NR １ -R ２ , and -NR １ —CO—NH—R ２ [In the formula, R １ are each independently a hydrogen atom or a monovalent hydrocarbon group having from 1 to 20 carbon atoms which may have a substituent, and R ２ and each independently represents a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.]. The repellent according to any one of claims 1 to 3, comprising at least one group selected from the group consisting of groups represented by the following formulas:

5. A repellent according to any one of claims 1 to 4, wherein the compound (a) is a modified polyamine having one or more amino groups or derivatives thereof, wherein the amino groups of the polyamine are modified with monovalent hydrocarbon groups having 6 to 40 carbon atoms, which may have a substituent.

6. The polyamine modification has the following formula: N(R ３ ) ｌ (-H) ｍ -L １ - [NR １ -L １ -] ｔ -N(-CO-R ２ ) ｐ (-H) ｑ [In the formula, L 1 are each independently a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, and R １ are each independently a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ２ are each independently a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, ３ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or —CO—R ２ 6. The repellent according to claim 5, wherein the compound is represented by the formula: wherein t is an integer of 0 or more and 10 or less, p is an integer of 1 or more and 2 or less, q is an integer of 0 or more and 2 or less, p+q is 2, l is an integer of 0 or more and 2 or less, m is an integer of 0 or more and 2 or less, and l+m is 2.

7. A repellent according to any one of claims 1 to 4, wherein the compound (a) is a modified polycarboxylic acid having one or more carboxyl groups or derivatives thereof, wherein the carboxyl groups of the polycarboxylic acid are modified with monovalent hydrocarbon groups having 6 to 40 carbon atoms, which may have a substituent.

8. The polycarboxylic acid modified product has the following formula: A{-CONR １ -R ２ } ｎ {-COOH} ｍ [wherein A is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent to tetravalent aromatic hydrocarbon group; R １ are each independently a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, ２ are each independently a monovalent hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, n is an integer of 1 to 4, m is an integer of 1 to 4, and n+m is an integer of 2 to 4.

9. The liquid repellent according to any one of claims 1 to 8, wherein the liquid repellent compound further comprises a moiety derived from compound (c), wherein compound (c) is a monocarboxylic acid or derivative thereof having a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent, and / or a monoamine or derivative thereof having a monovalent hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent.

10. The compound (a) is a modified polyamine obtained by modifying an amino group of a polyamine with a monovalent hydrocarbon group having 6 to 40 carbon atoms, which may have a substituent; the compound (b) is a polycarboxylic acid having 6 to 40 carbon atoms, which may have a substituent, but which does not have a monovalent hydrocarbon group; the moiety derived from the compound (a) and the moiety derived from the compound (b) are represented by the following formula: -X １ -CO-X ２ - [wherein, X １ and X ２ are each independently a group consisting of one or more selected from the group consisting of a direct bond, —O—, and —NH—.

11. A repellent according to any one of claims 1 to 10, wherein the compound (a) and the compound (b) are compounds other than sugar alcohols.

12. The liquid repellent according to any one of claims 1 to 11, wherein the liquid repellent compound does not contain a fluorine atom.

13. The repellent according to any one of claims 1 to 12, which is in the form of an organic solvent solution, an organic solvent dispersion, or an aqueous dispersion.

14. A method for producing a textile product, comprising applying to a textile substrate a repellent agent according to any one of claims 1 to 13.

15. A textile product having a textile substrate to which the liquid-repellent compound of the repellent agent according to any one of claims 1 to 13 is adhered.

Images