Oil resistant agent composition

Abstract

Provided is an oil resistant agent composition that is solid and contains a liquid-repellent compound, a dispersant, and a filler.

Description

Oil-resistant composition

[0001] The present disclosure relates to oil-resistant compositions.

[0002] Patent Document 1 discloses an aqueous dispersion of a powdery papermaking composition.

[0003] Japanese Patent Application Laid-Open No. 2005-60921

[0004] The powdery papermaking composition of Patent Document 1 is provided as an aqueous dispersion, and is thought to be stored and used at an appropriate time and place. The aqueous dispersion of the powdery papermaking composition may settle during storage or use after provision. An aqueous dispersion in which settling has occurred may fail to achieve the desired performance when used.

[0005] The present disclosure provides an oil-proofing composition that is solid and capable of providing an aqueous oil-proofing dispersion upon use.

[0006] The present disclosure includes the following aspects: [Item 1] An oil-proofing composition comprising a liquid-repellent compound, a dispersant, and an excipient, and being solid. [Item 2] The oil-proofing composition according to Item 1, wherein the liquid-repellent compound has a hydrocarbon group or a polysiloxane group having from 6 to 40 carbon atoms. [Item 3] The oil-proofing composition according to Item 1 or 2, wherein the liquid-repellent compound comprises at least one selected from the group consisting of amine-modified compounds, polyol-modified compounds, polycarboxylic acid-modified compounds, and other solid oils. [Item 4] The liquid-repellent compound is selected from the group consisting of amine-modified compounds, polyol-modified compounds, and polycarboxylic acid-modified compounds, and the amine-modified compound has an amine skeleton, and a group represented by the following formula: -Y Ｎ -Z Ｎ ｎ [Y Ｎ Is Y Ｎ１ and Y Ｎ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｎ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —C(═S)—, —S—, —S(═O) ２ -, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２(wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), and Y Ｎ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Ｎ is a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, and n is an integer of 1 to 3.] Ｎ -Z Ｎ ｎ is bonded to a nitrogen atom of the amine skeleton; and the polyol modification product is a compound in which one or more hydroxy groups of the polyol are bonded to a nitrogen atom of the following formula: Ｏ -Z Ｏ ｎ [In the formula, Y Ｏ Is Y Ｏ１ and Y Ｏ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｏ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —C(═S)—, —S—, —S(═O) ２ -, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), and Y Ｏ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Ｏis a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, and n is an integer of 1 to 3.]; the polycarboxylic acid modified product is a compound in which a hydroxy group of one or more carboxyl groups of the polycarboxylic acid is substituted with a group represented by the following formula: -Y Ｃ -Z Ｃ ｎ [In the formula, Y Ｃ Is Y Ｃ１ and Y Ｃ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｃ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —C(═S)—, —S—, —S(═O) ２ -, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), and Y Ｃ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Ｃis a monovalent hydrocarbon group having from 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, and n is an integer of from 1 to 3. [Item 5] The amine skeleton is a skeleton obtained by removing at least one hydrogen atom from a nitrogen atom of at least one amine compound selected from the group consisting of ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine; 2-amino-1,3-propanediol; o-, m-, or p-xylylenediamine; 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, and 4,4'-oxydianiline; and the polyol is glucose, fructose, galactose, xylose; sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, or sucralose; Sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, gellan gum, tamarind seed gum; kojic acid, quinic acid, chlorogenic acid, gluconic acid; glucosamine; ascorbic acid, inositol; catechin, quercetin, anthocyanin; glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane;The polycarboxylic acid is at least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer, and the polycarboxylic acid is selected from the group consisting of citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, and aldaric acid; tricarballylic acid, t-aconitic acid, and trimellitic acid; pyromellitic acid; and carboxylic acids represented by the following formula CH; ２Item 4. The oil-proofing composition according to Item 4, wherein the other solid oil is at least one selected from the group consisting of a polymer containing a repeating unit derived from a compound represented by the formula: =C(-Q)-C(=O)-OH [wherein Q is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom] and derivatives thereof. [Item 6] The oil-proofing composition according to Item 3, wherein the other solid oil is at least one selected from the group consisting of rice wax, carnauba wax, hydrogenated castor oil, hydrogenated soybean oil, hydrogenated jojoba oil, hydrogenated rapeseed oil, sunflower wax, candelilla wax, 12-hydroxystearic acid, and privet wax. [Item 7] The oil-proofing composition according to any one of Items 1 to 6, wherein the amount of the dispersant is 0.1 to 80 parts by weight and the amount of the excipient is 0.1 to 100 parts by weight per 100 parts by weight of the liquid-repellent compound. [Item 8] The oil-proofing agent composition according to any one of Items 1 to 7, wherein the excipient comprises at least one selected from the group consisting of saccharides, polysaccharides and polysaccharide derivatives, water-soluble vinyl polymers and salts thereof, and silicates. [Item 9] The oil-proofing agent composition according to any one of Items 1 to 8, wherein the excipient comprises at least one selected from the group consisting of glucose (grape sugar), fructose (fruit sugar), galactose, dextrin, sucrose, lactose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, starch, modified starch, pullulan, guar gum, locust bean gum, tamarin seed gum, chitosan, gum arabic, karaya gum, pectin, konjac mannan, carrageenan, isomaltodextrin, mannitol, sorbitol, agar, alginic acid, xanthan gum, gellan gum, Agrobacterius sinoglycan, cationized guar gum, polyvinyl alcohol, polyacrylic acid, and sodium polyacrylate. [Item 10] The oil-proof composition according to any one of Items 1 to 9, wherein the dispersant comprises at least one selected from the group consisting of a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a polymer dispersant. [Item 11] The oil-proof composition according to any one of Items 1 to 10, wherein the oil-proof composition is in the form of a tablet, and the particle size thereof is 2,000 to 100,000 μm.[Item 12] The oil waterproofing composition according to any one of Items 1 to 11, wherein the water content of the oil waterproofing composition is 0.01% by weight to 20% by weight. [Item 13] The oil waterproofing composition according to any one of Items 1 to 12, further comprising at least one selected from the group consisting of a lubricant, a binder, and a disintegrant. [Item 14] The liquid repellent compound is an amine-modified compound, and the amine-modified compound is represented by the following formula: N(-C(=O)-Z. N ) p (-H) q -L 1 -[N(-C(=O)-Z N ) r (-H) s -L 1 -] t -N(-C(=O)-Z N ) p (-H) q [In the formula, Z Ｎ is independently in each occurrence an alkyl group having from 14 to 24 carbon atoms; 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, p is independently in each occurrence an integer of 1 to 2, q is independently in each occurrence 0 or 1, and p+q is independently in each occurrence an integer of 1 to 2, N ) p (-H) q In the formula, r is 2, r in each occurrence is independently 0 or 1, s in each occurrence is independently 0 or 1, and r+s is each N(-C(=O)-Z N ) r (-H) s[Item 15] Grease-resistant paper comprising the liquid-repellent compound, dispersant, and excipient of the oil-proofing composition of any one of Items 1 to 14. [Item 16] Grease-resistant paper of Item 15, which is a pulp-molded product. [Item 17] A method for producing an oil-proofing composition, comprising mixing a liquid-repellent compound, dispersant, excipient, and liquid medium to obtain a precursor mixture, and subjecting the precursor mixture to a heat treatment or a drying treatment to obtain a solid oil-proofing composition. [Item 18] A method for producing the oil-proofing composition of Item 17, comprising tableting the oil-proofing composition. [Item 19] A method for producing a paper product, comprising mixing the oil-proofing composition of any one of Items 1 to 14 with water to prepare an aqueous dispersion of the oil-proofing composition, and treating paper with the aqueous dispersion by external or internal addition treatment. [Item 20] A method for producing a pulp mold, comprising: mixing the oil-proofing composition according to any one of Items 1 to 14 with water to prepare an aqueous dispersion of the oil-proofing composition; filling a mold with the aqueous dispersion and a pulp base material; and allowing the water to permeate out of the mold to form a pulp.

[0007] The oil-proofing agent composition of the present disclosure is solid, and can provide an oil-proofing agent aqueous dispersion at the time of use. The oil-proofing agent composition of the present disclosure can be provided in a solid state, and does not need to be stored as an aqueous dispersion until use.

[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 １－２０ Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

[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] <Oil-proofing composition> The oil-proofing composition of the present disclosure comprises a liquid-repellent compound, a dispersant, and an excipient, and is solid. The oil-proofing composition of the present disclosure adheres to a substrate (particularly 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 oil-proofing composition of the present disclosure comprises a liquid-repellent compound. The liquid-repellent compound may be used as the oil-proofing composition by itself, or may be used in combination with other components as described below as the oil-proofing composition.

[0013] The oil-proofing composition of the present disclosure is also useful as an additive for paper products, and paper products obtained from a pulp composition to which the oil-proofing composition has been added can have improved performance (e.g., water resistance, oil resistance, paper strength, etc.).

[0014] "Solid" means a state in which the shape is fixed and there is no fluidity. One state that indicates "solid" is solid. A state that is not "solid" is liquid. A substance is "solid" if it can maintain its shape even when subjected to external forces such as gravity when placed on a flat surface and does not flow out to the surroundings. Therefore, "solid" not only refers to a completely solid state, but also includes states such as gel, rubber, paste, glue, and viscous. Note that powder is "solid" because it is an aggregate of fine solid particles. From the viewpoint of ease of handling, the oil-proofing agent composition of the present disclosure may be solid.

[0015] The oil-proofing composition of the present disclosure can impart oil resistance to a substrate and is solid. The oil-proofing composition of the present disclosure can be provided in a solid state, eliminating the need to store it as an aqueous dispersion until use. Unlike conventional aqueous dispersions, the oil-proofing composition of the present disclosure is added to a liquid medium (e.g., water) at the time of use to form a dispersion. Therefore, the oil-proofing composition of the present disclosure does not undergo settling of dispersoids during storage.

[0016] The water content of the oil-proofing composition of the present disclosure may be 0.01 wt% or more, 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, 0.7 wt% or more, 1.0 wt% or more, 1.5 wt% or more, 2.0 wt% or more, 3.0 wt% or more, 3.5 wt% or more, 4.0 wt% or more, 4.5 wt% or more, or 5.0 wt% or more. The water content of the oil-proofing composition of the present disclosure may be 20 wt% or less, 10 wt% or less, 9.0 wt% or less, 8.0 wt% or less, 7.0 wt% or less, 6.5 wt% or less, 6.0 wt% or less, 5.5 wt% or less, or 5.0 wt% or less. The water content of the oil-proofing composition can be determined in accordance with the loss on drying method of JIS K0068:2001, "Method for determining water content in chemical products."

[0017] The oil-proofing composition of 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 oil-proofing composition of the present disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds.

[0018] The method for measuring the particle size of the solid oil-proofing composition of the present disclosure may be changed depending on the particle size. For example, when the oil-proofing composition is a powder, the average particle size of the oil-proofing composition can be measured by a laser diffraction scattering method. When the oil-proofing composition is in the form of a tablet, as described below, the particle size can be measured using a vernier caliper in accordance with JIS B7507.

[0019] The volumetric abundance ratio of particles of 100 μm or larger in the solid oil-proofing composition 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. The volumetric abundance ratio of particles of 100 μm or larger in the oil-proofing composition of the present disclosure, as measured by a laser diffraction scattering method, 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. The method for achieving the volumetric abundance ratio of particles of 100 μm or larger in the above range, as measured by a laser diffraction scattering method, 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.

[0020] The solid oil-proofing composition of the present disclosure may have an average particle size, as measured by a laser diffraction scattering method, of 0.1 μm or more, 0.25 μm or more, 0.5 μm or more, 0.75 μm or more, 1 μm or more, 3 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 30 μm or more, 50 μm or more, 100 μm or more, 200 μm or more, 400 μm or more, 800 μm or more, or 1500 μm or more. The solid oil-proofing composition of the present disclosure may have an average particle size, as measured by a laser diffraction scattering method, of 3000 μm or less, 1000 μm or less, 500 μm or less, 50 μm or less, 30 μm or less, 20 μm or less, 10 μm or less, 5 μm or less, or 1 μm or less. The average particle size in this paragraph refers to the volume median diameter (D50) in a volume-based particle size distribution measured by a laser diffraction scattering method. Measurement by the laser diffraction scattering method is suitable when the oil-proofing agent composition is in the form of a powder. The term "powder" means an aggregate of particles having a diameter of 3000 μm or less.

[0021] The volumetric abundance ratio of particles of 100 μm or larger, as measured by laser diffraction scattering, in an aqueous dispersion composition obtained by redispersing the oil-proofing composition of the present disclosure in water 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. The volumetric abundance ratio of particles of 100 μm or larger, as measured by laser diffraction scattering, in an aqueous dispersion composition obtained by redispersing the oil-proofing composition of the present disclosure in water 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. The method for achieving the volumetric abundance ratio of particles of 100 μm or larger, as measured by laser diffraction scattering, 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.

[0022] The average particle size, as measured by a laser diffraction scattering method, of the water-dispersed composition obtained by redispersing the oil-proofing agent composition of the present disclosure in water may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.25 μm or more, 0.5 μm or more, 0.75 μm or more, 1 μm or more, 3 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 30 μm or more, 50 μm or more, 100 μm or more, 200 μm or more, 400 μm or more, 800 μm or more, or 1500 μm or more. The average particle size of the water-dispersed composition obtained by redispersing the oil-proofing composition of the present disclosure in water, as measured by a laser diffraction scattering method, may be 5000 μm or less, 3000 μm or less, 1000 μm or less, 500 μm or less, 50 μm or less, 30 μm or less, 20 μm or less, 10 μm or less, 5 μm or less, or 1 μm or less. In the present disclosure, the average particle size refers to the volume median diameter (D50) in the volume-based particle size distribution measured by a laser diffraction scattering method.

[0023] The oil-proofing composition of the present disclosure may be in the form of a tablet. A tablet form refers to a solid that maintains a certain shape, for example, a tablet-shaped lump. The shape of the tablet-shaped oil-proofing composition is not particularly limited, and may be a cube, a rectangular parallelepiped, a sphere, a cylinder, a prism, a cone, a pyramid, an ellipsoid, a cylinder, or a combination thereof. Processing into a tablet form can further improve handleability.

[0024] The tablet-shaped oil-proofing composition may be, for example, a product obtained by compressing and molding a powder-shaped oil-proofing composition. For example, the tablet-shaped oil-proofing composition may be a shaped body formed into a predetermined shape by tableting under high pressure. In other words, the tablet-shaped oil-proofing composition may be an agglomerate formed by solidifying powders together. The tablet-shaped oil-proofing composition may be prepared by firing the powder-shaped oil-proofing composition. Alternatively, the tablet-shaped oil-proofing composition may be dissolved in a liquid medium or the like and molded into a predetermined shape.

[0025] When the solid oil-proofing composition of the present disclosure is in tablet form, the particle size of the oil-proofing composition measured with a vernier caliper may be 2000 μm or more, 3000 μm or more, 4000 μm or more, 5000 μm or more, 7000 μm or more, 9000 μm or more, 10000 μm or more, 20000 μm or more, 30000 μm or more, 40000 μm or more, or 50000 μm or more. When the solid oil-proofing composition of the present disclosure is in tablet form, the particle size of the oil-proofing composition measured with a vernier caliper may be 500,000 μm or less, 300,000 μm or less, 100,000 μm or less, 80,000 μm or less, 70,000 μm or less, 60,000 μm or less, 50,000 μm or less, 30,000 μm or less, 10,000 μm or less, 5,000 μm or less, 30,000 μm or less, 10,000 μm or less, or 5,000 μm or less.

[0026] The size of the tablet-shaped oil-resistant composition is 10 mm ３ More than 20 mm ３ Above, 30mm ３ Above 50 mm ３ Above 70 mm ３ Over 100mm ３ , 150 mm ３ More than 200 mm ３ Above, 250mm ３ Over 300 mm ３ Over 400mm ３ or more, or 500 mm ３ The size of the tablet-shaped oil-proofing composition may be 1000 mm or more. ３ Below, 900mm ３ Below, 800mm ３ Below, 750mm ３ Below, 600mm ３ Below, 550mm ３ Below, 500mm ３ It may be the following:

[0027] [Liquid-repellent Compound] The liquid-repellent compound in the present disclosure is capable of adhering to a substrate (particularly a pulp substrate) and imparting liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate.

[0028] [Characteristics, etc.] The characteristics, etc. that the liquid repellent compound may have are listed below. These characteristics, etc. may vary depending on the type of compound.

[0029] 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. The HD contact angle of the liquid-repellent compound 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 and measuring the contact angle 1 second after the drop has landed.

[0030] The water contact angle of the liquid-repellent compound may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more. The water contact angle of the liquid-repellent compound may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the liquid-repellent compound has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the 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 on the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0031] 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.

[0032] 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.

[0033] The melting point of the liquid repellent compound may be 30° C. or higher, 40° C. or higher, 60° C. or higher, 80° C. or higher, 100° C. or higher, or 120° C. or higher, and is preferably 40° C. or higher. The melting point of the liquid repellent compound 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.

[0034] [Structure, etc.] The liquid-repellent compound in the present disclosure does not necessarily have any group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the liquid-repellent compound does not contain these fluorine-containing groups, it can impart liquid repellency to a substrate.

[0035] The liquid-repellent compound may be a compound having a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group. From the viewpoint of liquid repellency, the liquid-repellent compound may have a hydrocarbon group having 6 to 40 carbon atoms (for example, an alkyl group).

[0036] (Optionally Substituted Monovalent Hydrocarbon Group) The liquid repellent compound may have a monovalent hydrocarbon group which may have a substituent.

[0037] The hydrocarbon group may be a monovalent hydrocarbon group having from 1 to 40 carbon atoms. The hydrocarbon group 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 may be branched, cyclic, or linear, and is more preferably linear.

[0038] The number of carbon atoms in the hydrocarbon group may be 1 or more, 3 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, and preferably 6 or more, 10 or more, 12 or more, or 16 or more. The number of carbon atoms in the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and preferably 30 or less, 25 or less, or 20 or less.

[0039] 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. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (eg, 1) -OR' (particularly -OH) as a substituent (eg, other than at the terminal).

[0040] (Monovalent Polysiloxane Group) The liquid repellent compound may have a monovalent polysiloxane group. Like a (monovalent) hydrocarbon group, the (monovalent) polysiloxane group can impart liquid repellency to the substrate.

[0041] The polysiloxane group has the following formula: —[—Si(R ｓ ) ２ -O-] ａ - [wherein, R ｓ is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and a is an integer of 5 or more and 10,000 or less.

[0042] R ｓ is a hydrocarbon group having 1 to 40 carbon atoms or a reactive group.

[0043] Examples of hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms and hydrocarbon groups having 6 to 40 carbon atoms.

[0044] Examples of the hydrocarbon group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and other hydrocarbon groups having 1 to 5 carbon atoms (particularly an aliphatic hydrocarbon group, particularly an alkyl group such as a methyl group or an ethyl group, particularly a methyl group).

[0045] The hydrocarbon group having 6 to 40 carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, preferably linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more. The number of carbon atoms in the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

[0046] Examples of reactive groups include groups having functional groups (e.g., hydroxy groups, amino groups, mercapto groups, epoxy groups, carboxyl groups, halogen-substituted alkyl groups, vinyl groups, (meth)acrylic groups, (meth)acryloyloxy groups, (meth)acrylamide groups, hydrogen atoms directly bonded to silicon atoms, etc.). These functional groups may be directly bonded to the silicon atom, or may be bonded to an organic group directly bonded to the silicon atom. The organic group may be a hydrocarbon group, such as an alkylene group or a divalent aromatic group. The hydrocarbon group may have from 2 to 12 carbon atoms, and the alkylene group preferably has from 2 to 10 carbon atoms. The divalent aromatic group preferably has from 6 to 12 carbon atoms. The reactive group may be a group selected from the group consisting of a hydroxy group, an epoxy ring, a carboxyl group, a (meth)acrylic group, and an amino group, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0047] a may be 3 or more, 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, and is preferably 10 or more. a may be 10,000 or less, 7,500 or less, 5,000 or less, 3,000 or less, 1,500 or less, 1,000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, and is preferably 500 or less.

[0048] In the polysiloxane group, R is a hydrocarbon group having 1 to 5 carbon atoms. ｓ The amount of R ｓ The proportion of R which is a hydrocarbon group having 1 to 5 carbon atoms may be 20 mol % or more, 40 mol % or more, 60 mol % or more, or 80 mol % or more, and preferably 50 mol % or more, based on the total of R ｓ The amount of R ｓ For example, the total of R ｓ With respect to the total number of groups, 50 mol % or more may be methyl groups or ethyl groups (particularly methyl groups).

[0049] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms.ｓ The amount of R ｓ R which is a hydrocarbon group having 6 to 40 carbon atoms may be 3 mol % or more, 10 mol % or more, 20 mol % or more, or 30 mol % or more relative to the total of ｓ The amount of R ｓ may be 100 mol % or less, 90 mol % or less, 80 mol % or less, or 70 mol % or less based on the total of

[0050] In the polysiloxane group, reactive groups R ｓ The amount of R ｓ The reactive group R may be 5 mol % or more, 10 mol % or more, 20 mol % or more, or 30 mol % or more relative to the total of ｓ The amount of R ｓ may be 50 mol % or less, 40 mol % or less, 30 mol % or less, or 20 mol % or less based on the total of

[0051] R ｓ The groups may be introduced randomly or in blocks, but are preferably introduced randomly.

[0052] The terminal structure of the polysiloxane group is not limited, but may be -OR ｓ , -Si(R ｓ ) ３ etc. The R of the terminal structure ｓ Examples of the reactive group are as described above, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0053] The polysiloxane group may have a linker, and the raw material compound and the polysiloxane group may be bonded via a linker. Such a linker may be, but is not limited to, a hydrocarbon group having 1 to 40 (e.g., 1 to 20) carbon atoms which may be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 (e.g., 1 to 20) carbon atoms.

[0054] Examples of polysiloxane groups include -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ )３ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３ -L ｓ１ -O-L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３ -L ｓ１ -O-L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３、 -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ [In the formula, R ｓ is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and the terminal R ｓ has one or more reactive groups, and R ｓ 50 mol % or more of the total groups are methyl groups, and L ｓ１ is a hydrocarbon group having 1 to 20 carbon atoms, and a is 5 or more and 10,000 or less. [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a+b) is 5 to 200, and n is an integer of 0 to 36.]

[0055] [Examples of Liquid-Repellent Compounds] Examples of liquid-repellent compounds include compounds having a hydrocarbon group having a carbon number of 6 to 40. Examples and preferred ranges of the hydrocarbon group are as described above.

[0056] Examples of liquid repellent compounds include compounds selected from the group consisting of amine-modified, polyol-modified, and polycarboxylic acid-modified compounds, and other liquid or solid oils (discussed in more detail below).

[0057] The liquid repellent compound may include an ester group, an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group (e.g., an ester group, an amide group, a urethane group, a urea group, or an imide group). For example, the liquid repellent compound may include —C(═O)—O—, —O—C(═O)—, —C(═O)—NR′—, —O—C(═O)—NR′—, —NR′—C(═O)—NR′—, or —SO ２ The liquid repellent compound may contain NR'- (R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)). The liquid repellent compound may be a compound in which a raw material compound and a modifying group (particularly the monovalent hydrocarbon group which may have the above-mentioned substituent) are bonded via at least one of these groups. The liquid repellent compound may contain an amide structure. When the liquid repellent compound contains at least an amide structure, the liquid repellency can be improved. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide structures in amide (acid amide) groups, urethane groups, urea groups, imide groups, thioamide groups, thiourethane groups, thiourea groups, thioimide groups, sulfonamide groups, sulfoneurethane groups, sulfoneurea groups, sulfonimide groups, etc. The amide structure is -(C=O)N(-) ２ , -(C=S)N(-) ２ , and -S(=O) ２ N (-) ２ (Note that each group may be inverted). At least one of the bonds of N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-) ２ and may be an amide structure in a group selected from the group consisting of an amide group, a urethane group, a urea group, and an imide group.

[0058] [Amount of Liquid-Repellent Compound] The amount of the liquid-repellent compound in the oil-resistant composition may be 0.01 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, or 30 wt% or more. The amount of the liquid-repellent compound in the oil-resistant composition may be 95 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, or 3 wt% or less. The liquid-repellent compound may be used alone in the oil-resistant composition.

[0059] [Amine-modified compound] As an example of a liquid-repellent compound, an amine-modified compound will be described. The amine-modified compound is a compound obtained by chemically modifying an amine compound so as to exhibit liquid-repellency.

[0060] Due to their structure, the amine-modified compounds disclosed herein have excellent dispersibility in liquid media, and the oil-proofing compositions disclosed herein can have stable performance. Oil-proofing compositions that use polymeric compounds as active ingredients tend to have broad molecular weight distributions and contain relatively large amounts of impurities. On the other hand, the amine-modified compounds can be made into low-molecular-weight compounds, narrowing (uniformizing) the molecular weight distribution and improving performance.

[0061] [Structure etc.] The molecular weight of the amine-modified product may be 200 or more, 300 or more, 350 or more, 400 or more, 500 or more, 550 or more, or 750 or more. The molecular weight of the amine-modified product may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 900 or less, 800 or less, 750 or less, or 500 or less.

[0062] The amine-modified product of the present disclosure may not have an active hydrogen-containing group. Examples of the active hydrogen-containing group include an amino group (an amino group that is not adjacent to a carbonyl group, such as a primary or secondary amino group), a hydroxyl group, and a carboxyl group. In particular, the amine-modified product of the present disclosure may not have a primary or secondary amino group that is not adjacent to a carbonyl group.

[0063] The amine-modified product in the present disclosure may be a polyamide having a plurality of amide structures, for example, a polyamide having a plurality of modifying groups (for example, Z Ｎ ) may be a polyamide modified 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.

[0064] The amine-modified product may be a compound obtained by modifying an amine (raw amine compound) with a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0065] In the amine-modified product, one or more amino groups of the amine are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the amine-modified product may have a structure in which an amine is modified with an alkyl group having 6 to 40 carbon atoms.

[0066] For details of the monovalent hydrocarbon group which may have a substituent and the monovalent polysiloxane group, the above descriptions of the (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0067] (Amine skeleton) The amine modified product in the present disclosure has an amine skeleton. The amine skeleton has one or more amino groups with a predetermined number of bonds (valence) obtained by removing a predetermined number of atoms or atomic groups (e.g., hydrogen) from an amine compound. The amino group in the amine skeleton has one or more —NH ２ , -NH-, and -N(-) ２ and includes an amino group adjacent to a carbonyl group contained in an amide group, a urethane group, a urea group, an imide group, etc. The amine skeleton may be an aliphatic or aromatic group having one or more amino groups, and does not exclude the presence of heteroatoms other than nitrogen.

[0068] The molecular weight of the amine backbone may be 30 or more, 50 or more, 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more. The molecular weight of the amine backbone may be 2800 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 600 or less, 450 or less, 300 or less, or 250 or less.

[0069] The number of carbon atoms in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more. The number of carbon atoms in the amine skeleton may be 100 or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less, preferably 50 or less, particularly 30 or less.

[0070] The amine skeleton has one or more amino groups. The amino group is a monovalent to trivalent amino group, and has the structure -NH ２ , -NH-, and -N(-) ２ The number of amino groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 2 or more. The number of amino groups in the amine skeleton may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0071] The amine skeleton has a hydrocarbon group (an aliphatic hydrocarbon group or an aromatic hydrocarbon group). The hydrocarbon group may be cyclic, branched, or linear. The hydrocarbon group may be saturated or unsaturated (e.g., saturated). Here, the hydrocarbon group may be interrupted by oxygen atoms and / or sulfur atoms, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms. The hydrocarbon group may be a hydrocarbon group that may be interrupted by oxygen atoms and / or sulfur atoms (e.g., a linear saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having one to two hydrocarbon aromatic rings), or may be a general hydrocarbon group (e.g., a linear saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having one to two hydrocarbon aromatic rings). When the hydrocarbon group is interrupted by oxygen atoms and / or sulfur atoms, it has an ether, thioether, polyether, or polythioether structure. The number of hydrocarbon groups in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more. The number of hydrocarbon groups in the amine skeleton may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.

[0072] The amine skeleton may be composed of a monovalent to trivalent amino group and a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be interrupted by an oxygen atom and / or a sulfur atom.

[0073] The molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more. The molar ratio of carbon atoms to nitrogen atoms (C / N ratio) in the amine skeleton may be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, and is preferably 6 or less or 4 or less.

[0074] (-Y Ｎ -Z Ｎ ｎ The amine-modified compound in the present disclosure is represented by the following formula: Ｎ -Z Ｎ ｎ [In the formula, Y Ｎ is a direct bond or a group having a valence of 1+n; Z Ｎis a monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group which may have a substituent, and n is an integer of 1 to 3.] Ｎ -Z Ｎ ｎ is bonded to the nitrogen atom of the amine skeleton.

[0075] The amine-modified compound has -Y Ｎ -Z Ｎ ｎ The number of -Y in the amine modified product may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 2 or more. Ｎ -Z Ｎ ｎ 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.

[0076] At least one -Y in the amine modification Ｎ -Z Ｎ ｎ is bonded to the nitrogen atom of the amine skeleton. Ｎ -Z Ｎ ｎ Among the number of -Y bonded to the nitrogen atom of the amine skeleton, Ｎ -Z Ｎ ｎ The proportion of the number of -Y in the amine-modified product may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%. Ｎ -Z Ｎ ｎ Among the number of -Y bonded to the nitrogen atom of the amine skeleton, Ｎ -Z Ｎ ｎ The proportion of the number of —Y groups not bonded to a nitrogen atom of the amine skeleton may be 75% or less, 50% or less, or 25% or less. Ｎ -Z Ｎ ｎ is bonded to another group (for example, a hydrocarbon group) on the amine skeleton.

[0077] (Y Ｎ ) Y Ｎrepresents a direct bond or a group with a valence of (1+n), preferably a group with a valence of (1+n). Ｎ is an amine skeleton and n Z Ｎ It acts as a linker connecting the

[0078] n is Y Ｎ Z combines with Ｎ and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0079] Y Ｎ may be an aliphatic group (unsaturated or saturated) or an aromatic group.

[0080] Y Ｎ The molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more. Ｎ may have a molecular weight of 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 300 or less.

[0081] Y Ｎ may have a carbonyl group. Ｎ may have one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group, or Y Ｎ may form one or more groups selected from the group consisting of an amide group, a urea group, a urethane group, and an imide group together with the amino group in the amine skeleton. Examples of such an amide group, a urea group, a urethane group, and an imide group include: -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'-C(=O)- (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Ｎ is preferably bonded to the nitrogen atom in the amine skeleton via a —(C═O)— group.

[0082] Y Ｎ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２-, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , -N(-) ２ a di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a di- to tetravalent hydrocarbon aromatic ring, and a di- to tetravalent heterocyclic ring (wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)).

[0083] Y Ｎ Is Y Ｎ１ and Y Ｎ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｎ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), and Y Ｎ２ is a group consisting of one or more selected from the group consisting of divalent to tetravalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, divalent to tetravalent hydrocarbon aromatic rings, and divalent to tetravalent heterocycles, and may be a 1+n-valent group consisting of one or more selected from the group consisting of. Ｎ The group shown as follows has an amine skeleton on the left and Z on the right. Ｎ Combine with.

[0084] 〇 Y Ｎ１ Y Ｎ１ is a non-hydrocarbon linker.

[0085] Y Ｎ１ is a direct bond or a divalent or higher valent group. Ｎ１ The valence of Y may be 2 to 4, 2 to 3, or 2. Ｎ１ is preferably not only a direct bond.

[0086] Y Ｎ１The molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more. Ｎ１ may have a molecular weight of 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0087] Y Ｎ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Ｎ１ Examples of include a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—O—, —C(═O)—NR′—, —C(═O)—NR′—, —C(═O)—NR′—C(═O)—NR′—, —C(═NR′)—, —S—, and —SO ２ -, -SO ２ NR'-, -C(OR')R'-, -C(OR')(-) ２ , -N(-) ２ [wherein, R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).] Ｎ１ is bonded to a nitrogen atom of the amine skeleton, the nitrogen atom is considered to be part of the amine skeleton (amino group).

[0088] 〇 Y Ｎ２ Y Ｎ２ is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent.

[0089] Y Ｎ２ Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). Ｎ２Y may be aliphatic or aromatic. Ｎ２ may be linear, branched or cyclic.

[0090] Y Ｎ２ is a divalent or higher valent group. Ｎ２ The valency of may be, for example, 2-4, 2-3, or 2.

[0091] Y Ｎ２ The number of carbon atoms in Y may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more. Ｎ２ may have 40 or fewer, 35 or fewer, 30 or fewer, 25 or fewer, 20 or fewer, 15 or fewer, 10 or fewer, or 5 or fewer carbon atoms.

[0092] Y Ｎ２ is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0093] The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 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 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 35 or less, 30 or less, 25 or less, 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 4 or less, 3 or less, or 2.

[0094] The aliphatic hydrocarbon group 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 aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the substituted aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0095] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0096] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -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 aromatic ring, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the substituted hydrocarbon aromatic ring, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0097] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of divalent to tetravalent heterocycles include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0098] The heterocycle may have a substituent. Examples of the substituent include -R', -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 heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more. In the substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0099] Y Ｎ２ Examples of -Ali- -Cy- -Ali(-) ２ -Cy(-) ２ (-) ２ Ali- (-) ２ Cy- (-) ２ Ali (-) ２ (-) ２ Cy(-) ２ -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- (wherein Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.)

[0100] Y Ｎ２ Specific examples of -(CH ２ ) ｐ -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0101] ・Y Ｎ Example of Y Ｎ In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0102] Y Ｎ An example of this is Y Ｎ When is divalent, -Y Ｎ１ -, -Y Ｎ１ -Y Ｎ２ -, -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -, -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -, -Y Ｎ２ -, -Y Ｎ２ -Y Ｎ１ -, -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -, -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -, etc.

[0103] Y Ｎ An example of this is Y Ｎ When is trivalent, -Y Ｎ１ (-) ２ , -Y Ｎ１ -Y Ｎ２ (-) ２ , -Y Ｎ１ -(Y Ｎ２ -) ２ , -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ (-) ２ , -Y Ｎ１ -Y Ｎ２ (-Y Ｎ１ -) ２ , -Y Ｎ１ -(Y Ｎ２ -Y Ｎ１ -) ２ , -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ (-) ２ , -YＮ１ -Y Ｎ２ -Y Ｎ１ -(Y Ｎ２ -) ２、 -Y Ｎ１ -Y Ｎ２ -(Y Ｎ１ -Y Ｎ２ -) ２、 -Y Ｎ１ -(Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -) ２ ; -Y Ｎ２ (-) ２ ,-Y Ｎ２ -Y Ｎ１ (-) ２ ,-Y Ｎ２ -(Y Ｎ１ -) ２ ,-Y Ｎ２ -Y Ｎ１ -Y Ｎ２ (-) ２ ,-Y Ｎ２ -Y Ｎ１ (-Y Ｎ２ -) ２ ,-Y Ｎ２ -(Y Ｎ１ -Y Ｎ２ -) ２ ,-Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ (-) ２ ,-Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -(Y Ｎ１ -) ２、 -Y Ｎ２ -Y Ｎ１ -(Y Ｎ２ -Y Ｎ１ -) ２、 -Y Ｎ２ -(Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -) ２ etc. can be cited.

[0104] Y Ｎ As an example of Y Ｎ when Y is tetravalent, -Y Ｎ１ (-) ３ ,-Y Ｎ１ -Y Ｎ２ (-) ３、-Y Ｎ１ -(Y Ｎ２ -) ３ 、-Y Ｎ１ -Y Ｎ２ -Y Ｎ１ (-) ３ 、-Y Ｎ１ -Y Ｎ２ (-Y Ｎ１ -) ３ 、-Y Ｎ１ -(Y Ｎ２ -Y Ｎ１ -) ３ 、-Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ (-) ３ 、-Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -(Y Ｎ２ -) ３、 -Y Ｎ１ -Y Ｎ２ -(Y Ｎ１ -Y Ｎ２ -) ３、 -Y Ｎ１ -(Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -) ３ ; -Y Ｎ２ (-) ３ 、-Y Ｎ２ -Y Ｎ１ (-) ３ 、-Y Ｎ２ -(Y Ｎ１ -) ３ 、-Y Ｎ２ -Y Ｎ１ -Y Ｎ２ (-) ３ 、-Y Ｎ２ -Y Ｎ１ (-Y Ｎ２ -) ３ 、-Y Ｎ２ -(Y Ｎ１ -Y Ｎ２ -) ３ 、-Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ (-) ３ 、-Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -(Y Ｎ１ -)３、 -Y Ｎ２ -Y Ｎ１ -(Y Ｎ２ -Y Ｎ１ -) ３、 -Y Ｎ２ -(Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -) ３ ; etc.

[0105] Y Ｎ Preferred examples of -Y Ｎ１ -, -Y Ｎ１ -Y Ｎ２ -, -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -, -Y Ｎ１ -Y Ｎ２ (-) ２ , -Y Ｎ２ -, -Y Ｎ２ -Y Ｎ１ -, -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -, -Y Ｎ２ -Y Ｎ１ (-) ２ In the amine-modified compound, one or more Y Ｎ However, it is preferred that the terminal on the amine skeleton side is —(C═O)— and that it is bonded to a nitrogen atom in the amine skeleton.

[0106] Y Ｎ is preferably -Y Ｎ１ -, -Y Ｎ１ -Y Ｎ２ -, -Y Ｎ１ -Y Ｎ２ -Y Ｎ１ -, -Y Ｎ１ -Y Ｎ２ (-) ２ , -Y Ｎ２ -, -Y Ｎ２ -Y Ｎ１ -, -Y Ｎ２ -Y Ｎ１ -Y Ｎ２ -, -Y Ｎ２ -Y Ｎ１ (-) ２ , [wherein, Y Ｎ１is independently in each occurrence a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—O—, or —C(═O)-NR′— —C(═O)-NR′-C(═O)— (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), and Y Ｎ２ is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group or a divalent triazole group). This makes it possible to impart good liquid repellency to the substrate.

[0107] Y Ｎ Further specific examples include *-(C=O)- -O-(C=O)-NR'- (wherein * means that the group is bonded to the nitrogen atom of the amine skeleton, and R' is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)).

[0108] (Z Ｎ ) Z Ｎ represents a monovalent hydrocarbon group or monovalent polysiloxane group having from 1 to 40 carbon atoms which may have a substituent, and the above descriptions of (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0109] [Examples of Amine Modified Compounds] (Amine Modified Compound Example 1) Examples of amine modified compounds include those having the following formula: N(-Y Ｎ -Z Ｎ n ) p (-H) q -L 1 -[N(-Y Ｎ -Z Ｎ n ) r (-H) s -L 1 -] t -N(-Y Ｎ -Z Ｎ n )p (-H) q [In the formula, Y Ｎ is independently in each occurrence a direct bond or a group with a valence of 1+n; Z Ｎ is independently in each occurrence an optionally substituted linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms; L 1 is independently in each occurrence a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom and / or a sulfur atom, n is independently in each occurrence an integer of 1 or more and 3 or less, p is independently in each occurrence an integer of 0 or more and 2 or less, q is independently in each occurrence an integer of 0 or more and 2 or less, and p+q is a substituted or unsubstituted group of each N(-Y Ｎ -Z Ｎ n ) p (-H) q In the formula, r is 2, r is independently in each occurrence 0 or 1, s is independently in each occurrence 0 or 1, and r+s is a 0 or 1 group for each N(-Y Ｎ -Z Ｎ n ) r (-H) s In the formula (Amine Modification Example 1), p is 1, the sum of all p's and all r's is 1 or more, and t is an integer of 0 or more and 10 or less.

[0110] In the amine modified example 1, Y Ｎ , Z Ｎ , and n are described in detail above.

[0111] In the amine modified example 1, L １ is a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. １ The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms.１ L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. １ is preferably a cyclic group having both a ring (for example, an aromatic ring) and a chain structure (for example, a linear structure, ether oxygen, or thioether sulfur), and specific examples include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. １ The number of carbon atoms in L may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more. １ may have 20 or fewer, 18 or fewer, 16 or fewer, 14 or fewer, 12 or fewer, 10 or fewer, 8 or fewer, 6 or fewer, 4 or fewer, or 3 or fewer carbon atoms.

[0112] In Amine Modification Example 1, p, in each occurrence, is independently an integer of 0 to 2, and q, in each occurrence, is independently an integer of 0 to 2, and p+q is a sum of the ... Ｎ -Z Ｎ n ) p (-H) q In the formula, p is 2. Preferably, p may be independently in each occurrence 1 or more, for example 2.

[0113] In Amine Modification Example 1, r is independently in each occurrence 0 or 1, s is independently in each occurrence 0 or 1, and r+s is independently in each occurrence 0 or 1. Ｎ -Z Ｎ n ) r (-H) s In the formula, p is 1. Preferably, p is independently in each occurrence 1 or more, for example 2.

[0114] The sum of all p's and all r's is 1 or greater, i.e., Amine Modification Example 1 contains one or more -Y Ｎ -Z Ｎ ｎThe sum of all p's and all r's may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, or 12 or more (the sum of all q's and all s's may be 0). The sum of all p's and all r's may be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0115] In Amine Modification Example 1, t is an integer of 0 or more and 10 or less. t may be 0 or more, 1 or more, 2 or more, 4 or more, or 6 or more, and is preferably 0 or more or 2 or more. t may be 8 or less, 6 or less, 4 or less, or 3 or less.

[0116] (Amine Modification Example 2) Other examples of amine modifications include those represented by the following formula: N(-Y Ｎ -Z Ｎ n ) p (-H) q -L ２ (-Y Ｎ -Z Ｎ n ) u [In the formula, Y Ｎ is independently in each occurrence a direct bond or a group with a valence of 1+n; Z Ｎ is independently in each occurrence an optionally substituted linear or branched monovalent hydrocarbon group having from 6 to 40 carbon atoms; L ２ is a 1+u valent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by oxygen atoms and / or sulfur atoms, n is independently an integer of 1 or greater and 3 or less in each occurrence, p is an integer of 0 or greater and 2 or less, q is an integer of 0 or greater and 2 or less, p+q is 2, u is an integer of 1 or greater and 3 or less, and the sum of p and u is 1 or greater.] (Amine Modification Example 2)

[0117] In the amine modified example 2, Y Ｎ , Z Ｎ The above explanation is used for details of and n.

[0118] In the amine modified example 2, L ２is an aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms and a valence of 1+u, which may be interrupted by oxygen atoms and / or sulfur atoms, and may be a cyclic, branched, or straight-chain hydrocarbon group, and is preferably a straight-chain hydrocarbon group or an aromatic hydrocarbon. ２ The hydrocarbon group in the above description of the [amine skeleton] may be used as L, and the hydrocarbon group may be interrupted by an oxygen atom and / or a sulfur atom, or may consist of only carbon atoms, nitrogen atoms, and hydrogen atoms. ２ L may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 hydrocarbon aromatic rings. ２ is preferably a cyclic group having both a ring (for example, an aromatic ring) and a chain structure (for example, a linear structure, ether oxygen, or thioether sulfur), and specific examples include a 1,3-phenylenebisalkylene group, a 1,4-phenylenebisalkylene group, a diphenyletherdiyl group, and a diphenylthioetherdiyl group. ２ The number of carbon atoms in L may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more. ２ may have 20 or fewer, 18 or fewer, 16 or fewer, 14 or fewer, 12 or fewer, 10 or fewer, 8 or fewer, 6 or fewer, 4 or fewer, or 3 or fewer carbon atoms.

[0119] In the amine modification example 2, p is an integer of 0 to 2, q is an integer of 0 to 2, and p+q is 2. Preferably, p may be 1 or more, for example, 2.

[0120] In the amine modification example 2, u is an integer of 1 or more and 3 or less. u is 1, 2, or 3, for example, 2 or 3.

[0121] In the amine modified example 2, the sum of p and u is 1 or more, that is, the amine modified example 2 has one or more -Y Ｎ -Z Ｎ ｎ The sum of all p's and u's may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the sum of all q's may be 0). The sum of p's and u's may be 5 or less, 4 or less, 3 or less, or 2 or less.

[0122] (Specific Example) Specific examples of the amine-modified compound include compounds represented by the following formula: Ｎ , Z Ｎ , and n are described in detail above.

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130] The amine-modified wax may be a synthetic wax derived from animal or vegetable oils. The synthetic wax may be obtained by condensing a fatty acid derived from animal or vegetable oils with an aliphatic amine or an aromatic amine. Examples of the synthetic wax include fatty acid amide compounds such as hydroxy fatty acid amide compounds, palmitic acid amide compounds, octadecanoic acid amide compounds, stearic acid amide compounds, arachidic acid amide compounds, behenic acid amide compounds, lignoceric acid amide compounds, oleic acid amide compounds, linoleic acid amide compounds, α-linolenic acid amide compounds, γ-linolenic acid amide compounds, arachidonic acid amide compounds, eicosapentaenoic acid amide compounds, and docosahexaenoic acid amide compounds.

[0131] [Production Method] The method for producing the amine-modified compound is not limited, but may be carried out by reacting various amines (raw material amines) with Z in the presence of a condensing agent as needed. Ｎ A method for synthesizing by reacting a carboxylic acid containing a Z group with various amines. Ｎ Examples of the synthesis method include a method of reacting a group-containing carboxylic acid with an acid chloride, acid anhydride, isocyanate, etc. The condensing agent may be a known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, or Py-Bop.

[0132] (Amine (raw material amine)) Examples of amines (raw material amines) that are precursors of the amine skeleton are those that can constitute an amine skeleton, and include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine, and methylenebiscyclohexylamine; diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminopropyl)amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl)ether, bis[2-(2-aminoethoxy)ethyl]ether, and bis[2-(3-aminoprotoxy)ethyl] polyalkylenepolyamines such as ether, spermine, and spermidine; oxygen- or sulfur-containing aliphatic amines such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine, and polyoxyethylenediamine; aromatic monoamines such as aniline, 1- or 2-naphthylamine, 1-, 2-, or 9-aminoanthracene, 9-aminophenanthracene, and 2-, 3-, or 4-aminobiphenyl; monocyclic aromatic polyamines such as o-, m-, or p-phenylenediamine, o-, m-, or p-xylylenediamine, diaminotoluene, and 2,3-, 2,4-, or 2,5-tolylenediamine;Diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenyl phenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, aminophenoxybiphenyl, 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, Polycyclic aromatic polyamines such as diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, and 4,4'-bis(aminophenyl)amine; oxygen- or sulfur-containing polycyclic aromatic polyamines such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfide;Examples of the polyamine include 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 product of a polymerizable compound such as allylamine.

[0133] [Modified Polyol] As an example of a liquid-repellent compound, a modified polyol will be described. The modified polyol is a compound obtained by chemically modifying a polyol so as to exhibit liquid-repellency.

[0134] [Structure etc.] The polyol modified product may be a polymer having a degree of polymerization of 1 or more. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol modified product may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more. From the viewpoint of improving the handleability of the oil-resistant composition, the degree of polymerization of the polyol modified product may be 100 or less, preferably 50 or less, more preferably 30 or less, and even more preferably 15 or less. Here, the degree of polymerization means the number of repeating monomer units constituting the polymer.

[0135] The degree of polymerization in the present disclosure refers to the average degree of polymerization. The average degree of polymerization in the present disclosure refers to the polymerization obtained by measurement under the following conditions. When the polyol-modified product in the present disclosure is a polyglycerol-modified product obtained by modifying polyglycerol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyglycerol. The average degree of polymerization of polyglycerol is the average degree of polymerization (n) calculated from the hydroxyl value by end group analysis. Specifically, the average degree of polymerization and the average molecular weight are calculated from the following formulas (Formula 1) and (Formula 2). (Formula 1) Average molecular weight = 74n + 18 (Formula 2) Hydroxyl value = 56110(n + 2) / average molecular weight The hydroxyl value in the above (Formula 2) is a numerical value that serves as an index of the number of hydroxyl groups contained in the polyglycerol. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize the acetic acid required to acetylate the free hydroxyl groups contained in 1 g of polyglycerol, and is calculated in accordance with "Standard Test Methods for the Analysis of Fats, Oils and Related Compounds (I), 2003 Edition," compiled by the Japan Oil Chemists' Society. The hydroxyl value of the raw material polyglycerol is measured according to the above-mentioned Standard Test Methods for the Analysis of Fats, Oils and Related Compounds, and the average degree of polymerization and average molecular weight of the polyglycerol can be calculated from the above-mentioned relational equation.

[0136] When the polyol-modified product in the present disclosure is a polyvinyl alcohol-modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyvinyl alcohol, which can be measured in accordance with JIS K 6726, Testing Method for Polyvinyl Alcohol.

[0137] When the polyol-modified product in the present disclosure is a polysaccharide-modified product obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polysaccharide. Analysis of the average degree of polymerization of a polysaccharide can be performed as follows. The degree of polymerization refers to the number of monosaccharide units (fructose and glucose units) in the polysaccharide, and the average degree of polymerization is determined, for example, by taking the top of the peak in each analysis result obtained by a conventional analytical method such as HPLC, GC, or HPAEC as the average degree of polymerization. Measurements can be performed using, for example, an ULTRON PS-80N (8 x 300 mm) column manufactured by Shinwa Chemical Industry Co., Ltd. (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) or a TSK-GEL G30000 PWXL (7.8 x 300 mm) column manufactured by TOSOH Corporation (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) and a differential refractometer as a detector.

[0138] The polyol-modified product may be low molecular weight (e.g., weight average molecular weight less than 1500, less than 1000, or 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol-modified product 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. The weight average molecular weight of the polyol-modified product 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.

[0139] The substitution rate of hydroxy groups in the modified polyol may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, and is preferably 10% or more, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, and particularly 80% or more. The substitution rate of hydroxy groups in the modified polyol may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, or 15% or less, for example, 95% or less. Here, the "substitution rate" refers to the proportion (mol %) of hydroxy groups derived from a polyol that are modified, and may refer to the proportion (mol %) that are modified with a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0140] The residual rate of hydroxyl groups in the polyol-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more. The residual rate of hydroxyl groups in the polyol-modified product may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual rate" refers to the proportion (mol %) of hydroxyl groups derived from the polyol that are not modified.

[0141] The number of modifying groups in the polyol modified product may be 2 or more, 5 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 15 or more, 30 or more, or 50 or more. The number of modifying groups in the polyol modified product may be 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. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0142] The modifying group equivalent weight of the polyol modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more. The modifying group equivalent weight of the polyol modified product may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polyol modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0143] The polyol-modified product has one or more hydroxy groups of a polyol substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the polyol-modified product may have a structure in which a polyol is modified with an alkyl group having 6 to 40 carbon atoms.

[0144] For details of the monovalent hydrocarbon group which may have a substituent and the monovalent polysiloxane group, the above descriptions of the (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0145] (-Y Ｏ -Z Ｏ ｎ In the present disclosure, the modified polyol is a polyol in which one or more hydroxy groups of the polyol are represented by the following formula: Ｏ -Z Ｏ ｎ [In the formula, Y Ｏ Is Y Ｏ１ and Y Ｏ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｏ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), and YＯ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Ｏ is a monovalent hydrocarbon group having from 1 to 40 carbon atoms which may have a substituent, or a monovalent polysiloxane group, and n is an integer of from 1 to 3.

[0146] (Y Ｏ ) Y Ｏ Is Y Ｏ１ and Y Ｏ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｏ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), and Y Ｏ２ is a group composed of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0147] n is Y Ｏ Z combines with Ｏ and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0148] Y Ｏ The molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more. Ｏmay have a molecular weight of 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0149] Y Ｏ may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. Ｏ is -C(=O)-NR'-, -C(=S)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may contain NR'-. Ｏ By including these groups, the liquid repellency can be improved.

[0150] ○ Y Ｏ１ Y Ｏ１ is a non-hydrocarbon linker.

[0151] Y Ｏ１ is a direct bond or a divalent or higher valent group. Ｏ１ The valence of Y may be 2 to 4, 2 to 3, or 2. Ｏ１ is preferably not only a direct bond.

[0152] Y Ｏ１ The molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more. Ｏ１ may have a molecular weight of 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0153] Y Ｏ１ represents a direct bond, —O—, —C(═O)—, —S(═O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Ｏ１Examples of include a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, —SO ２ -, -SO ２ NR'-, -C(OR')R'-, -C(OR')(-) ２ and the like (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (eg, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0154] Y Ｏ１ may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. Ｏ２ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may contain NR'-. Ｏ１ By including these groups, the liquid repellency can be improved.

[0155] ○ Y Ｏ２ Y Ｏ２ is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent.

[0156] Y Ｏ２ Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). Ｏ２ Y may be aliphatic or aromatic. Ｏ２ may be linear, branched or cyclic.

[0157] Y Ｏ２ is a divalent or higher valent group. Ｏ２ The valency of may be, for example, 2-4, 2-3, or 2.

[0158] Y Ｏ２The number of carbon atoms in Y 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. Ｏ２ may have 40 or fewer, 35 or fewer, 30 or fewer, 25 or fewer, 20 or fewer, 15 or fewer, 10 or fewer, or 5 or fewer carbon atoms.

[0159] Y Ｏ２ is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0160] The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 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 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 35 or less, 30 or less, 25 or less, 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 4 or less, 3 or less, or 2.

[0161] The aliphatic hydrocarbon group 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 aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the substituted aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0162] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0163] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -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 aromatic ring, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the substituted hydrocarbon aromatic ring, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0164] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of divalent to tetravalent heterocycles include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0165] The heterocycle may have a substituent. Examples of the substituent include -R', -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 heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more. In the substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0166] Y Ｏ２ Examples of -Ali- -Cy- -Ali(-) ２ -Cy(-) ２ (-) ２ Ali- (-) ２ Cy- (-) ２ Ali (-) ２ (-) ２ Cy(-) ２ -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- (wherein Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.)

[0167] Y Ｏ２ Specific examples of -(CH ２ ) ｐ -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0168] (Y Ｏ Example: Y Ｏ In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0169] Y Ｏ An example of this is Y Ｏ When is divalent, -Y Ｏ１ -, -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -, -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ２ -, -Y Ｏ２ -Y Ｏ１ -, -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ - etc.

[0170] Y Ｏ An example of this is Y Ｏ When is trivalent, -Y Ｏ１ (-) ２ , -Y Ｏ１ -Y Ｏ２ (-) ２ , -Y Ｏ１ -(Y Ｏ２ -) ２ , -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ (-) ２ , -Y Ｏ１ -Y Ｏ２ (-Y Ｏ１ -) ２ , -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -) ２ , -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ (-) ２ , -YＯ１ -Y Ｏ２ -Y Ｏ１ -(Y Ｏ２ -) ２、 -Y Ｏ１ -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -) ２、 -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -) ２ ; -Y Ｏ２ (-) ２ ,-Y Ｏ２ -Y Ｏ１ (-) ２ ,-Y Ｏ２ -(Y Ｏ１ -) ２ ,-Y Ｏ２ -Y Ｏ１ -Y Ｏ２ (-) ２ ,-Y Ｏ２ -Y Ｏ１ (-Y Ｏ２ -) ２ ,-Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -) ２ ,-Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ (-) ２ ,-Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -(Y Ｏ１ -) ２、 -Y Ｏ２ -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -) ２、 -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -) ２ etc. can be cited.

[0171] Y Ｏ As an example of Y Ｏ when Y is tetravalent, -Y Ｏ１ (-) ３ ,-Y Ｏ１ -Y Ｏ２ (-) ３、-Y Ｏ１ -(Y Ｏ２ -) ３ 、-Y Ｏ１ -Y Ｏ２ -Y Ｏ１ (-) ３ 、-Y Ｏ１ -Y Ｏ２ (-Y Ｏ１ -) ３ 、-Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -) ３ 、-Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ (-) ３ 、-Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -(Y Ｏ２ -) ３、 -Y Ｏ１ -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -) ３、 -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -) ３ ; -Y Ｏ２ (-) ３ 、-Y Ｏ２ -Y Ｏ１ (-) ３ 、-Y Ｏ２ -(Y Ｏ１ -) ３ 、-Y Ｏ２ -Y Ｏ１ -Y Ｏ２ (-) ３ 、-Y Ｏ２ -Y Ｏ１ (-Y Ｏ２ -) ３ 、-Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -) ３ 、-Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ (-) ３ 、-Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -(Y Ｏ１ -)３、 -Y Ｏ２ -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -) ３、 -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -) ３ ; etc.

[0172] Y Ｏ Preferred examples of -Y Ｏ１ -, -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -, -Y Ｏ１ -Y Ｏ２ (-) ２ , -Y Ｏ２ -, -Y Ｏ２ -Y Ｏ１ -, -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ２ -Y Ｏ１ (-) ２ , etc.

[0173] (Preferred Y Ｏ Preferably, Y Ｏ ga -O-Y Ｏ１１ - or -O-Y Ｏ１１ -Y Ｏ２１ -Y Ｏ１２ wherein each symbol represents independently at each occurrence: Y Ｏ１１ is a direct bond, —C(═O)—, —C(═O)—NR′—, or —C(═S)—NR′—; Y Ｏ２１ is a hydrocarbon group having 1 to 40 carbon atoms, and Y Ｏ１２ is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(= O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２], or

[0174] Y Ｏ１１ is a non-hydrocarbon linker, which is a direct bond or a divalent or higher valent group.

[0175] Y Ｏ１１ The molecular weight of Y may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. Ｏ１１ may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0176] Y Ｏ１１ may be a direct bond, —C(═O)—, —C(═O)—NR′—, or —C(═S)—NR′—.

[0177] Y Ｏ２１ is a divalent hydrocarbon linker, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0178] Y Ｏ２１ The number of carbon atoms in Y 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. Ｏ２１ may have 40 or fewer, 35 or fewer, 30 or fewer, 25 or fewer, 20 or fewer, 15 or fewer, 10 or fewer, or 5 or fewer carbon atoms.

[0179] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group, and may be a saturated or unsaturated (eg, saturated) aliphatic hydrocarbon group.

[0180] Y Ｏ２１ Specific examples of -(CH ２ ) ｐ -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0181] Y Ｏ１２ -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, - NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ It may be.

[0182] Y Ｏ１２ may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. Ｏ１２ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may be NR'-. Ｃ１２ By including these groups, the liquid repellency can be improved.

[0183] (Z Ｏ ) Z Ｏ represents a monovalent hydrocarbon group or monovalent polysiloxane group having from 1 to 40 carbon atoms which may have a substituent, and the above descriptions of (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0184] [Other modifying groups] The hydroxy group of the polyol is -Y Ｏ -Z Ｏ ｎ Examples of modifying groups are anionic and / or cationic groups.

[0185] Examples of the anionic group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0186] Examples of salts of anionic groups include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0187] The cationic group is an amino group, preferably a tertiary amino group or a quaternary amino group. In the tertiary amino group, two groups bonded to the nitrogen atom may be the same or different and may be an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0188] The cationic group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred.

[0189] [Production Method] The modified polyol may be produced by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with a hydroxy group of a polyol.

[0190] (Polyol) A polyol is a compound having two or more hydroxy groups and is a compound that serves as a raw material for a modified 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.

[0191] 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.

[0192] When the polyol is a polymer, the repeating structure of the monomer unit may contain a hydroxy group and an ether bond.

[0193] 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. The weight average molecular weight of the polyol 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, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0194] 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. The number of hydroxy groups in the polyol 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.

[0195] 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. The hydroxy group equivalent weight of the polyol 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.

[0196] The polyol 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 above natural products also include compounds converted from microorganisms. Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxy group-containing compound polymers, polyether polyols, polymer polyols, polyester polyols, and other polyols.

[0197] Examples of monosaccharides include glucose, fructose, galactose, and xylose.

[0198] Examples of oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, and sucralose.

[0199] Examples of sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, and lactitol.

[0200] Examples of polysaccharides include starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, gellan gum, and tamarind seed gum.

[0201] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, and gluconic acid.

[0202] Examples of amino acids include glucosamine.

[0203] Examples of vitamins include ascorbic acid and inositol.

[0204] Examples of flavonols include catechin, quercetin, and anthocyanin.

[0205] Examples of hydroxy hydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, etc. Hydroxy hydrocarbons are hydrocarbons having a hydroxy group and may be aromatic or aliphatic, but are preferably aliphatic. The term "hydroxy hydrocarbon" may also refer to hydroxy hydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxy hydrocarbons).

[0206] Examples of the hydroxy group-containing compound polymer include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer.

[0207] An example of a polyether polyol may be a compound obtained by addition polymerization of an alkylene oxide with an initiator. Examples of initiators include compounds having two or more functional hydroxyl groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamines, diethylenetriamine, sorbitol, and sucrose. Examples of alkylene oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by addition polymerization of alkylene oxide with the above initiators are also referred to as polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triols obtained by addition polymerization of propylene oxide with glycerin, and polyoxypropylene polyglyceryl ethers obtained by addition polymerization of propylene oxide with polyglycerin.

[0208] An example of a polymer polyol is a compound obtained by polymerizing at least a portion of a polyether polyol with an ethylenically unsaturated monomer, such as acrylonitrile or styrene.

[0209] Examples of polyester polyols include compounds obtained by dehydration condensation of a compound having a bifunctional or higher carboxyl group and a compound having a bifunctional or higher hydroxyl group. Examples of compounds having a bifunctional or higher carboxyl group include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and acid anhydrides thereof. Examples of compounds having a bifunctional or higher hydroxyl group include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0210] (Modifying Agent) The modifying agent is a compound reactive with polyol, and is preferably a compound having the above-mentioned monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0211] Examples of modifying agents are: Acid halides G(O=)C-Z Ｏ Acid anhydride O(C(=O)-Z Ｏ ) ２ Carboxylic acid HO(O=)C-Z Ｏ Isocyanate O=C=N-Z Ｏ Thioisocyanate S=C=N-Z Ｏ Epoxy (CH ２ OCH)CH ２ O-Z Ｏ Halide G-Z Ｏ Amine H ２ N-Z ＯHydroxy HO-Z Ｏ [In the formula, Z Ｏ is as defined above, and G is a halogen atom (e.g., F, Cl, Br, or I).

[0212] Z in the structure of the above-mentioned modifier Ｏ may be replaced with any group constituting the modifying group, for example, Z Ｏ may be a group having a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, or, for example, Z Ｏ Wo-Y Ｏ -Z Ｏ ｎ It may also be possible to use the following.

[0213] The modified polyol may be synthesized by reacting a polyol with a modifying agent. For example, a modified polyol can be synthesized by reacting a modifying agent such as an acid halide compound, an acid anhydride, or a carboxylic acid with a hydroxy group of a polyol to form an ester bond. Alternatively, a modified polyol can be produced by reacting a modifying agent such as a halide or an epoxy compound with a hydroxy group of a polyol to form an ether bond. Those skilled in the art can appropriately design the reaction conditions between the polyol and the modifying agent, such as by using a catalyst (e.g., an acid catalyst or a base catalyst) or a condensing agent, depending on the desired product.

[0214] [Polycarboxylic Acid Modified Compound] As an example of a liquid-repellent compound, a polycarboxylic acid modified compound will be described. A polyol modified compound is a compound obtained by chemically modifying a polycarboxylic acid modified compound so as to exhibit liquid repellency.

[0215] [Structure etc.] The polycarboxylic acid modified product may be a low molecular weight (e.g., weight average molecular weight less than 1500, less than 1000, or 500 or less) and / or a polymer. The weight 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, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100,000 or more, 300,000 or more, or 500,000 or more. The weight average molecular weight of the polycarboxylic acid modified product 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.

[0216] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polycarboxylic acid-modified product may be values ​​measured by GFC analysis using polyethylene glycol / polyethylene oxide as a standard sample with the following equipment and conditions: Separation column: SB-806M (8 mm x 30 mm, Shodex) Column temperature: 40°C Mobile phase solvent: ion-exchanged water Mobile phase flow rate: 1.0 mL / min Sample concentration: 0.5 wt% Injection volume: 50 μL Detector: RI detector (Waters 2414, Waters Corporation)

[0217] The weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity index (Mw / Mn) of the polycarboxylic acid modified product, calculated in terms of polystyrene, may be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent and Shodex KF400RL and KF400RH columns (polystyrene gel) manufactured by Showa Denko K.K.

[0218] The substitution rate of hydroxy groups for carboxyl groups in the modified polycarboxylic acid may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, and is preferably 10% or more, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, and particularly 80% or more. The substitution rate of hydroxy groups for carboxyl groups in the modified polycarboxylic acid may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, or 15% or less, for example, 95% or less. Here, the "substitution rate" refers to the proportion (mol %) of hydroxy groups in carboxyl groups derived from polycarboxylic acid that are modified, and may refer to the proportion (mol %) that are modified with a monovalent hydrocarbon group having from 1 to 40 carbon atoms, or a monovalent polysiloxane group, which may have a substituent.

[0219] The residual ratio of hydroxy groups in carboxyl groups in the polycarboxylic acid-modified product may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more. The residual ratio of hydroxy groups in carboxyl groups in the polycarboxylic acid-modified product may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual ratio" refers to the proportion (mol %) of hydroxy groups in carboxyl groups derived from the polycarboxylic acid that are not modified.

[0220] The number of modifying groups contained in the polycarboxylic acid modified product may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, or 50 or more. The number of modifying groups contained in the polycarboxylic acid modified product may be 1,000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0221] The modifying group equivalent weight of the polycarboxylic acid modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more. The modifying group equivalent weight of the polycarboxylic acid modified product may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. It is the value obtained by dividing the weight average molecular weight of the polycarboxylic acid modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0222] In the polycarboxylic acid modified product, one or more hydroxy groups of the polycarboxylic acid are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the polycarboxylic acid modified product may have an alkyl group having 6 to 40 carbon atoms relative to the polycarboxylic acid.

[0223] For details of the monovalent hydrocarbon group which may have a substituent and the monovalent polysiloxane group, the above descriptions of the (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0224] (-Y Ｃ -Z Ｃ ｎ In the present disclosure, the modified polycarboxylic acid is a polycarboxylic acid in which the hydroxy group of one or more carboxyl groups is represented by the following formula: -Y Ｃ -Z Ｃ ｎ [In the formula, Y Ｃ Is Y Ｃ１ and Y Ｃ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｃ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２(wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), and Y Ｃ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Ｃ is a monovalent hydrocarbon group having from 1 to 40 carbon atoms which may have a substituent, or a monovalent polysiloxane group, and n is an integer of from 1 to 3.

[0225] (Y Ｃ ) Y Ｃ Is Y Ｃ１ and Y Ｃ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｃ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), and Y Ｃ２ is a group composed of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0226] n is Y Ｃ Z combines with Ｃ and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0227] Y ＣThe molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more. Ｃ may have a molecular weight of 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0228] Y Ｃ may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. Ｃ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may be NR'-. Ｃ By including these groups, the liquid repellency can be improved.

[0229] ○ Y Ｃ１ Y Ｃ１ is a non-hydrocarbon linker.

[0230] Y Ｃ１ is a direct bond or a divalent or higher valent group. Ｃ１ The valence of Y may be 2 to 4, 2 to 3, or 2. Ｃ１ is preferably not only a direct bond.

[0231] Y Ｃ１ The molecular weight of Y may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more. Ｃ１ may have a molecular weight of 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0232] Y Ｃ１ represents a direct bond, —O—, —C(═O)—, —S(═O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２(wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Ｃ１ Examples of include a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, —SO ２ -, -SO ２ NR'-, -C(OR')R'-, -C(OR')(-) ２ and the like (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (eg, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0233] Y Ｃ１ may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. Ｃ１ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ NR'- may be included. Ｃ１ By including these groups, the liquid repellency can be improved.

[0234] ○ Y Ｃ２ Y Ｃ２ is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent.

[0235] Y Ｃ２ Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). Ｃ２ Y may be aliphatic or aromatic. Ｃ２ may be linear, branched or cyclic.

[0236] Y Ｃ２ is a divalent or higher valent group.Ｃ２ The valency of may be, for example, 2-4, 2-3, or 2.

[0237] Y Ｃ２ The number of carbon atoms in Y 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. Ｃ２ may have 40 or fewer, 35 or fewer, 30 or fewer, 25 or fewer, 20 or fewer, 15 or fewer, 10 or fewer, or 5 or fewer carbon atoms.

[0238] Y Ｃ２ is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0239] The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 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 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 35 or less, 30 or less, 25 or less, 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 4 or less, 3 or less, or 2.

[0240] The aliphatic hydrocarbon group 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 aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the substituted aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0241] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0242] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -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 aromatic ring, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more. In the substituted hydrocarbon aromatic ring, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0243] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of divalent to tetravalent heterocycles include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0244] The heterocycle may have a substituent. Examples of the substituent include -R', -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 heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more. In the substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0245] Y Ｃ２ Examples of -Ali- -Cy- -Ali(-) ２ -Cy(-) ２ (-) ２ Ali- (-) ２ Cy- (-) ２ Ali (-) ２ (-) ２ Cy(-) ２ -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- (wherein Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.)

[0246] Y Ｃ２ Specific examples of -(CH ２ ) ｐ -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0247] (Y Ｃ Example: Y Ｃ In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0248] Y Ｃ An example of this is Y Ｃ When is divalent, -Y Ｃ１ -, -Y Ｃ１ -Y Ｃ２ -, -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -, -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -Y Ｃ２ -, -Y Ｃ２ -, -Y Ｃ２ -Y Ｃ１ -, -Y Ｃ２ -Y Ｃ１ -Y Ｃ２ -, -Y Ｃ２ -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ - etc.

[0249] Y Ｃ An example of this is Y Ｃ When is trivalent, -Y Ｃ１ (-) ２ , -Y Ｃ１ -Y Ｃ２ (-) ２ , -Y Ｃ１ -(Y Ｃ２ -) ２ , -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ (-) ２ , -Y Ｃ１ -Y Ｃ２ (-Y Ｃ１ -) ２ , -Y Ｃ１ -(Y Ｃ２ -Y Ｃ１ -) ２ , -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -Y Ｃ２ (-) ２ , -YＣ１ -Y Ｃ２ -Y Ｃ１ -(Y Ｃ２ -) ２、 -Y Ｃ１ -Y Ｃ２ -(Y Ｃ１ -Y Ｃ２ -) ２、 -Y Ｃ１ -(Y Ｃ２ -Y Ｃ１ -Y Ｃ２ -) ２ ; -Y Ｃ２ (-) ２ ,-Y Ｃ２ -Y Ｃ１ (-) ２ ,-Y Ｃ２ -(Y Ｃ１ -) ２ ,-Y Ｃ２ -Y Ｃ１ -Y Ｃ２ (-) ２ ,-Y Ｃ２ -Y Ｃ１ (-Y Ｃ２ -) ２ ,-Y Ｃ２ -(Y Ｃ１ -Y Ｃ２ -) ２ ,-Y Ｃ２ -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ (-)[[ID= / / ID=78]] ２ ,-Y<000 / / ID=1101>-Y Ｃ１ -Y Ｃ２ -(Y Ｃ１ -) ２、 -Y Ｃ２ [[ID=9 / / ID=1]]-Y Ｃ１ -(Y Ｃ２ -Y Ｃ１ -) ２、 -Y Ｃ２ -(Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -) ２ etc. can be cited.

[0250] Y Ｃ As an example of Y Ｃ when Y is tetravalent, -Y Ｃ１ (-) ３ ,-Y Ｃ１ -Y Ｃ２ (-) ３、-Y Ｃ１ -(Y Ｃ２ -) ３ 、-Y Ｃ１ -Y Ｃ２ -Y Ｃ１ (-) ３ 、-Y Ｃ１ -Y Ｃ２ (-Y Ｃ１ -) ３ 、-Y Ｃ１ -(Y Ｃ２ -Y Ｃ１ -) ３ 、-Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -Y Ｃ２ (-) ３ 、-Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -(Y Ｃ２ -) ３、 -Y Ｃ１ -Y Ｃ２ -(Y Ｃ１ -Y Ｃ２ -) ３、 -Y Ｃ１ -(Y Ｃ２ -Y Ｃ１ -Y Ｃ２ -) ３ ; -Y Ｃ２ (-) ３ 、-Y Ｃ２ -Y Ｃ１ (-) ３ 、-Y Ｃ２ -(Y Ｃ１ -) ３ 、-Y Ｃ２ -Y Ｃ１ -Y Ｃ２ (-) ３ 、-Y Ｃ２ -Y Ｃ１ (-Y Ｃ２ -) ３ 、-Y Ｃ２ -(Y Ｃ１ -Y Ｃ２ -) ３ 、-Y Ｃ２ -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ (-) ３ 、-Y Ｃ２ -Y Ｃ１ -Y Ｃ２ -(Y Ｃ１ -)３、 -Y Ｃ２ -Y Ｃ１ -(Y Ｃ２ -Y Ｃ１ -) ３、 -Y Ｃ２ -(Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -) ３ ; etc.

[0251] Y Ｃ Preferred examples of -Y Ｃ１ -, -Y Ｃ１ -Y Ｃ２ -, -Y Ｃ１ -Y Ｃ２ -Y Ｃ１ -, -Y Ｃ１ -Y Ｃ２ (-) ２ , -Y Ｃ２ -, -Y Ｃ２ -Y Ｃ１ -, -Y Ｃ２ -Y Ｃ１ -Y Ｃ２ -, -Y Ｃ２ -Y Ｃ１ (-) ２ , etc.

[0252] (Preferred Y Ｃ Preferably, Y Ｃ is -Y Ｃ１１ - or -Y Ｃ１１ -Y Ｃ２１ -Y Ｃ１２ wherein each symbol represents independently at each occurrence: Y Ｃ１１ is —O— or —NR′—, and Y Ｃ２１ is a hydrocarbon group having 1 to 40 carbon atoms, and Y Ｃ１２ is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(= O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ ], or

[0253] Y Ｃ１１ is a non-hydrocarbon linker, which is a direct bond or a divalent or higher valent group.

[0254] Y Ｃ１１ The molecular weight of Y may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less. Ｃ１１ may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.

[0255] Y Ｃ１１ may be a direct bond, —C(═O)—, —C(═O)—NR′—, or —C(═S)—NR′—.

[0256] Y Ｃ２１ is a divalent hydrocarbon linker, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0257] Y Ｃ２１ The number of carbon atoms in Y 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. Ｃ２１ may have 40 or fewer, 35 or fewer, 30 or fewer, 25 or fewer, 20 or fewer, 15 or fewer, 10 or fewer, or 5 or fewer carbon atoms.

[0258] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group, and may be a saturated or unsaturated (eg, saturated) aliphatic hydrocarbon group.

[0259] Y Ｃ２１ Specific examples of -(CH ２ ) ｐ -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0260] YＣ１２ -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, - NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ It may be.

[0261] Y Ｃ１２ may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. Ｃ１２ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may be NR'-. Ｃ１２ By including these groups, the liquid repellency can be improved.

[0262] (Z Ｃ ) Z Ｃ represents a monovalent hydrocarbon group or monovalent polysiloxane group having from 1 to 40 carbon atoms which may have a substituent, and the above descriptions of (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0263] [Other modifying groups] The hydroxy group of the polycarboxylic acid is -Y Ｃ -Z Ｃ ｎ The polyol may be substituted with a modifying group other than the above. Examples of the modifying group include an anionic group and / or a cationic group. The above description of [Other modifying groups] in the polyol is applicable to the anionic group and / or the cationic group.

[0264] [Production Method] The modified polycarboxylic acid may be produced by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with a hydroxy group of the polycarboxylic acid.

[0265] (Polycarboxylic Acid) Polycarboxylic acid is a compound having two or more carboxyl groups and is a compound that can be used as a raw material for a modified polycarboxylic acid. 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.

[0266] 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. The weight average molecular weight of the polycarboxylic acid may be 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.

[0267] 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. The number of carboxyl groups in the polycarboxylic acid may be 3,000 or less, 1,000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0268] 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. The carboxyl group equivalent of the polycarboxylic acid 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.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] Tricarboxylic acids are compounds having three carboxyl groups, and examples thereof include citric acid, tricarballylic acid, t-aconitic acid, trimellitic acid, and salts thereof.

[0273] The tetracarboxylic acid is a compound having four carboxyl groups, and examples thereof include pyromellitic acid and its salts.

[0274] 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.

[0275] Polycarboxylic acids are represented by the formula CH ２ ═C(-Q)-C(═O)-OH [wherein Q is a hydrogen atom, a monovalent organic group, or a halogen atom].

[0276] Q is a hydrogen atom, a monovalent organic group, or a halogen atom excluding a fluorine atom. Q may be a hydrogen atom, a methyl group, a halogen, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of Q include a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. Q is preferably a hydrogen atom, a methyl group, or a chlorine atom. It is particularly preferred that Q is a hydrogen atom.

[0277] (Modifying Agent) The modifying agent is a compound reactive with polycarboxylic acid, and is preferably a compound having the above-mentioned monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0278] Examples of modifiers are: Epoxy (CH ２ OCH)CH ２ O-Z Ｃ Amine H ２ N-Z Ｃ Hydroxy HO-Z Ｃ [In the formula, Z Ｃ is as described above.]

[0279] Z in the structure of the above-mentioned modifier Ｃ may be replaced with any group constituting the modifying group, for example, Z Ｃ may be a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or may be, for example, Z Ｃ Wo-Y Ｃ -Z Ｃ ｎ It may also be possible to use the following.

[0280] The modified polycarboxylic acid may be synthesized by reacting a polycarboxylic acid with a modifying agent. For example, the modifying agent, which is an epoxy compound, may be reacted with the carboxyl group of the polycarboxylic acid to form an ester bond, thereby producing the modified polycarboxylic acid. 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 (e.g., an acid catalyst or a base catalyst) or a condensing agent, depending on the desired product.

[0281] [Vinyl Polymer] As an example of a liquid-repellent compound, a vinyl polymer will be described. A vinyl polymer is a polymer obtained by polymerizing a vinyl monomer, and exhibits liquid-repellency.

[0282] [Characteristics, etc.] The vinyl polymer is preferably a compound containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content of the vinyl polymer 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 reduced. From this perspective, the higher the biobased content of the vinyl polymer, the better.

[0283] The melting point of the vinyl polymer may be 30° C. or higher, 40° 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. The melting point of the vinyl polymer 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.

[0284] [Structure etc.] The weight average molecular weight of the vinyl polymer may be 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. The weight average molecular weight of the vinyl polymer may be 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, 30,000 or less, 10,000 or less, or 5,000 or less. The weight average molecular weight may be a polystyrene-equivalent molecular weight measured by GPC.

[0285] (a) Hydrocarbon Group-Containing Monomer The vinyl polymer may have a repeating unit derived from a monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms.

[0286] The hydrocarbon group contained in the monomer (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 may be 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, and preferably 10 or more, 12 or more, 14 or more, or 16 or more. The number of carbon atoms in the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and preferably 30 or less, 25 or less, or 20 or less.

[0287] The monomer (a) may contain an amide group, a urea group, or a urethane group. The hydrocarbon-based monomer may be a combination of a hydrocarbon-based monomer having an amide group, a urea group, or a urethane group and a hydrocarbon-based monomer not having an amide group, a urea group, or a urethane group. By including such a group in the monomer (a), the effects of the present disclosure can be effectively achieved.

[0288] The monomer (a) having a hydrocarbon group having 6 to 40 carbon atoms is represented by the formula: CH2=C(-X ａ )-C(=O)-Y ａ (R ａ ) ｋ [In the formula, R ａ are each independently a hydrocarbon group having 6 to 40 carbon atoms; ａ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ represents a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, —CH ２ -, -CH=), -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NH- (excluding hydrocarbon groups), and k is 1 to 3.

[0289] X ａmay be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. ａ Examples of X are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. ａ is preferably a hydrogen atom, a methyl group, or a chlorine atom. ａ is particularly preferably a hydrogen atom.

[0290] Y ａ is a divalent to tetravalent group. ａ is preferably a divalent group. ａ represents a hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ A group consisting of at least one selected from - and -NH- (excluding hydrocarbon groups) is preferred. Examples of hydrocarbon groups having one carbon atom include -CH ２ -, a branched -CH=, or a branched -C≡.

[0291] Y ａ -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [In the formula, Y' is a direct bond, -O-, -NH- or -S(=O) ２ - and R' is -(CH ２ ) m - (m is an integer of 1 to 5) or -C ６ H ４ -(phenylene group).

[0292] Y ａ Specific examples of are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４ -, -O-(CH ２ )m -O-、-NH-(CH ２ ) m -NH-、-O-(CH ２ ) m -NH-、-NH-(CH ２ ) m -O-、-O-(CH ２ ) m -O-C(=O)-、-O-(CH ２ ) m -C(=O)-O-,-NH-(CH ２ ) m -O-C(=O)-,-NH-(CH ２ ) m -C(=O)-O-、-O-(CH ２ ) m -O-C(=O)-NH-,-O-(CH ２ ) m -NH-C(=O)-O-,-O-(CH ２ ) m -C(=O)-NH-,-O-(CH ２ ) m -NH-C(=O)-,-O-(CH ２ ) m -NH-C(=O)-NH-,-O-(CH ２ ) m -O-C ６ H ４ -、-O-(CH ２ ) m -NH-S(=O) ２ -、-O-(CH ２ ) m -S(=O) ２ -NH-、-NH-(CH ２ ) m -O-C(=O)-NH-,-NH-(CH ２ ) m -NH-C(=O)-O-,-NH-(CH ２ ) m -C(=O)-NH-,-NH-(CH ２ ) m -NH-C(=O)-,-NH-(CH ２ ) m -NH-C(=O)-NH-,-NH-(CH ２ ) m -O-C ６ H４ -, -NH-(CH ２ ) m -NH-C ６ H ４ -, -NH-(CH ２ ) m -NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH-, wherein m is 1 to 5, particularly 2 or 4.

[0293] Y ａ is -O-, -NH-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -NH-S(=O) ２ -, -O-(CH ２ ) m -S(=O) ２ -NH-, -NH-(CH ２ ) m -NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH- [wherein m is an integer of 1 to 5, particularly 2 or 4] is preferred. ａ is -O- or -O-(CH ２ ) m —NH—C(═O)—, particularly —O—(CH ２ ) m It is more preferably —NH—C(═O)—.

[0294] R ａis preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22 carbon atoms.

[0295] Examples of the monomer (a) are: (a1) a monomer of the formula: CH2=C(-X ａ１ )-C(=O)-Y ａ１ -R ａ１ [In the formula, R ａ１ is a hydrocarbon group having 6 to 40 carbon atoms, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ１ is —O— or —NH—.], and (a2) a monomer represented by the formula: CH═C(—X ａ２ )-C(=O)-Y ａ２１ -Z (-Y ａ２２ -R ａ２ ) ｎ [In the formula, R ａ２ are each independently a hydrocarbon group having 6 to 40 carbon atoms; ａ２ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ２１ is —O— or —NH—, and Y ａ２２ are each independently a direct bond, or —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ -, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.

[0296] (a1) Monomer The monomer (a1) is a monomer represented by the formula: CH2=C(-X ａ１ )-C(=O)-Y ａ１ -R ａ１ [In the formula, R ａ１ is a hydrocarbon group having 6 to 40 carbon atoms, ａ１ is a hydrogen atom, a monovalent organic group or a halogen atom, ａ１is —O— or —NH—.]

[0297] The monomer (a1) is Y ａ１ a long chain acrylate ester monomer in which Y is —O—; ａ１ is a long chain acrylamide monomer in which R is —NH—. ａ１ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ａ１ In the formula (I), the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example, 16 to 26, and particularly preferably 18 to 22. ａ１ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0298] Preferred examples of the long-chain acrylate ester monomer include lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, icosyl α-chloroacrylate, and behenyl α-chloroacrylate. Preferred examples of the long-chain acrylamide monomer include stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0299] Monomer (a2) Monomer (a2) is a monomer different from monomer (a1). Monomer (a2) is a monomer having —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ The monomer (a2) is a (meth)acrylate or (meth)acrylamide having a group consisting of at least one selected from the formula: CH2=C(-X ａ２ )-C(=O)-Y ａ２１ -Z (-Y ａ２２ -R ａ２ ) ｎ [In the formula, R ａ２ are each independently a hydrocarbon group having 6 to 40 carbon atoms; ａ２ is a hydrogen atom, a monovalent organic group or a halogen atom,ａ２１ is —O— or —NH—, and Y ａ２２ are each independently a direct bond, or —O—, —C(═O)—, —S(═O) ２ -, -NH- or -CH ２ -, Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2. ａ２２ and / or Z may not be a direct bond. ａ２２ and Z may not be a direct bond at the same time.

[0300] R ａ２ is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. ａ２ In the formula (I), the hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22 carbon atoms.

[0301] X ａ２ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0302] Y ａ２２ represents -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'-, wherein each Y' independently represents a direct bond, -O-, -NH-, or -S(=O) ２ - and R' is -(CH ２ ) ｍ - (m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH ２ ) ｌ -C ６ H ４ -(CH ２ ) ｌ- (each l is independently an integer of 0 to 5; -C ６ H ４ - is a phenylene group.

[0303] Y ａ２２ Specific examples include direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S(=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ -, -NH-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ ) m -O-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -C(=O)-O-, -NH-(CH ２ ) m -OC(=O)-, -NH-(CH ２ ) m -C(=O)-O-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m-OC(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-O-, -NH-(CH ２ ) m -C(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-, -NH-(CH ２ ) m -NH-C(=O)-NH-, -NH-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m -NH-C ６ H ４ wherein m is an integer of 1 to 5.

[0304] Y ａ２２ is -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S(=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ - is preferred. ａ２２ is more preferably —NH—C(═O)—, —C(═O)—NH—, —O—C(═O)—NH—, —NH—C(═O)—O— or —NH—C(═O)—NH—. ａ２２ may not be a direct bond.

[0305] Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a linear or branched structure. Z preferably has 2 to 4 carbon atoms, and particularly preferably 2. Specific examples of Z include a direct bond, -CH ２ -, -CH ２ CH ２ -, -CH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ CH ２ -, -CH２ CH ２ CH ２ CH ２ CH ２ -, -CH having a branched structure ２ CH=, -CH having a branched structure ２ (CH-)CH ２ -, -CH having a branched structure ２ CH ２ CH=, -CH having a branched structure ２ CH ２ CH ２ CH ２ CH=, -CH having a branched structure ２ CH ２ (CH-)CH ２ -, -CH having a branched structure ２ CH ２ CH ２ Z does not have to be a direct bond.

[0306] Monomer (a2) is CH2=C(-X ａ２ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ２ , C.H. ２ =C(-X ａ２ )-C(=O)-O-(CH ２ ) ｍ -OC(=O)-NH-R ａ２ , C.H. ２ =C(-X ａ２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-OR ａ２ , C.H. ２ =C(-X ａ２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-NH-R ａ２ Preferably, R ３ and X ａ２ has the same meaning as above.]. The monomer (a2) is CH2=C(-X ａ２ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ２It is particularly preferred that:

[0307] Monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, monomer (a2) can be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or a long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0308] Preferred examples of the monomer (a) are as follows: stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate; stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0309]

[0310]

[0311]

[0312]

[0313]

[0314] [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.] The compound of the above chemical formula is an acrylic compound having a hydrogen atom at the α-position, but specific examples may be a methacryl compound having a methyl group at the α-position and an α-chloroacrylic compound having a chlorine atom at the α-position.

[0315] The monomer (a2) has the formula: ａ２２ -C(=O)-NH-R ａ２３ -O-R ａ２１ [In the formula, R ａ２１ represents an organic residue having an ethylenically unsaturated polymerizable group, R ａ２２ represents a hydrocarbon group having 6 to 40 carbon atoms, R ａ２３ is a hydrocarbon group having 1 to 5 carbon atoms.]

[0316] R ａ２１ is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a carbon-carbon double bond. ａ２１１ =CH ２ , -CHR ａ２１１ =CH ２ , -CH ２ CHR ａ２１１ =CH ２ and the like. ａ２１１ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ２１ R may have various organic groups in addition to the ethylenically unsaturated polymerizable group, such as organic groups of chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. ａ２１ is -C(=O)CR ａ２１１ =CH ２ It is preferable that:

[0317] R ａ２２ R is a hydrocarbon group having 6 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbon groups and cyclic hydrocarbon groups. Among these, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred. ａ２２The number of carbon atoms is 6 or more and 40 or less, preferably 11 to 27, and particularly preferably 15 to 23.

[0318] R ａ２３ is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched, and may have an unsaturated bond, but is preferably linear. ａ２３ The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. ａ２３ is preferably an alkylene group.

[0319] The amide group-containing monomer is R ａ２２ is one type (for example, R ａ２２ is only a compound having 17 carbon atoms), or R ａ２２ A combination of multiple ａ２２ a compound having 17 carbon atoms, and R ａ２２ and a compound having 15 carbon atoms.

[0320] An example of the amide group-containing monomer is carboxylic acid amide alkyl (meth)acrylate.Specific examples of the amide group-containing monomer include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristate amide ethyl (meth)acrylate, laurate amide ethyl (meth)acrylate, isostearate ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tertiary butylcyclohexyl caproate amide ethyl (meth)acrylate, adamantanecarboxylic acid ethyl amide (meth)acrylate, naphthalenecarboxylic acid amide ethyl (meth)acrylate, anthracenecarboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)acrylate, stearic acid amide propyl (meth)acrylate, palmitic acid amide ethyl vinyl ether, stearic acid amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, stearic acid amide ethyl allyl ether, and mixtures thereof.

[0321] The amide group-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamidoethyl (meth)acrylate, the amount of stearamidoethyl (meth)acrylate may be, for example, 40 wt% or more, 50 wt% or more, 60 wt% or more, or 70 wt% or more, based on the total weight of the amide group-containing monomers. The amount of stearamidoethyl (meth)acrylate may be 90 wt% or less, 80 wt% or less, or 70 wt% or less, based on the total weight of the amide group-containing monomers. The remaining monomer may be, for example, palmitamidoethyl (meth)acrylate.

[0322] The amount of monomer (a2) in monomer (a) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, and is preferably 30% by weight or more.

[0323] (b) Hydrophilic Group-Containing Monomer The vinyl polymer may contain a hydrophilic group-containing monomer (b). Monomer (b) is a monomer other than monomer (a) that has a hydrophilic group. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms), particularly an oxyethylene group. In particular, monomer (b) is preferably an oxyalkylene (meth)acrylate, such as polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or polyalkylene (or monoalkylene) glycol di(meth)acrylate, or polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0324] Monomer (b) has the formula: CH ２ =CX ｂ C(=O)-Y ｂ - (R ｂ O) ｎ -A ｂ [In the formula, X ｂ is a hydrogen atom or a methyl group, and Y ｂ is —O— or —NH—, Rｂ are each independently an alkylene group having 2 to 6 carbon atoms, ｂ represents a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH ２ =CX ｂ C(═O)—, and n is an integer of 1 to 90.

[0325] Examples of monomer (b) are those of the formula: CH ２ =CX ｂ C(=O)-O-(R ｂ O) ｎ -A ｂｉ (b1) and CH ２ =CX ｂ C(=O)-O-(R ｂ O) ｎ -C(=O)CX ｂ =CH ２ (b2), CH ２ =CX ｂ C(=O)-NH-(R ｂ O) ｎ -A ｂｉ (b3) wherein X ｂ are each independently a hydrogen atom or a methyl group; ｂｉ are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, ｂ are each independently an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 90.

[0326] n may be, for example, 1 to 50, particularly 1 to 30, and especially 1 to 15 or 2 to 15. Alternatively, n may be, for example, 1. R ｂ may be a linear or branched alkylene group, for example, a group of the formula -(CH ２ ) ｘ - or - (CH ２ ) ｘ１ -(CH(CH ３ )) ｘ２ - [wherein x1 and x2 are 0 to 6, for example, 2 to 5, and the sum of x1 and x2 is 1 to 6. -(CH ２ )ｘ１ - and - (CH (CH ３ )) ｘ２ The order of - is not limited to the illustrated formula and may be random. ｂ O) n In -, R may be two or more types (for example, two to four types, particularly two types), and -(R ｂ O) n - is, for example, -(R １ O) ｎ１ - and - (R ２ O) ｎ２ - [wherein, R １ and R ２ are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90.

[0327] R in formulas (b1), (b2) and (b3) ｂ is particularly preferably an ethylene group, a propylene group or a butylene group, and particularly preferably a butylene group. ｂ R may be a combination of two or more alkylene groups. In this case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. ｂ Examples of the combination include a combination of an ethylene group / propylene group, a combination of an ethylene group / butylene group, and a combination of a propylene group / butylene group. The monomer (b) may be a mixture of two or more types. In this case, at least one of the monomers (b) is a mixture of R in formula (b1), (b2), or (b3). ｂ is preferably an ethylene group, a propylene group, or a butylene group. When a polyalkylene glycol di(meth)acrylate represented by formula (b2) is used, it is not preferable to use it alone as the monomer (b), but it is preferable to use it in combination with the monomer (b1). In that case, it is also preferable to keep the content of the compound represented by formula (b2) to less than 30% by weight of the monomer (b) used.

[0328] Specific examples of the monomer (b) can be exemplified by, for example, the following, but are not limited thereto. CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)O-H CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)O-H CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)O-H CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)O-H CH2=CHCOO-C(CH3)(CH2CH3)O-H CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)5-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O)5-CH3 CH2=CHCOO-(CH2CH2O)9-CH3 CH2=CHCOO-(CH2CH2O) 23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3

[0329] CH2=CHCOO-(CHzCH(CH3)O)9-H CH2=CHCOO-(CH2CH(CH3)O)9-CH3 CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3 CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=CHCOO-(CH2CH2O) 20 [[ID=第十三条]]-(CH2CH(CH3)O)5-CH2-CH=CH2 It should be noted that there seems to be a typo in your original text where "CHzCH(CH3)O" should probably be "CH2CH(CH3)O". I translated it as it was but this might need to be corrected in the original for a more accurate representation.

[0330] CH2=CHCOO-(CH2CH2O)9-H CH2=C(CH3)COO-CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH3)O-H CH2=C(CH3)COO-CH(CH3)CH2O-H CH2=C(CH3)COO-CH2CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH(CH3)O-H CH2=C(CH3)COO-CH2CH(CH3)CH2O-H CH2=C(CH3)COO-CH(CH3)CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH2CH3)O-H CH2=C(CH3)COO-CH2C(CH3)2O-H CH2=C(CH3)COO-CH(CH2CH3)CH2O-H CH2=C(CH3)COO-C(CH3)2CH2O-H CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H CH2=C(CH3)COO-(CH2CH2O)2-H CH2=C(CH3)COO-(CH2CH2O)4-H CH2=C(CH3)COO-(CH2CH2O)5-H CH2=C(CH3)COO-(CH2CH2O)6-H CH2=C(CH3)COO-(CH2CH2O)9-H CH2=C(CH3)COO-(CH2CH2O)5-CH3 CH2=C(CH3)COO-(CH2CH2O)9-CH3 CH2=C(CH3)COO-(CH2CH2O) 23 -CH3 CH2=C(CH3)COO-(CH2CH2O) 90 -CH3 CH2=C(CH3)COO-(CH2CH(CH3)O)9-H

[0331] CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)COO-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0332] CH2=CH-C(=O)-NH-CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2C(CH3)2O-H CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=CH-C(=O)-NH-C(CH3)2CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=CH-C(=O)-NH-(CH2CH2O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)4-H CH2=CH-C(=O)-NH-(CH2CH2O)5-H CH2=CH-C(=O)-NH-(CH2CH2O)6-H CH2=CH-C(=O)-NH-(CH2CH2O)9-H CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 23-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0333] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0334] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0335] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0336] The monomer (b) may be X ２ is a hydrogen atom. The monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0337] (c) Ion-donating group-containing monomer The vinyl polymer may contain an ion-donating group-containing monomer (c). The monomer (c) is preferably a monomer containing an olefinic carbon-carbon double bond and an ion-donating group (particularly, an acrylic monomer). The ion-donating group is an anion-donating group and / or a cation-donating group.

[0338] Examples of the monomer having an anion donating group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having an anion donating group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphate, vinylbenzenesulfonic acid, acrylamido-tertiarybutylsulfonic acid, and salts thereof.

[0339] Salts of anion-donating groups include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0340] In the monomer having a cation donating group, examples of the cation donating group are amino groups, preferably tertiary amino groups and quaternary amino groups. In the tertiary amino group, two groups bonded to the nitrogen atom may be the same or different and may be an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an aromatic aliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cation donating group may be in the form of a salt.

[0341] The cation-donating group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and salts thereof are preferred.

[0342] Specific examples of the monomer having a cation donor group are as follows: CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0343] The ion-donating group-containing monomer (c) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0344] (d) Halogenated Olefin Monomer The vinyl polymer may have a repeating unit derived from a halogenated olefin monomer (d). The halogenated olefin monomer (d) may not contain fluorine atoms. The halogenated olefin monomer (d) is preferably an olefin having 2 to 20 carbon atoms and substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. The halogenated olefin monomer (d) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred examples of the halogenated olefin monomer (d) include vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride or vinylidene chloride is preferred because it enhances water repellency (particularly the durability of water repellency). The presence of repeating units derived from the halogenated olefin monomer (d) provides the vinyl polymer with enhanced wash durability.

[0345] (e) Crosslinkable Monomer The crosslinkable monomer of the vinyl polymer has at least two reactive groups and / or ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), and the crosslinkable monomer (e) may be a monomer that does not contain fluorine atoms. It may also be a compound that does not contain fluorine atoms. The crosslinkable monomer (e) may be a compound that has at least two ethylenically unsaturated double bonds (preferably, (meth)acrylate groups), or a compound that has at least one ethylenically unsaturated double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, etc.

[0346] The crosslinking monomer may be a mono(meth)acrylate, di(meth)acrylate or di(meth)acrylamide having a reactive group.

[0347] One example of a crosslinkable monomer is a vinyl monomer having a reactive group.

[0348] Examples of crosslinkable monomers include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0349] (f) Cyclic Hydrocarbon Group-Containing Monomer The vinyl polymer may have a repeating unit derived from a cyclic hydrocarbon group-containing monomer (f). The cyclic hydrocarbon group-containing monomer (f) is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0350] The cyclic hydrocarbon group-containing monomer (f) preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0351] The cyclic hydrocarbon group may be alicyclic or aromatic, preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a linear or branched chain hydrocarbon group).

[0352] The cyclic hydrocarbon group may have 4 or more, 6 or more, or 8 or more carbon atoms, and may have 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less carbon atoms.

[0353] Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a bornyl group, an isobornyl group, a norbornyl group, a dicyclopentanyl group, a dicyclopentenyl group, a benzyl group, a phenyl group, a naphthyl group, a 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (for example, a cyclohexylene group, an adamantylene group, a phenylene group, a naphthylene group, etc.), and groups which are substitution products thereof.

[0354] Specific examples of the cyclic hydrocarbon group-containing monomer include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and compounds in which these acrylates are substituted with acrylamide, etc. These may be used alone or in combination of two or more.

[0355] (g) Other Monomers The other monomers are not limited to these examples and include acrylonitrile, organosiloxane-containing (meth)acrylates, short-chain alkyl (meth)acrylates, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, vinyl alkyl ethers, etc. The other monomers (g) may be used alone or in combination of two or more.

[0356] [Polymer composition] The combination of monomers (a) to (g) constituting the repeating units of the vinyl polymer is not particularly limited, but examples are as follows (brackets omitted): a b c a+b a+b+c a+c a+d a+b+c+d a+b+c+d+e a+b+c+d+e+f Furthermore, another monomer (g) may be used in combination with the above combinations. In the case of pulp products, it is preferable to use the monomer (a), monomer (b), and monomer (c) in combination.

[0357] The amount of repeating units derived from monomer (a) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the vinyl polymer. The amount of repeating units derived from monomer (a) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer.

[0358] The amount of repeating units derived from monomer (b) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the vinyl polymer. The amount of repeating units derived from monomer (b) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (b) 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, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a). The amount of repeating units derived from monomer (b) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (a).

[0359] The amount of repeating units derived from monomer (c) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the vinyl polymer. The amount of repeating units derived from monomer (c) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (c) 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, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a). The amount of repeating units derived from monomer (c) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (a).

[0360] The amount of repeating units derived from monomer (d) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the vinyl polymer. The amount of repeating units derived from monomer (d) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (d) 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, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a). The amount of repeating units derived from monomer (d) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (a).

[0361] The amount of repeating units derived from monomer (e) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the vinyl polymer. The amount of repeating units derived from monomer (e) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (e) 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, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a). The amount of repeating units derived from monomer (e) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (a).

[0362] The amount of repeating units derived from monomer (f) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the vinyl polymer. The amount of repeating units derived from monomer (f) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (f) 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, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a). The amount of repeating units derived from monomer (f) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (a).

[0363] The amount of repeating units derived from monomer (g) may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the vinyl polymer. The amount of repeating units derived from monomer (g) may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less, based on the vinyl polymer. The amount of the repeating units derived from monomer (g) 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, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 100 parts by weight of the amount of the repeating units derived from monomer (a). The amount of repeating units derived from monomer (g) may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 10 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the amount of repeating units derived from monomer (a).

[0364] [Polymerization Method] Vinyl polymers can be produced by known polymerization methods, and the polymerization reaction conditions can be selected arbitrarily. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0365] In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of the monomers.

[0366] The organic solvent is inert to the monomers and dissolves them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically, ethanol, butanol, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3,000 parts by weight, for example, 50 to 2,000 parts by weight, per 100 parts by weight of the total of the monomers.

[0367] Emulsion polymerization involves emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, purging with nitrogen, and then polymerizing the mixture at a temperature ranging from 50 to 80°C for 1 to 20 hours with stirring. Examples of polymerization initiators that can be used include water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount ranging from 0.01 to 10 parts by weight per 100 parts by weight of the monomer.

[0368] To obtain a polymer aqueous dispersion with excellent shelf stability, it is desirable to polymerize the monomer by microparticulating it in water using an emulsifying device capable of applying powerful crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer. Furthermore, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and are used in a range of 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsification and copolymerization properties.

[0369] The water-soluble organic solvent may be any of the organic solvents described above. Examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. These may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0370] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomers.

[0371] [Oil] Oil will be described as an example of a liquid-repellent compound. The oil may be liquid or solid (wax) at room temperature. The oil may be selected from synthetic oils, mineral oils, animal oils, and vegetable oils. The oil may be a hydrocarbon oil or a non-hydrocarbon oil, and is typically a compound having a higher hydrocarbon structure (e.g., having 10 or more, 20 or more, or 30 or more carbon atoms). The hydrocarbon group that the oil may have is as described above. The oil may be different from the amine-modified, polyol-modified, and polycarboxylic acid-modified compounds described above. The oil is a non-volatile oily compound, and the boiling point may be, for example, 200°C or higher, 250°C or higher, or 300°C or higher.

[0372] The melting point of the oil may be -100°C or higher, -75°C or higher, -50°C or higher, 0°C or higher, 30°C or higher, 40°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, 50°C or higher, 60°C or higher, 70°C or higher, or 80°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, 50°C or lower, 25°C or lower, 0°C or lower, -25°C or lower, -50°C or lower, -75°C or lower, or -100°C or lower, for example, 150°C or lower, 100°C or lower, 50°C or lower, 0°C or lower, or -50°C or lower. The melting point of the oil may be measured in accordance with JIS K 2235-1991.

[0373] The oil may be low molecular weight (e.g., molecular weight of 1000 or less, or 500 or less) or high molecular weight. When the oil is high molecular weight, 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, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 75000 or less, 50000 or less, or 3,000 or less.

[0374] [Synthetic Oil] Synthetic oil is an oil (oily compound) obtained by chemical synthesis, and may be liquid or solid (wax) at room temperature. Examples of synthetic oils include hydrocarbon oils, ester oils, ether oils, amide oils, and silicone oils.

[0375] [Mineral Oil] The mineral oil may be liquid or solid (wax) at room temperature. Examples of the mineral oil include petrolatum, liquid paraffin, paraffin wax, microcrystalline wax, montan wax, ozokerite wax, ceresin wax, and petrolatum wax.

[0376] [Vegetable Oil / Animal Oil] The vegetable oil or animal oil may be liquid or solid (wax) at room temperature. Soybean oil, hydrogenated soybean oil, rapeseed oil, sunflower oil, safflower oil, peanut oil, corn oil, cottonseed oil, rice bran oil, kapok oil, sesame oil, olive oil, linseed oil, castor oil, hydrogenated jojoba oil, cocoa oil, palm oil, palm kernel oil, coconut oil, rapeseed oil, hydrogenated rapeseed oil, hemp seed oil, rice oil, tea seed oil, castor oil, hydrogenated castor oil, sesame oil, fish oil, shark liver oil, squalene oil, squalene, beef tallow, lard (pork fat), mutton tallow, beef foot oil, whale oil, salmon oil, bonito oil, herring oil, cod oil, etc., hydrogenated oils and hydrogenated oils thereof; rice wax, carnauba wax, sunflower wax, candelilla wax, sumac Examples of suitable fatty acids include wax, beeswax, lanolin, spermaceti, and privet wax; fatty acids such as stearic acid, capric acid, caproic acid, linoleic acid, linolenic acid, palmitic acid, lauric acid, and eleostearic acid; fatty alcohols such as lauryl alcohol, cetostearyl alcohol, stearyl alcohol, cetyl alcohol, and myristyl alcohol; fatty acid esters such as glycerol monostearate, glycerol monooleate, acetylated monoglyceride, tristearin, tripalmitin, and cetyl ester glyceryl palmitostearate; glyceryl behenate; and medium-chain triglycerides.

[0377] [Dispersant] The oil-proofing agent composition of the present disclosure may contain a dispersant. The dispersant may be at least one selected from organic dispersants and inorganic dispersants. The dispersant may be at least one selected from anionic dispersants, nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants.

[0378] 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.

[0379] 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.

[0380] The dispersant may be fluorine-free.

[0381] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant, which may be a nonionic surfactant.

[0382] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100,000 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.

[0383] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0384] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0385] 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.

[0386] 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.

[0387] 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.

[0388] 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).

[0389] 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.

[0390] 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.

[0391] 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.

[0392] 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.

[0393] R １ R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. １Preferred 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.

[0394] 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.

[0395] 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.

[0396] [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.

[0397] 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. The molecular weight of the cationic dispersant 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.

[0398] 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.

[0399] 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 ２４ Specific examples of X are alkyl groups (e.g., methyl, butyl, stearyl, and palmityl). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). The cationic dispersant may be a monoalkyltrimethylammonium salt (wherein the alkyl has 4 to 40 carbon atoms).

[0400] 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.

[0401] 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.

[0402] 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.

[0403] [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.

[0404] The anionic dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100,000 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.

[0405] 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).

[0406] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant, which may be an amphoteric surfactant.

[0407] The amphoteric dispersant may be a low molecular weight or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more. The molecular weight may be 100,000 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.

[0408] 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.

[0409] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0410] 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. The average primary particle size of the inorganic dispersant 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.

[0411] 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.

[0412] [Amount of Dispersant] The amount of the 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. The amount of the dispersant may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the liquid repellent compound.

[0413] [Excipient] The oil-proofing composition of the present disclosure contains an excipient. The excipient is included for the purpose of molding, extending, diluting, etc., of the oil-proofing composition of the present disclosure. The excipient may be at least one selected from an organic excipient and an inorganic excipient. The excipient may be either an organic excipient or an inorganic excipient, or a combination of an organic excipient and an inorganic excipient.

[0414] [Organic excipient] The excipient may contain an organic excipient. The organic excipient may be either a natural organic excipient or a synthetic organic excipient. Examples of natural organic excipients include lactose, cellulose and its derivatives, starch and its derivatives, and sugar alcohols. Derivatives include products decomposed by enzymes, etc. Specific examples of natural organic excipients include glucose (grape sugar), fructose (fruit sugar), galactose, dextrin, sucrose, lactose, lactose composition, lactose hydrate, crystalline cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, isomaltodextrin (an enzymatic hydrolysis product of starch), mannitol, sorbitol, trehalose, maltose, erythritol, xylitol, carrageenan, xanthan gum, chitosan, guar gum, glucomannan, gluten, pullulan, locust bean gum, tamarin seed gum, gum arabic, karaya gum, pectin, konjac mannan, agar, alginic acid, gellan gum, Agrobacterius sinoglycan, cationized guar gum, rice bran, rice bran oil cake, corn starch, α-starch, carboxymethyl starch, corn starch, and potato starch. Examples of synthetic organic excipients include polyvinyl alcohol, poly(meth)acrylic acid and its salts, polymethyl methacrylate, polyvinylpyrrolidone, and sucrose fatty acid esters.

[0415] The cellulose may be a cellulose nanofiber. Cellulose nanofibers are obtained by pulp, a raw material for cellulose, being refined to the nanometer level, and are fine fibers with a fiber width of, for example, about 1 to 500 nm. The cellulose nanofiber may be an unmodified cellulose nanofiber, or an anionized or cationized nanofiber. For example, the cellulose nanofiber may be a carboxymethyl cellulose nanofiber.

[0416] The sucrose fatty acid ester may be at least one selected from the group consisting of sucrose laurate, sucrose myristate, sucrose palmitate, sucrose stearate, and sucrose oleate.

[0417] [Inorganic excipients] Examples of inorganic excipients include silicic acid, silicates (e.g., calcium silicate, magnesium silicate), light anhydrous silicic acid, diatomaceous earth, zeolite, talc, vermiculite, bentonite, dicalcium phosphate, calcium sulfate, calcium carbonate, and magnesium carbonate.

[0418] In one embodiment, the excipient may include at least one selected from the group consisting of saccharides, polysaccharides and polysaccharide derivatives, water-soluble vinyl polymers and salts thereof, and silicates.

[0419] [Amount of excipient] The amount of excipient 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. The amount of excipient 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, 80 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the liquid repellent compound.

[0420] [Lubricant] The oil-proofing composition of the present disclosure may contain a lubricant. The lubricant adheres to the particle surfaces of the liquid-repellent compound, dispersant, excipient, etc., and tends to weaken the adhesive force between particles. Therefore, the particles are less likely to adhere to each other and are more likely to peel off. Furthermore, when molding the oil-proofing composition, adhesion of the oil-proofing composition to molding equipment, etc. is likely to be suppressed, which can prevent the molding equipment from becoming dirty. Examples of lubricants include magnesium stearate, calcium stearate, anhydrous silicic acid, talc, sucrose fatty acid esters, glycerin fatty acid esters, polyethylene glycol, hydrogenated oil, and sodium stearyl fumarate.

[0421] [Amount of Lubricant] The amount of lubricant 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. The amount of lubricant 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, 80 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the liquid repellent compound.

[0422] [Binder] The oil-proofing composition of the present disclosure may contain a binder. The binder can contribute to integrating the liquid-repellent compound, dispersant, and excipient. In particular, when the liquid-repellent compound, dispersant, and excipient are powders, the binder facilitates aggregation of these powders, making it easier to mold the oil-proofing composition. The inclusion of a binder can improve the strength of the oil-proofing composition, making it easier to prevent cracking, chipping, and the like of the oil-proofing composition during transportation. Examples of binders include cellulose-based binders such as hydroxypropyl cellulose, hypromellose phthalate, hydroxypropyl methylcellulose acetate succinate, crystalline cellulose, powdered cellulose, low-substituted hydroxypropyl cellulose, carmellose sodium, ethyl cellulose, methyl cellulose, and hypromellose; starch-based binders such as corn starch, potato starch, wheat starch, rice starch, partially pregelatinized starch, and pregelatinized starch; silicic acid-based binders such as magnesium aluminometasilicate, synthetic aluminum silicate, light anhydrous silicic acid, and calcium silicate; gum arabic, sodium alginate, dextrin, gelatin, pullulan, povidone, and carboxyvinyl polymers; preferably, cellulose-based binders are used, and particularly preferably, hydroxypropyl cellulose.

[0423] [Amount of Binder] The amount of binder 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. The amount of binder 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, 80 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the liquid repellent compound.

[0424] [Disintegrant] The oil-proofing composition of the present disclosure may contain a disintegrant. Disintegrants easily absorb the surrounding liquid medium. Therefore, an oil-proofing composition containing a disintegrant is more likely to absorb the liquid medium, which is expected to promote dissolution, reduce mechanical strength due to swelling, and increase the rate of penetration into the oil-proofing composition, and make it easier to finely disintegrate the oil-proofing composition in the liquid medium. When the oil-proofing composition is in tablet form (e.g., a tablet), the tablet is more likely to disintegrate and become coarse particles, making it easier to prepare a dispersion of the oil-proofing composition more efficiently.

[0425] Disintegrants include sodium starch glycolate, croscarmellose sodium, low-substituted hydroxypropyl cellulose, croscarmellose polyvinylpyrrolidone, carboxymethyl cellulose, and calcium carboxymethyl cellulose.

[0426] [Amount of Disintegrant] The amount of the disintegrant 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. The amount of the disintegrant 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, 80 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the liquid-repellent compound.

[0427] [Liquid Medium] The oil-proofing composition 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 oil-proofing composition may be a dispersion or a solution. The oil-proofing composition of the present disclosure may contain at least water.

[0428] 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.

[0429] [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, relative to 1 part by weight of the liquid repellent compound. The amount of the liquid medium may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

[0430] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 1 part by weight of the liquid-repellent compound. The amount of water may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid-repellent compound.

[0431] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 1 part by weight of the liquid repellent compound. The amount of the organic solvent may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, relative to 1 part by weight of the liquid repellent compound.

[0432] [Silicone] The oil-proofing composition of the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, the oil-proofing composition has good liquid repellency.

[0433] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0434] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more. The weight average molecular weight of the silicone may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[0435] [Amount of Silicone] The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound. The amount of silicone may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the liquid repellent compound.

[0436] [Wax] The oil-proofing composition according to the present disclosure may contain a wax, which can impart good liquid repellency to the substrate.

[0437] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, mineral wax, etc. Paraffin wax is preferred. Specific examples of compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane), and normal alkenes (e.g., 1-eicosane, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane). The number of carbon atoms in the compounds constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be from 200 to 2000, for example, from 250 to 1500, or from 300 to 1000. These may be used alone or in combination of two or more.

[0438] The melting point of the wax may be 50° C. or higher, 55° C. or higher, 60° C. or higher, 65° C. or higher, or 70° C. or higher, preferably 55° C. or higher, more preferably 60° C. or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0439] [Amount of Wax] The amount of wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound. The amount of wax may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the liquid repellent compound.

[0440] [Organic Acid] The oil-proofing agent composition 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 organic acid may be used, or two or more organic acids may be used in combination.

[0441] [Amount of Organic Acid] The amount of the organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid-repellent compound. The amount of the organic acid may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the liquid-repellent compound. The amount of the organic acid may be adjusted so that the pH of the oil-proofing composition is 3 to 10, for example, 5 to 9, particularly 6 to 8. The oil-proofing composition may be acidic (pH 7 or less, for example, 6 or less).

[0442] Curing Agent The oil-proofing composition of the present disclosure may contain a curing agent (active hydrogen-reactive compound or active hydrogen-containing compound).

[0443] The curing agent (crosslinking agent) in the oil-resistant composition can effectively cure the liquid-repellent compound. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of the liquid-repellent compound. Examples of the active hydrogen-reactive compound include isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0444] 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.

[0445] 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.

[0446] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0447] 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.

[0448] 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.

[0449] 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.

[0450] 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 even in solution and can be used in the same solution as the oil-resistant agent composition.

[0451] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination of two or more.

[0452] 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.

[0453] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resins and methyl etherified melamine resins.

[0454] [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. The amount of the curing agent may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the liquid repellent compound.

[0455] [Other Components] The oil-proofing composition may contain components other than those described above. Examples of other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, sizing agents, fillers, preservatives, antibacterial agents, deodorizers, and fragrances. These may be used alone or in combination of two or more. In addition to the above-mentioned components, other components may be blended, such as other water and / or oil repellents, dispersants, softeners, flame retardants, paint fixatives, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, viscosity modifiers, pH adjusters, insect repellents, antifoaming agents, shape-retaining agents, clays, pigments, polymer dispersants, soil release agents, fiber surface modifiers such as enzymes (e.g., cellulase, amylase, protease, lipase, and keratinase), and foam inhibitors. These may be used alone or in combination of two or more.

[0456] [Polysaccharides] Examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofiber, cellulose nanofiber, pullulan, etc. The polysaccharide may be a substituted modified polysaccharide (excluding the above-mentioned liquid repellent compounds), and in particular may be a modified polysaccharide into which a hydroxyl group or a cationic group has been introduced.

[0457] [Paper Strength Agents, Flocculants, Retention Aids, or Coagulants] Examples of paper strength agents, flocculants, retention aids, or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formalin condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0458] Sizing Agents Examples of sizing agents include cellulose-reactive sizing agents, e.g., rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, e.g., emulsions / dispersions of acid anhydrides such as alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, e.g., copolymers of styrene and acrylate.

[0459] [Antistatic Agent] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate ester salts, phosphonates, and phosphate ester salts; amphoteric antistatic agents such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, and nonionic antistatic agents such as aminoalcohols and its derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives. Ion-conductive polymers obtained by polymerizing or copolymerizing monomers having these cationic, anionic, or amphoteric ionic conductive groups may also be used. These may be used alone or in combination of two or more.

[0460] [Preservatives] Preservatives can be used mainly to enhance antiseptic and bactericidal properties and maintain antiseptic properties during long-term storage. Examples of preservatives include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol.

[0461] [Ultraviolet Absorber] An ultraviolet absorber is a chemical agent that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays and converts them into infrared rays, visible light, etc. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0462] [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.

[0463] [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).

[0464] [Amount of Other Components] The amount of each of the other components or the total amount thereof may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid repellent compound. The amount of each of the other components or the total amount thereof may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, relative to 100 parts by weight of the liquid repellent compound.

[0465] <Pulp Composition> The pulp composition of the present disclosure includes a liquid repellent compound and a pulp base material. The pulp composition of the present disclosure may have excellent oil resistance and / or water resistance, preferably both.

[0466] The pulp composition of the present disclosure is obtained by adding a liquid-repellent compound to a pulp base material. The pulp composition may be obtained by treating the pulp base material with an oil-proofing composition containing the liquid-repellent compound, and the amount of the oil-proofing composition added and the composition of the oil-proofing composition may be adjusted so that each component is present in a desired amount. Each component that can be contained in the oil-proofing composition may be added to the pulp composition as a separate additive.

[0467] The pulp composition of 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 pulp composition of the present disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds.

[0468] The pH of the pulp composition may be 3 to 10, for example 5 to 9, particularly 6 to 8, and the amount of each component may be adjusted to achieve such a pH.

[0469] [Pulp Base Material] The pulp composition includes a pulp base material. The pulp base material is made of pulp, and the pulp may be wood pulp, non-wood pulp, recycled paper pulp, or the like, and may include at least bagasse pulp.

[0470] [Wood Pulp] Wood pulp includes softwood kraft pulp obtained from species such as Abies and Pinus, and hardwood kraft pulp obtained from species such as Acacia, Eucalyptus, Beech, and Populus (e.g., poplar). Examples of softwood kraft pulp include unbleached softwood kraft pulp (NUKP), bleached softwood pulp (NBKP), semi-bleached softwood kraft pulp (NSBKP), and softwood sulfite pulp. Examples of hardwood kraft pulp include unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), and hardwood sulfite pulp. The pulps used may be used alone or in combination. In addition to kraft pulp, there are also softwood kraft pulp and hardwood kraft pulp, as well as mechanical pulps such as stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), thermoground pulp (TGP), chemiground pulp (CGP), groundwood pulp (GP), thermomechanical pulp (TMP), etc. Furthermore, waste paper pulp includes disintegrated waste paper pulp, disintegrated and deinked waste paper pulp, or disintegrated, deinked and bleached waste paper pulp, which are produced from brown waste paper, recycled kraft envelope paper, recycled magazine paper, recycled newspaper paper, recycled flyer paper, recycled office paper, recycled corrugated cardboard paper, white recycled paper, Kent recycled paper, imitation recycled paper, recycled land paper, etc.

[0471] [Non-wood Pulp] Examples of non-wood pulp include pulp obtained from bagasse, kenaf, bamboo, linter, cotton, linen, hemp, ramie, straw, esparto, Manila hemp, sisal, jute, flax, ganpi, mitsumata, and paper mulberry. [Synthetic Fiber] The pulp composition may contain synthetic fiber. Examples of synthetic fibers that can be used include polyester fibers such as polyamide fiber and polyethylene terephthalate fiber (hereinafter also referred to as PET or PET fiber), acrylic fiber, polyolefin fibers such as polyethylene fiber and polypropylene fiber, aramid fiber, polyethylene naphthalate fiber, polybutylene terephthalate fiber, polyphenylene sulfide fiber (hereinafter also referred to as PPS fiber), polyacetal fiber, liquid crystal polymer fiber, glass fiber, and polyimide fiber. Examples of non-wood pulp include pulp obtained from oak, etc.

[0472] [Pulp fiber length] From the viewpoint of improving oil resistance, the average fiber length of the pulp is preferably 0.1 mm or more, more preferably 0.3 mm or more, and even more preferably 0.5 mm or more, and from the viewpoint of ease of production, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, even more preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.2 mm or less.

[0473] [Pulp Fiber Width] From the viewpoint of improving oil resistance, the average fiber diameter of the pulp is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more, and is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less.

[0474] [Composition of Pulp Base Material] When bagasse pulp is used, it may account for more than 0% by weight, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more in the pulp base material, preferably 20% by weight or more, and may also account for 100% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less, for example, 80% by weight or less.

[0475] The total amount of pulp other than bagasse in the pulp base material may be 0% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 99% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less.

[0476] The amount of wood pulp in the pulp base material may be 0% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 99% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less.

[0477] [Form of Pulp Base Material] The form of the pulp base material when the liquid-repellent compound is added may be pulp alone, a pulp slurry, a pulp product, etc. Specific examples include pulp such as 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; pulp slurries containing the above pulp; and pulp products such as paper, paper containers, and pulp molded products.

[0478] [Amount of Pulp Base Material] The amount of the pulp base material in the pulp composition may be 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, 75 wt% or more, or 90 wt% or more, and may be 99 wt% or less, 75 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, 4 wt% or less, or 3 wt% or less. Typically, when the pulp composition is prepared by internal addition, the amount of the pulp base material in the pulp composition is 30 wt% or less, and when the pulp composition is prepared by external addition, the amount of the pulp base material in the pulp composition may be 75 wt% or more.

[0479] The amount of the pulp base material may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more in the pulp composition excluding the liquid medium, and may be 99.9% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, or 55% by weight or less.

[0480] [Liquid Medium] The pulp composition may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, and is typically an aqueous medium, particularly water. The liquid medium may also contain a liquid medium derived from an oil-proofing agent composition.

[0481] The amount of the liquid medium in the pulp composition may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more, and may be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium in the pulp composition is 50% by weight or more, particularly 90% by weight or more, and when the pulp composition is prepared by external addition, the amount of the liquid medium in the pulp composition is 30% by weight or less, particularly 10% by weight or less.

[0482] [Liquid-repellent compound] The pulp composition contains a liquid-repellent compound. For details of the types of liquid-repellent compounds, the explanation of the liquid-repellent compounds in <Oil-proofing composition> is incorporated herein by reference.

[0483] [Amount of Liquid-Repellent Compound] The amount of the liquid-repellent compound relative to the pulp base material may be 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, 0.75 wt% or more, 1.0 wt% or more, 2.0 wt% or more, or 3.0 wt% or more, and is preferably 0.5 wt% or more, and may be 25 wt% or less, 20 wt% or less, 15 wt% or less, 10 wt% or less, 7.5 wt% or less, 5.0 wt% or less, 4.0 wt% or less, 3.0 wt% or less, 2.0 wt% or less, 1.0 wt% or less, 0.75 wt% or less, or 0.5 wt% or less, for example, 15 wt% or less, 5.0 wt% or less, or 3.0 wt% or less.

[0484] The amount of the amine-modified liquid repellent compound relative to the pulp base material may be 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, 0.75 wt% or more, 1.0 wt% or more, 2.0 wt% or more, or 3.0 wt% or more, and is preferably 0.5 wt% or more, and may be 25 wt% or less, 20 wt% or less, 15 wt% or less, 10 wt% or less, 7.5 wt% or less, 5.0 wt% or less, 4.0 wt% or less, 3.0 wt% or less, 2.0 wt% or less, 1.0 wt% or less, 0.75 wt% or less, or 0.5 wt% or less, for example, 15 wt% or less, 5.0 wt% or less, or 3.0 wt% or less.

[0485] The amount of the polyol-modified liquid repellent compound relative to the pulp base material may be 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, 0.75 wt% or more, 1.0 wt% or more, 2.0 wt% or more, or 3.0 wt% or more, and is preferably 0.5 wt% or more, and may be 25 wt% or less, 20 wt% or less, 15 wt% or less, 10 wt% or less, 7.5 wt% or less, 5.0 wt% or less, 4.0 wt% or less, 3.0 wt% or less, 2.0 wt% or less, 1.0 wt% or less, 0.75 wt% or less, or 0.5 wt% or less, for example, 15 wt% or less, 5.0 wt% or less, or 3.0 wt% or less.

[0486] The amount of the polycarboxylic acid-modified liquid repellent compound relative to the pulp base material may be 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, 0.75 wt% or more, 1.0 wt% or more, 2.0 wt% or more, or 3.0 wt% or more, and is preferably 0.5 wt% or more, and may be 25 wt% or less, 20 wt% or less, 15 wt% or less, 10 wt% or less, 7.5 wt% or less, 5.0 wt% or less, 4.0 wt% or less, 3.0 wt% or less, 2.0 wt% or less, 1.0 wt% or less, 0.75 wt% or less, or 0.5 wt% or less, for example, 15 wt% or less, 5.0 wt% or less, or 3.0 wt% or less.

[0487] The liquid-repellent compound may be added externally to the surface of a pulp substrate (e.g., a pulp product such as paper, a paper container, or a pulp molded product), and the amount of the liquid-repellent compound contained in the coating layer formed by the external addition treatment is 0.01 g / m ２Above, 0.03g / m ２ Above, 0.05g / m ２ Above, 0.1g / m ２ Above, 0.3g / m ２ Above, 0.5g / m ２ or more, or 1.0 g / m ２ or more, and ２ Below, 4.0g / m ２ Below, 3.0g / m ２ Below, 2.0g / m ２ Below, 1.0g / m ２ Below, 0.5g / m ２ Below, 0.3g / m ２ or less, or 0.1 g / m ２ It may be the following:

[0488] [Dispersant] The pulp composition may contain a dispersant. For details of the types of dispersants, the description of the dispersant in <Oil-proofing composition> is incorporated herein by reference.

[0489] [Amount of Dispersant] The amount of dispersant relative to the pulp base material may be 0.001% by weight or more, 0.01% by weight or more, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, preferably 5.0% by weight or less, more preferably 3.0% by weight or less.

[0490] [Paper Strength Agent] The pulp composition may contain a paper strength agent. Examples of the paper strength agent include polyacrylamide-based paper strength agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; polysaccharide-based paper strength agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde-modified starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofiber, cellulose nanofiber, cellulose nanocrystal, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides into which a hydroxyl group or a cationic group has been introduced); Polyamide-based paper strength agents such as polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; urea / melamine-based paper strength agents such as urea resins, melamine resins, urea-formaldehyde resins, and melamine-formaldehyde resins; polyvinyl alcohol-based paper strength agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, ethylene-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, diacetone group-modified polyvinyl alcohol, and terminal alkyl-modified polyvinyl alcohol; styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid esters, fatty acid diamides, polyethyleneimine resins, and ketone aldehyde resins. The paper strength agent in the present disclosure is preferably a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent, or a polyamide-based paper strength agent.

[0491] [Amount of Paper Strength Agent] The amount of the paper strength agent may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is preferably 5.0% by weight or less, based on the pulp.

[0492] [Sizing Agent] The pulp composition may contain a sizing agent. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, neutral sizing agents, and amphoteric sizing agents, such as rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents), alkyl ketene dimers, and alkenyl succinic anhydrides.

[0493] [Amount of Sizing Agent] The amount of sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, based on the pulp.

[0494] [Binder] A binder such as a water-soluble polymer such as casein, or a polyester resin, a polyurethane resin, a styrene-butadiene resin, a vinyl acetate resin, an ethylene-vinyl acetate resin, an acrylonitrile-butadiene resin, a polyethylene resin, a polypropylene resin, a carboxymethyl cellulose resin, a polyamide resin, a vinyl chloride resin, or a vinylidene chloride resin may be contained.

[0495] [Pigments] Inorganic pigments such as kaolin, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, magnesium oxide, aluminum hydroxide, alumina, silica, magnesium aluminosilicate, calcium silicate, white carbon, bentonite, zeolite, sericite, smectite, calcium sulfate, barium sulfate, synthetic mica, titanium dioxide, and zinc oxide may also be included; and organic pigments such as polydienes such as polyisoprene, polyneoprene, and polybutadiene; polyalkenes such as polybutene, polyisobutylene, and polypropylene; polymers and copolymers of vinyl monomers such as vinyl acetate, styrene, (meth)acrylic acid, (meth)acrylic acid alkyl esters, (meth)acrylamide, and methyl vinyl ether; polyurethane resins, polyester resins, polyamide resins, urea resins, melamine resins, and benzoguanamine resins may also be included.

[0496] [Other Additives] In addition to the above, the pulp composition may contain other additives such as paper co-agents used in the production of pulp products, such as fixing agents (aluminum sulfate, etc.), coagulants / flocculants (polyamine resins, etc.), retention aids (polyacrylamide resins, etc.), organic acids (formic acid, acetic acid, etc.), dyes, slime control agents, defoamers, polycarboxylic acids, waxes, and penetrants.

[0497] [Amount of Other Additives] The amount of other additives may be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, or 5% by weight or more, and may be 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less, based on the pulp base material.

[0498] Specific examples of pulp products include paper, paper containers, pulp molded products, food packaging materials, food containers, gypsum board base paper, coated base paper, medium paper, general liners and corrugating media, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper, etc. Suitable examples of pulp products include food packaging materials and food containers, and particularly pulp molded products for food contact applications.

[0499] <Method for Producing Oil-Resistant Composition> The method for producing the oil-resistant composition of the present disclosure includes: mixing a liquid-repellent compound, a dispersant, an excipient, and a liquid medium to obtain a precursor mixture; and subjecting the precursor mixture to a heating treatment or drying treatment to obtain a solid oil-resistant composition.

[0500] [Mixing step] The mixing step is a step of mixing a liquid-repellent compound, a dispersant, and an excipient to obtain a precursor mixture. In this step, components other than the liquid-repellent compound, the dispersant, and the excipient (for example, components of the present disclosure such as a binder and a disintegrant) may be mixed.

[0501] The mixing method is not particularly limited, and known mixing devices can be used. For example, a paddle mixer, ribbon mixer, butterfly mixer, drum mixer, etc. can be used. For example, mixing and / or kneading may be performed using a medicine spoon. Also, known granulation devices capable of mixing and / or kneading may be used. For example, extrusion granulators, stirring granulators, fluidized bed granulators, compression granulators, etc. can be used as granulators. Since the precursor mixture obtained by the granulator is in a particulate form, the handleability of the precursor mixture in subsequent steps can be improved.

[0502] From the viewpoint of more efficient mixing, the liquid repellent compound, dispersant, and / or excipient may be pulverized before mixing using a known pulverizer such as a jet mill, a ball mill, etc. By pulverizing the particles, the liquid repellent compound, dispersant, and excipient can be more easily mixed uniformly.

[0503] A small amount of a liquid medium may be added together with the liquid repellent compound, dispersant, and excipient. Alternatively, a dispersion or aqueous solution of the liquid repellent compound, dispersant, and / or excipient may be used. Adding a small amount of a liquid medium makes kneading easier.

[0504] [Heating Step and Drying Step] The heating step and drying step are steps for vaporizing and reducing the liquid medium contained in the precursor mixture. By subjecting the precursor mixture to a heating treatment or drying treatment, the oil-resistant composition of the present disclosure in a solid form can be obtained.

[0505] The heating time and drying time may be, for example, 30 minutes or more, 60 minutes or more, 90 minutes or more, 120 minutes or more, 180 minutes or more, 240 minutes or more, or 300 minutes or more. The heating time and drying time may be, for example, 600 minutes or less, 480 minutes or less, 420 minutes or less, 360 minutes or less, 300 minutes or less, 240 minutes or less, 180 minutes or less, or 120 minutes or less.

[0506] The heating temperature and drying temperature may be, for example, 100° C. or higher, 120° C. or higher, or 150° C. or higher. The heating time and drying time may be, for example, 200° C. or lower, 180° C. or lower, 150° C. or lower, or 130° C. or lower.

[0507] [Molding Step] In one embodiment, the method may include a molding step of molding the oil-proofing composition. The molding step may be performed after the mixing step and before the heating step or the drying step, or may be performed after the heating step or the drying step.

[0508] In molding the oil-proofing composition, the oil-proofing composition may be molded into tablets. A tablet press may be used as a device that enables such molding. That is, the oil-proofing composition of the present disclosure may be tableted. The type of tablet press is not particularly limited, and known tablet presses can be used. For example, the tablet press may be a single-punch tablet press that uses a pair of upper and lower punches to compress and mold the oil-proofing composition filled in a die to produce tablets, or a rotary tablet press in which dies are embedded at equal intervals around the periphery of a horizontally rotating turntable, and a series of operations of filling, compressing, and discharging the oil-proofing composition are continuously performed while the turntable rotates.

[0509] In molding the oil-proofing agent composition, the solid oil-proofing composition obtained by heating or drying may be crushed or pulverized. Although the crushed or pulverized product will have an irregular shape, this method is efficient for manufacturing when the oil-resistant composition of the present disclosure does not need to be molded into a specific shape and only needs to be adjusted to a predetermined size or smaller. Crushing or pulverization may be carried out using a known crusher or pulverizer.

[0510] <Method for Producing Treated Textile or Paper Products> The method for producing a product treated with an oil-proofing composition according to the present disclosure includes a treatment step of treating a substrate with the oil-proofing composition described above.

[0511] The term "treatment" means applying the oil-proofing composition to a substrate by immersion, spraying, coating, or the like. The treatment causes the liquid-repellent compound, which is an active ingredient of the oil-proofing composition, to adhere to the interior and / or surface of the substrate. Here, "adhesion" may be physical or chemical; for example, the liquid-repellent compound may be physically or chemically modified (by reacting with) hydroxyl groups of the substrate (fiber, paper, glass, etc.).

[0512] [Substrate] The substrate to be treated with the oil-proofing composition of the present disclosure is not limited, but is preferably a textile product or a paper product, particularly a paper product.

[0513] The oil-proofing composition according to the present disclosure imparts liquid repellency to a substrate (e.g., a fiber substrate or a paper substrate) and can function as at least one selected from the group consisting of a water repellent, an oil repellent, an oil-proofing agent, and a water-resistant agent. The substrate treated with the oil-proofing composition according to the present disclosure is, for example, oil-resistant paper or water-resistant paper.

[0514] Examples of substrates for textile products include natural fibers of animal or plant origin such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or mixtures of these fibers. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics, as well as cloth in the form of clothing (for example, water-repellent clothing such as raincoats) 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 cloth.

[0515] Examples of substrates for paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine paper, recycled corrugated cardboard or deinked recycled paper, paper containers, paper molded articles, etc. Specific examples of paper products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-quality paper, general liners and corrugating media, neutral white roll paper, neutral liner, rust-proof liner and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc., and suitable examples include food packaging materials and food containers.

[0516] Substrates to be treated with the oil-proofing composition of the present disclosure are not limited to textiles or paper products, but also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, plaster, and the like.

[0517] When the substrate is glass, the produced glass product may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflection layer, may be formed on the surface (outermost layer) of the glass substrate. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO ２ , SiO, ZrO ２ , TiO ２ , TiO, Ti ２ O ３ , Ti ２ O ５ , Al ２ O ３ , Ta ２ O ５ , CeO ２ , MgO, Y ２ O ３ , SnO ２ , MgF ２ , W.O. ３ These inorganic substances may be used alone or in combination of two or more (for example, as a mixture). When a multi-layer antireflection layer is formed, the outermost layer may contain SiO ２ and / or SiO is preferably used. When the article to be manufactured is an optical glass component for a touch panel, a transparent electrode, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomization film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, or the like, depending on its specific specifications.

[0518] [Treatment Method] The oil-resistant composition of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may involve dispersing and diluting the oil-resistant composition of the present disclosure in an organic solvent or water, as needed, and applying it to the interior and / or surface of the substrate by a known method such as dip coating, spray coating, or foam coating, followed by drying. After drying, a textile product is obtained to which the solid components of the oil-resistant composition are attached. If necessary, the composition may be applied together with an appropriate crosslinking agent and cured. The oil-resistant composition of the present disclosure may also be used in combination with various additives, such as water and / or oil repellents, antislip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint adhesion promoters, 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." The concentration of the oil-proofing composition in the treating 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.

[0519] The oil-proofing composition can be applied to a substrate by any method known for treating a substrate with a liquid. The substrate may be immersed in the oil-proofing composition, or a solution may be applied or sprayed onto the substrate. The treated substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the textile product is paper, the oil-proofing composition may be coated on the paper, or the solution may be applied or sprayed onto the paper, or the composition may be mixed with a pulp slurry before papermaking. The treatment may be an external or internal addition treatment. Alternatively, the oil-proofing composition may be applied to the textile product by a cleaning method, such as washing or dry cleaning.

[0520] [Treatment of Paper Products] Examples of paper substrates include paper, paper containers, and paper molded articles (for example, pulp molds).

[0521] The method for producing a paper product of the present disclosure includes mixing the oil-proofing composition of the present disclosure with a liquid medium to prepare an aqueous dispersion of the oil-proofing composition, and treating paper with the aqueous dispersion by external or internal addition treatment.

[0522] Because the oilproofing composition of the present disclosure is solid, it is dispersed in a liquid medium before treating paper with the oilproofing composition of the present disclosure. Because the oilproofing composition of the present disclosure contains a dispersant, a dispersion of the oilproofing composition (e.g., an aqueous dispersion) can be obtained by adding it to a liquid medium. From the viewpoint of more efficiently preparing the dispersion, the oilproofing composition may be stirred for a predetermined period of time after being added to the liquid medium. The liquid medium may be any of the liquid mediums disclosed herein, and may be, for example, water.

[0523] The amount of the oil anti-oil composition in the dispersion of the oil anti-oil composition of the present disclosure may be 1 wt% or more, 3 wt% or more, 5 wt% or more, 7 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, or 25 wt% or more. The amount of the oil anti-oil composition in the dispersion of the oil anti-oil composition of the present disclosure may be 50 wt% or less, 40 wt% or less, 30 wt% or less, 25 wt% or less, 20 wt% or less, or 15 wt% or less.

[0524] The amount of the liquid repellent compound in the dispersion of the oil proof composition of the present disclosure may be 1 wt% or more, 3 wt% or more, 5 wt% or more, 7 wt% or more, 10 wt% or more, 15 wt% or more, 20 wt% or more, or 25 wt% or more. The amount of the liquid repellent compound in the dispersion of the oil proof composition of the present disclosure may be 50 wt% or less, 40 wt% or less, 30 wt% or less, 25 wt% or less, 20 wt% or less, or 15 wt% or less.

[0525] The paper can be produced by a conventional papermaking method, such as an internal treatment method in which the oil-proofing composition is added to a pulp slurry before papermaking, or an external treatment method in which the oil-proofing composition is applied to paper after papermaking.

[0526] Size presses using external additive treatment methods can also be divided into the following categories based on the application method. One application method is the so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to the nip formed by passing paper between two rubber rolls, creating a pool of coating liquid called a pond, and the paper is passed through this pool of coating liquid to apply the size liquid to both sides of the paper. Other application methods include the gate roll type, in which the size liquid is applied using a surface transfer method, and the rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates into the paper, while in the surface transfer type, the size liquid components tend to remain on the paper surface. In the surface transfer type, the coating layer tends to remain on the paper surface compared to the pond-type two-roll size press, and the coating layer formed on the surface is larger than in the pond-type two-roll size press. In the present disclosure, performance can be imparted to paper even when the former pond-type two-roll size press is used. Papers treated in this way may exhibit excellent oil and water resistance etc., after simple drying at room temperature or at elevated temperatures, optionally followed by a heat treatment which may range in temperature up to 300°C, e.g. up to 200°C, especially 80°C to 180°C, depending on the properties of the paper.

[0527] The internal treatment method may refer to a treatment method in which an oil-proofing composition is added to a pulp slurry before papermaking. As an internal treatment method, a pulp molded product can be produced by filling a mold with pulp slurry containing the oil-proofing composition and allowing water to permeate outside the mold to form the pulp. Specifically, the method may include, but is not limited to, one or more of the following steps: adding an aqueous dispersion of the oil-proofing composition to the pulp slurry and stirring and mixing it; suction-dehydrating the pulp composition prepared in this step through a mesh body of a predetermined shape to deposit the pulp composition and form a pulp molded intermediate; and molding and drying the pulp molded intermediate in a heated mold to obtain a pulp molded product, specifically paper, a paper container, or a paper molded article. Methods for permeating the water in the pulp slurry outside the mold include natural water permeation at normal pressure and forced water permeation by reducing the pressure outside the mold. The treated paper may be simply dried at room temperature or at an elevated temperature, and then optionally subjected to a heat treatment depending on the paper's properties. The temperature of the heat treatment may be 150° C. or higher, 180° C. or higher, or 210° C. or higher, and may be 300° C. or lower, 250° C. or lower, or 200° C. or lower, and may particularly be in the range of 80° C. to 180° C. By carrying out the heat treatment in this temperature range, excellent oil resistance, water resistance, etc. can be exhibited.

[0528] The present disclosure can be used in gypsum board base paper, coated base paper, medium paper, general liners and mediums, neutral pure white roll paper, neutral liners, anti-rust liners and metal interleaving paper, kraft paper, etc. It can also be used in neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper.

[0529] Pulp raw materials that can be used include bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as groundwood pulp, mechanical pulp or thermomechanical pulp, and recycled paper pulp such as recycled newspapers, recycled magazines, recycled corrugated cardboard, and deinked recycled paper. Mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.

[0530] A sizing agent can be added to improve the water resistance of paper. Examples of sizing agents include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents and neutral rosin-based sizing agents). The amount of sizing agent may be 0.01 to 5% by weight of the pulp.

[0531] If necessary, the paper may contain additives used in paper production, such as paper strength agents such as starch, modified starch, carboxymethyl cellulose, and polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, retention aids, dyes, fluorescent dyes, slime control agents, and antifoaming agents, in amounts commonly used in papermaking. Starch and modified starch are preferably used. If necessary, the oil-proofing composition can be applied to the paper using starch, polyvinyl alcohol, dyes, coating colors, anti-slip agents, etc., using a size press, gate roll coater, bill blade coater, calendar, etc.

[0532] In the case of external addition, the amount of the liquid repellent compound contained in the coating layer is 0.01 to 2.0 g / m ２ , particularly 0.1 to 1.0 g / m ２ The coating layer is preferably formed from an oil-proofing composition and starch and / or modified starch. The solid content of the oil-proofing composition for paper in the coating layer is preferably 2 g / m ２ In the internal addition, the oil-proofing composition is preferably mixed with the pulp so that the amount of the oil-proofing composition is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, particularly 0.2 to 5.0 parts by weight, per 100 parts by weight of the pulp forming the paper.

[0533] In the external addition, oil resistance can also be imparted to paper by using a so-called pond-type two-roll size press treatment, in which a treatment solution is accumulated between rolls and the base paper is passed through the treatment solution between the rolls at any roll speed and nip pressure.

[0534] In the external additive treatment, the paper substrate may contain additives such as sizing agents, strength agents, flocculants, retention agents, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives may be -10,000 to 10,000 μeq / g, preferably -4,000 to 8,000 μeq / g, and more preferably -1,000 to 7,000 μeq / g. Additives such as sizing agents, strength agents, flocculants, retention agents, or coagulants (solids or active ingredients) are generally used in amounts of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) based on the pulp. In the case of paper substrates containing cationic additives (e.g., sizing agents, strength agents, flocculants, retention agents, or coagulants), the oilproofing agent composition is preferably anionic.

[0535] In the internal addition treatment, it is preferable to make paper from a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (e.g., 2.5 to 4.0% by weight).Additives (e.g., sizing agents, paper strength agents, flocculants, retention agents, or coagulants) and liquid-repellent compounds can be added to the pulp slurry. Examples of additives (for example, sizing agents, paper strength agents, flocculants, retention agents, or coagulants) include alkylketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylenepolyamines, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0536] [Pretreatment of Textile Products] The textile product may be pretreated before being treated with the oil-proofing composition of the present disclosure. Pretreatment of the textile product can impart excellent fastness to the textile product after treatment with the oil-proofing composition.

[0537] Examples of pretreatments for textile products include cationization treatment by reaction with a reactive quaternary ammonium salt, anionization treatment such as sulfonation, carboxylation, and phosphate, acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, and polymer coating treatment.

[0538] The method for pretreating a textile product is not limited, and the textile product can be pretreated by a conventionally known method. The pretreatment liquid may be dispersed and diluted in an organic solvent or water as necessary, and applied to the interior and / or surface of the textile product by a known method such as dip coating, spray coating, foam coating, etc., followed by drying. The pH and temperature of the pretreatment liquid may be adjusted depending on the desired degree of treatment. As an example of a method for pretreating a textile product, a method for pretreating a textile product with the above-mentioned treatment agent will be described in detail.

[0539] The pretreatment method for textile products is to add -SO ３ M １ (In the formula, M １ represents a monovalent cation), ２ (In the formula, M ２ represents a monovalent cation), and —O—P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ and each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms) (hereinafter, also referred to as "specific functional groups").

[0540] M １ Examples of M include H, K, Na, and ammonium ions which may have a substituent. ２ Examples of X include H, K, Na, and ammonium ions which may have a substituent. １ or X ２ When is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0541] 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.

[0542] 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.

[0543] The material of the fiber material is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and composite fibers and blended fibers thereof. The form of the fiber material may be any form such as fiber (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, etc.

[0544] In this embodiment, from the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use a textile material containing polyamide and polyester as raw materials, and it is particularly preferable to use nylons such as nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate and polylactic acid, and mixed fibers containing these.

[0545] 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:

[0546] [In the formula, X ２ Ha-SO ３ M ３ (In the formula, M ３represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.

[0547] [In the formula, M ４ represents a monovalent cation.

[0548] The above M ３ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0549] The above M ４ Examples of the cation include H, K, Na, and an ammonium ion which may have a substituent.

[0550] 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.

[0551] Above - COOM ２ Examples of compounds having the formula include polycarboxylic acid polymers.

[0552] 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.

[0553] 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.

[0554] 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.

[0555] 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.

[0556] The weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.

[0557] 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.

[0558] 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.

[0559] 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.

[0560] From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.

[0561] 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.

[0562] 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.

[0563] 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.

[0564] 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.

[0565] The treatment temperature in the immersion treatment can be 60 to 130° C. The treatment time can be 5 to 60 minutes.

[0566] 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.

[0567] 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.

[0568] 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.

[0569] 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 the above-mentioned treatment agent.

[0570] (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).

[0571] 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.).

[0572] <Method for Producing Pulp Composition / Pulp Product> The pulp composition of the present disclosure can be obtained by treating a pulp substrate with an oil-proofing composition containing a liquid-repellent compound.

[0573] The resulting pulp composition can be subjected to treatment steps such as drying, heating, molding, etc., as required, to obtain a pulp product.

[0574] The oil-proofing composition of the present disclosure can be applied to a pulp substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may involve dispersing and diluting the oil-proofing composition of the present disclosure in an organic solvent or water, as nece...

Claims

1. An oil-resistant agent composition, which is solid and contains a liquid-repellent compound, a dispersant, and an excipient.

2. The oil-resistant agent composition according to claim 1, wherein the liquid-repellent compound has a hydrocarbon group or a polysiloxane group having 6 to 40 carbon atoms.

3. The oil-resistant agent composition according to claim 1 or 2, wherein the liquid-repellent compound contains at least one selected from the group consisting of amine-modified products, polyol-modified products, polycarboxylic acid-modified products, and other solid oils.

4. The liquid-repellent compound is selected from the group consisting of an amine-modified product, a polyol-modified product, and a polycarboxylic acid-modified product, and the amine-modified product has an amine skeleton and the following formula: -Y Ｎ -Z Ｎ ｎ [where Y Ｎ is a 1 + n-valent group composed of one or more selected from the group consisting of Y Ｎ１ and Y Ｎ２ , Y Ｎ１ is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O) ２ -, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), Y Ｎ２ is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 2 to 4 valences and 1 to 40 carbon atoms, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 valences, Z Ｎ is an optionally substituted monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms or a monovalent polysiloxane group, and n is an integer of 1 or more and 3 or less.], has one or more groups represented by the formula, and at least one -Y Ｎ -Z Ｎ ｎ is bonded to the nitrogen atom of the amine skeleton; the polyol-modified product has one or more hydroxy groups of the polyol represented by the following formula: -Y Ｏ -Z Ｏ ｎ [wherein Y Ｏ is a 1 + n-valent group composed of one or more selected from the group consisting of Y Ｏ１ and Y Ｏ２ , Y Ｏ１ is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O) ２ -, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (In the formula, R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.), and is a group composed of one or more selected from the group consisting of, Y Ｏ２ is a group composed of one or more selected from the group consisting of an aliphatic hydrocarbon group having 2 to 4 valences and 1 to 40 carbon atoms which may have a substituent, a hydrocarbon aromatic ring having 2 to 4 valences which may have a substituent, and a heterocyclic ring having 2 to 4 valences which may have a substituent, Z Ｏ is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, and n is an integer of 1 or more and 3 or less.], and is a compound substituted with a group represented by: The polycarboxylic acid modifier is a hydroxy group of one or more carboxyl groups of a polycarboxylic acid represented by the following formula: -Y Ｃ -Z Ｃ ｎ [In the formula, Y Ｃ is a (1 + n)-valent group composed of one or more selected from the group consisting of Y Ｃ１ and Y Ｃ２ , Y Ｃ１ is a direct bond, -O-, -C(=O)-, -C(=NR')-, -C(=S)-, -S-, -S(=O) ２ -, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (In the formula, R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.), and is a group composed of one or more selected from the group consisting of, Y Ｃ２ is a group composed of one or more selected from the group consisting of an aliphatic hydrocarbon group having 2 to 4 valences and 1 to 40 carbon atoms which may have a substituent, a hydrocarbon aromatic ring having 2 to 4 valences which may have a substituent, and a heterocyclic ring having 2 to 4 valences which may have a substituent, Z Ｃ is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, and n is an integer of 1 or more and 3 or less.], and is a compound substituted with a group represented by: The oil-resistant agent composition according to any one of claims 1 to 3. 5.The amine skeleton is a skeleton obtained by removing at least one hydrogen atom from a nitrogen atom of at least one amine compound selected from the group consisting of ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine; 2-amino-1,3-propanediol; o-, m- or p-xylylenediamine; 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-oxydianiline; The polyol is glucose, fructose, galactose, xylose; sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomalto-dextrin, gellan gum, tamarind seed gum; kojic acid, quinic acid, chlorogenic acid, gluconic acid; glucosamine; ascorbic acid, inositol; catechin, quercetin, anthocyanin; glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer, and the polycarboxylic acid is citric acid, malic acid, glutaric acid, adipic acid, phthalic acid, alginic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aldic acid; tricarballylic acid, t-aconitic acid, trimellitic acid; pyromellitic acid; the following formula CH. ２ A polymer containing a repeating unit derived from a compound represented by =C(-Q)-C(=O)-OH [wherein Q is a hydrogen atom, a monovalent organic group, or a halogen atom]; and at least one selected from the group consisting of derivatives thereof, the oil-resistant agent composition according to claim 4.

6. The oil-resistant agent composition according to any one of claims 3 to 5, wherein the other solid oil contains at least one selected from the group consisting of rice wax, carnauba wax, hydrogenated castor oil, hydrogenated soybean oil, hydrogenated jojoba oil, hydrogenated rapeseed oil, sunflower wax, candelilla wax, 12-hydroxystearic acid, and candelilla wax.

7. The oil-resistant agent composition according to any one of claims 1 to 6, wherein the amount of the dispersant is 0.1 to 80 parts by weight and the amount of the excipient is 0.1 to 100 parts by weight with respect to 100 parts by weight of the liquid-repellent compound.

8. The oil-resistant agent composition according to any one of claims 1 to 7, wherein the excipient contains at least one selected from the group consisting of saccharides, polysaccharides and polysaccharide derivatives, water-soluble vinyl polymers and their salts, and silicates.

9. The oil-resistant agent composition according to any one of claims 1 to 8, wherein the excipient contains at least one selected from the group consisting of glucose, fructose, galactose, dextrin, sucrose, lactose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, starch, modified starch, pullulan, guar gum, locust bean gum, tamarind seed gum, chitosan, gum arabic, karaya gum, pectin, konjac mannan, carrageenan, isomalto dextrin, mannitol, sorbitol, agar, alginic acid, chitosan gum, gellan gum, Agrobacterium sinoglycan, cationized guar gum, polyvinyl alcohol, polyacrylic acid, and sodium polyacrylate.

10. The oil-resistant agent composition according to any one of claims 1 to 9, wherein the dispersant contains at least one selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and polymer dispersants.

11. The oil-resistant composition according to any one of claims 1 to 10, wherein the oil-resistant composition is in tablet form and has a particle size of 2,000 to 100,000 μm.

12. The oil-resistant composition according to any one of claims 1 to 11, wherein the water content of the oil-resistant composition is 0.01% by weight to 20% by weight.

13. The oil-resistant composition according to any one of claims 1 to 12, further comprising at least one selected from the group consisting of a lubricant, a binder, and a disintegrant.

14. The liquid-repellent compound is an amine-modified product, and the amine-modified product has the following formula: N(-C(=O)-Z N ) p (-H) q -L 1 -[N(-C(=O)-Z N ) r (-H) s -L 1 -] t -N(-C(=O)-Z N ) p (-H) q [In the formula, Z Ｎ is, in each occurrence, independently an alkyl group having 14 to 24 carbon atoms, and L 1 is, in each occurrence, independently a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, p is, in each occurrence, independently an integer of 1 or more and 2 or less, q is, in each occurrence, independently 0 or 1, and p + q is 2 in each N(-C(=O)-Z N ) p (-H) q , r is, in each occurrence, independently 0 or 1, s is, in each occurrence, independently 0 or 1, and r + s is 1 in each N(-C(=O)-Z N ) r (-H) s , and t is an integer of 0 or more and 3 or less. ] The oil-resistant agent composition according to claim 1, which is a compound represented by the formula.

15. An oil-resistant paper comprising a liquid-repellent compound, a dispersant, and an excipient in the oil-resistant composition according to any one of claims 1 to 14.

16. The oil-resistant paper according to claim 15, which is a pulp molded product.

17. A method for producing an oil-resistant composition, comprising mixing a liquid-repellent compound, a dispersant, an excipient, and a liquid medium to obtain a precursor mixture, and subjecting the precursor mixture to a heat treatment or a drying treatment to obtain a solid oil-resistant composition.

18. The method for producing an oil-resistant composition according to claim 17, comprising tableting the oil-resistant composition.

19. A method for producing a paper product, comprising mixing the oil-resistant composition according to any one of claims 1 to 14 and water to prepare an aqueous dispersion of the oil-resistant composition, and treating the paper by external addition treatment or internal addition treatment using the aqueous dispersion.

20. A method for producing a pulp mold, comprising mixing the oil-resistant composition according to any one of claims 1 to 14 and water to prepare an aqueous dispersion of the oil-resistant composition, filling the aqueous dispersion and a pulp base material into a mold, and permeating water outside the mold to form the pulp.

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